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
ROTATING BIOLOGICAL CONTACTORS - SECOND ORDER KINETICS
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...
TRANSPORT OF DISSOLVED SUBSTANCES WITH SECOND-ORDER REACTION
A mass transport equation which allows coupled second-order reaction between two chemical components in groundwater systems is described. everal analytical solutions to the system of nonlinear equations for advective flow systems have been found, and the features of the solution ...
Catalysis Letters Vol. 76, No. 12, 2001 35 Second order isothermal desorption kinetics
Asscher, Micha
Catalysis Letters Vol. 76, No. 12, 2001 35 Second order isothermal desorption kinetics Y. Lilach desorption; second order kinetics; recombinative desorption 1. Introduction Temperature-programmed desorption species, and for obtaining their desorption kinetics. Comprehensive reviews on the subject exist
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)
Estimation of second order rate constants using chemometric methods with kinetic constraints.
Thurston, Tom J; Brereton, Richard G
2002-05-01
Several methods are described for determining rate constants for second order reactions of the form U + V --> W using chemometrics and hard modelling to analyse UV absorption spectroscopic data, where all species absorb with comparable concentrations and extinctions. An interesting feature of this type of reaction is that the number of steps in the reaction is less than the number of absorbing species, resulting in a rank-deficient response matrix. This can cause problems when using some of the methods described in the literature. The approaches discussed in the paper depend, in part, on what knowledge is available about the system, including the spectra of the reactants and product, the initial concentrations and the exact kinetics. Sometimes some of this information may not be available or may be hard to estimate. Five groups of methods are discussed, namely use of multiple linear regression to obtain concentration profiles and fit kinetics information, rank augmentation using multiple batch runs, difference spectra based approaches, mixed spectral approaches which treat the reaction as two independent pseudospecies, and principal components regression. Two datasets are simulated, one where the spectra are quite different and the other where the spectrum of one reactant and the product share a high degree of overlap. Three sources of error are considered, namely sampling error, instrumental noise and errors in initial concentrations. The relative merits of each method are discussed. PMID:12081045
Chen, Jiale; Center for Magnetic Fusion Theory, Chinese Academy of Sciences, Hefei ; Gao, Zhe; Center for Magnetic Fusion Theory, Chinese Academy of Sciences, Hefei
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.
Temporal Frequency Modulates Reaction Time Responses to First-Order and Second-Order Motion
Nottingham, University of
Temporal Frequency Modulates Reaction Time Responses to First-Order and Second-Order Motion Claire the effect of temporal frequency and modulation depth on reaction times for discriminating the direction using equal multiples of direction-discrimination threshold. Results showed that reaction times were
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.
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…
Integrated rate equations for irreversible enzyme-catalysed first-order and second-order reactions.
Boeker, E A
1985-01-01
Integrated rate equations are presented that describe irreversible enzyme-catalysed first-order and second-order reactions. The equations are independent of the detailed mechanism of the reaction, requiring only that it be hyperbolic and unbranched. The results should be directly applicable in the laboratory. PMID:3977872
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...
Second order equation of motion for electromagnetic radiation back-reaction
Tamás Matolcsi; Tamás Fülöp; Mihály Weiner
2014-10-26
We take the viewpoint that the physically acceptable solutions of the Lorentz-Dirac equation for radiation back-reaction are actually determined by a second order equation of motion in such a way that the self-force can be given as a function of spacetime location and velocity. This self-force function turns out to be determined by a first order partial differential equation. In view of possible practical difficulty in solving that partial differential equation, we propose two iteration methods, too, for obtaining the self-force function. For two example systems, the second order equation of motion is obtained exactly in the nonrelativistic regime via each of the three methods, and the three results are found to coincide. We reveal that, for both systems, back-reaction induces a damping proportional to velocity and, in addition, it decreases the effect of the external force.
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 may be applicable and problems it creates for the conventional picture of first-order fermi shock acceleration. It will also discuss results from the kinetic Monte-Carlo simulation described above (including second-order fermi) in the vicinity of shocks.
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)
Nottingham, University of
Choice reaction times for identifying the direction of first-order motion and different varieties of the human visual system by measuring forced-choice reaction times for dis- criminating the drift direction of stimulus modulation depths. In general, reaction times for all types of second-order motion were slower
Positronium formation as a three-body reaction. II. The second-order nuclear amplitudes
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.
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.
NASA Astrophysics Data System (ADS)
Saiers, James E.; Hornberger, George M.; Liang, Liyuan
1994-09-01
We present results from experiments on the migration of inorganic colloids through laboratory columns containing clean quartz sand. Particle retention on the quartz collectors was found to be substantially less in experiments using negatively charged silica (SiO2) colloids than in experiments using positively charged anatase (TiO2) or boehmite (AlOOH) colloids. Analysis of these data with respect to two different advection-dispersion models indicates that deposition of colloidal silica follows a first-order, reversible kinetics process, while deposition of both anatase and boehmite is more closely depicted by second-order kinetics. Fitted values of the rate constant used to describe particle attachment vary consistently with the mean grain size of the sand and, for anatase and boehmite, are within a factor of 2 of the values predicted on the basis of colloid filtration theory.
NASA Astrophysics Data System (ADS)
Mazur, O. Yu.; Stefanovich, L. I.; Yurchenko, V. M.
2015-07-01
The effect of hydrostatic pressure on the kinetics of the formation of electrical domains in ferroelectric materials that undergo second-order phase transitions has been considered. It has been shown using the example of triglycine sulfate ferroelectric crystals undergoing an order-disorder phase transition that the applied pressure increases the ordering temperature and thus accelerates the ordering process. It has been found that, by increasing the hydrostatic pressure applied to the sample after quenching, it is possible to obtain a single-domain state, instead of the multi-domain type of ordering. The evolution curves for the average value of the order parameter and its dispersion have been obtained by numerical integration. These curves indicate that quasi-stationary multi-domain structures of the asymmetric type can be formed at specially selected pressures. It has been established that the kinetics of the formation of electrical domains in ferroelectrics depends significantly on the initial relaxation conditions, which are determined by the technological prehistory of the quenching.
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.
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
Ben O'Shaughnessy; Dimitrios Vavylonis
1999-09-10
We study irreversible A-B reaction kinetics at a fixed interface separating two immiscible bulk phases, A and B. We consider general dynamical exponent $z$, where $x_t\\sim t^{1/z}$ is the rms diffusion distance after time $t$. At short times the number of reactions per unit area, $R_t$, is {\\em 2nd order} in the far-field reactant densities $n_A^{\\infty},n_B^{\\infty}$. For spatial dimensions $d$ above a critical value $d_c=z-1$, simple mean field (MF) kinetics pertain, $R_t\\sim Q_b t n_A^{\\infty} n_B^{\\infty}$ where $Q_b$ is the local reactivity. For low dimensions $d Q_b^* \\sim (n_B^{\\infty})^{[z-(d+1)]/d}$. Logarithmic corrections arise in marginal cases. At long times, a cross-over to {\\em 1st order} DC kinetics occurs: $R_t \\approx x_t n_A^{\\infty}$. A density depletion hole grows on the more dilute A side. In the symmetric case ($n_A^{\\infty}=n_B^{\\infty}$), when $dd_c$ fluctuations are unimportant: local mean field theory applies at the interface (joint density distribution approximating the product of A and B densities) and $n_A^s \\sim t^{(1-z)/(2z)}$. We apply our results to simple molecules (Fickian diffusion, $z=2$) and to several models of short-time polymer diffusion ($z>2$).
Second-Order Algebraic Theories
NASA Astrophysics Data System (ADS)
Fiore, Marcelo; Mahmoud, Ola
Fiore and Hur [10] recently introduced a conservative extension of universal algebra and equational logic from first to second order. Second-order universal algebra and second-order equational logic respectively provide a model theory and a formal deductive system for languages with variable binding and parameterised metavariables. This work completes the foundations of the subject from the viewpoint of categorical algebra. Specifically, the paper introduces the notion of second-order algebraic theory and develops its basic theory. Two categorical equivalences are established: at the syntactic level, that of second-order equational presentations and second-order algebraic theories; at the semantic level, that of second-order algebras and second-order functorial models. Our development includes a mathematical definition of syntactic translation between second-order equational presentations. This gives the first formalisation of notions such as encodings and transforms in the context of languages with variable binding.
Combustion kinetics and reaction pathways
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.
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.
Reaction Kinetics in Polymer Melts
Ben O'Shaughnessy; Dimitrios Vavylonis
1998-07-09
We study the reaction kinetics of end-functionalized polymer chains dispersed in an unreactive polymer melt. Starting from an infinite hierarchy of coupled equations for many-chain correlation functions, a closed equation is derived for the 2nd order rate constant $k$ after postulating simple physical bounds. Our results generalize previous 2-chain treatments (valid in dilute reactants limit) by Doi, de Gennes, and Friedman and O'Shaughnessy, to arbitrary initial reactive group density $n_0$ and local chemical reactivity $Q$. Simple mean field (MF) kinetics apply at short times, $k \\sim Q$. For high $Q$, a transition occurs to diffusion-controlled (DC) kinetics with $k \\approx x_t^3/t$ (where $x_t$ is rms monomer displacement in time $t$) leading to a density decay $n_t \\approx n_0 - n_0^2 x_t^3$. If $n_0$ exceeds the chain overlap threshold, this behavior is followed by a regime where $n_t \\approx 1/x_t^3$ during which $k$ has the same power law dependence in time, $k \\approx x_t^3/t$, but possibly different numerical coefficient. For unentangled melts this gives $n_t \\sim t^{-3/4}$ while for entangled cases one or more of the successive regimes $n_t \\sim t^{-3/4}$, $t^{-3/8}$ and $t^{-3/4}$ may be realized depending on the magnitudes of $Q$ and $n_0$. Kinetics at times longer than the longest polymer relaxation time $\\tau$ are always MF. If a DC regime has developed before $\\tau$ then the long time rate constant is $k \\approx R^3/\\tau$ where $R$ is the coil radius. We propose measuring the above kinetics in a model experiment where radical end groups are generated by photolysis.
Modelling reaction kinetics inside cells
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
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.
Kinetic studies of elementary chemical reactions
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.
Ultracold Chemistry and its Reaction Kinetics
Florian Richter; Daniel Becker; Cédric Bény; Torben A. Schulze; Silke Ospelkaus; Tobias J. Osborne
2015-01-08
We study the reaction kinetics of chemical processes occurring in the ultracold regime and systematically investigate their dynamics. Quantum entanglement is found to play a key role in driving an ultracold reaction towards a dynamical equilibrium. In case of multiple concurrent reactions Hamiltonian chaos dominates the phase space dynamics in the mean field approximation.
Thermodynamically Feasible Kinetic Models of Reaction Networks
Ederer, Michael; Gilles, Ernst Dieter
2007-01-01
The dynamics of biological reaction networks are strongly constrained by thermodynamics. An holistic understanding of their behavior and regulation requires mathematical models that observe these constraints. However, kinetic models may easily violate the constraints imposed by the principle of detailed balance, if no special care is taken. Detailed balance demands that in thermodynamic equilibrium all fluxes vanish. We introduce a thermodynamic-kinetic modeling (TKM) formalism that adapts the concepts of potentials and forces from irreversible thermodynamics to kinetic modeling. In the proposed formalism, the thermokinetic potential of a compound is proportional to its concentration. The proportionality factor is a compound-specific parameter called capacity. The thermokinetic force of a reaction is a function of the potentials. Every reaction has a resistance that is the ratio of thermokinetic force and reaction rate. For mass-action type kinetics, the resistances are constant. Since it relies on the thermodynamic concept of potentials and forces, the TKM formalism structurally observes detailed balance for all values of capacities and resistances. Thus, it provides an easy way to formulate physically feasible, kinetic models of biological reaction networks. The TKM formalism is useful for modeling large biological networks that are subject to many detailed balance relations. PMID:17208985
Modeling the enzyme kinetic reaction.
Atangana, Abdon
2015-09-01
The Enzymatic control reactions model was presented within the scope of fractional calculus. In order to accommodate the usual initial conditions, the fractional derivative used is in Caputo sense. The methodologies of the three analytical methods were used to derive approximate solution of the fractional nonlinear system of differential equations. Two methods use integral operator and the other one uses just an integral. Numerical results obtained exhibit biological behavior of real world problem. PMID:25930963
statistical physics reaction kinetics Oceanic CO2
feedback" loop in global warming caused by CO2 is that rising temperatures push more of the Earth's CO2statistical physics reaction kinetics Oceanic CO2 One of the major concerns about a "positive into the atmosphere, which further causes warming. In this problem, we will explore, in a quantitative sense
Calcite Reaction Kinetics in Saline Waters
Finneran, David
2012-02-14
The effect of ionic strength (I), pCO2, and temperature on the reaction kinetics of calcite was investigated in magnesium-free, phosphate-free, low calcium (mCa^2 ? 0.01 – 0.02 molal) simple KCl and NaCl solutions from both undersaturated...
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.
Binocular Combination of Second-Order Stimuli
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
Paper # XXX Topic: Reaction Kinetics Eastern State Fall Technical Meeting
Knyazev, Vadim D.
Paper # XXX Topic: Reaction Kinetics 1 Eastern State Fall Technical Meeting Chemical & Physical 1017 s-1 #12;Paper # XXX Topic: Reaction Kinetics 2 and activation energy values close to the C-C bond
An Analysis of Second-Order Autoshaping
ERIC Educational Resources Information Center
Ward-Robinson, Jasper
2004-01-01
Three mechanisms can explain second-order conditioning: (1) The second-order conditioned stimulus (CS2) could activate a representation of the first-order conditioned stimulus (CS1), thereby provoking the conditioned response (CR); The CS2 could enter into an excitatory association with either (2) the representation governing the CR, or (3) with a…
Kinetic analysis of complex reactions using FEMLAB
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.
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.
Second-order gravitational self-force.
Pound, Adam
2012-08-01
Using a rigorous method of matched asymptotic expansions, I derive the equation of motion of a small, compact body in an external vacuum spacetime through second order in the body's mass (neglecting effects of internal structure). The motion is found to be geodesic in a certain locally defined regular geometry satisfying Einstein's equation at second order. I outline a method of numerically obtaining both the metric of that regular geometry and the complete second-order metric perturbation produced by the body. PMID:23006161
Spectroscopy and reaction kinetics of HCO
Guo, Yili
1989-01-01
The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ..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.
Modeling the Kinetics of Bimolecular Reactions Antonio Fernandez-Ramos
Truhlar, Donald G
Assumption 4548 2.5.2. Variational Transition State Theory for Barrierless Addition Reactions 4549 2Modeling the Kinetics of Bimolecular Reactions Antonio Ferna´ndez-Ramos Departamento de Quimica-Phase Thermal Reactions 4518 2.1. Thermodynamics: Enthalpies and Free Energies of Reaction 4518 2.2. Kinetics
Understanding Arsenate Reaction Kinetics with Ferric Hydroxides
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 adsorption and desorption can be attributed to the high Gibbs free energies of activation for forming and breaking bonds with the ferric hydroxide. PMID:23806140
Reaction rate kinetics for in situ combustion retorting of Michigan Antrim oil shale
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.
Reaction kinetics of dolomite rim growth
NASA Astrophysics Data System (ADS)
Helpa, V.; Rybacki, E.; Abart, R.; Morales, L. F. G.; Rhede, D.; Je?ábek, P.; Dresen, G.
2014-04-01
Reaction rims of dolomite (CaMg[CO3]2) were produced by solid-state reactions at the contacts of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals at 400 MPa pressure, 750-850 °C temperature, and 3-146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO3 interface with length ranging from about 6 to 41 µm. At the same time, a 5-71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO3. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12-80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E a (CaO) = 192 ± 54 kJ/mol and E a (MgO) = 198 ± 44 kJ/mol, respectively.
Reaction rates for mesoscopic reaction-diffusion kinetics.
Hellander, Stefan; Hellander, Andreas; Petzold, Linda
2015-02-01
The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results. PMID:25768640
Reaction rates for mesoscopic reaction-diffusion kinetics
Stefan Hellander; Andreas Hellander; Linda Petzold
2015-01-28
The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework, frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a mixed boundary condition at the reaction radius of two molecules. We also establish fundamental limits for the range of mesh resolutions for which this approach yields accurate results, and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics.
Variable separation and second order superintegrability
Ciocan-Fontanine, Ionut
Variable separation and second order superintegrability Willard Miller (Joint with E describe clearly what "separation of variables" means in general, the mechanism of variable separation order su- perintegrable systems. IMA Talk Â p.2/59 #12;SEPARABILITY: Intuitive Partial differential
Software for Second-order Cone Programming
the code from matlab4. Compiled mex- les for some platforms are included; for other platforms you can compile the interface from its source code socp mex.c. See x4. A Matlab routine socp.m. Although the mex the general second- order cone programming problem. See x4. A Matlab4 interface, which allows the user to call
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…
Second order noncommutative corrections to gravity
Calmet, Xavier; Kobakhidze, Archil
2006-08-15
In this work, we calculate the leading order corrections to general relativity formulated on a canonical noncommutative spacetime. These corrections appear in the second order of the expansion in theta. First order corrections can only appear in the gravity-matter interactions. Some implications are briefly discussed.
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.
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)
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…
Second-order gravitational self-force
Eran Rosenthal
2006-09-18
We derive an expression for the second-order gravitational self-force that acts on a self-gravitating compact-object moving in a curved background spacetime. First we develop a new method of derivation and apply it to the derivation of the first-order gravitational self-force. Here we find that our result conforms with the previously derived expression. Next we generalize our method and derive a new expression for the second-order gravitational self-force. This study also has a practical motivation: The data analysis for the planned gravitational wave detector LISA requires construction of waveforms templates for the expected gravitational waves. Calculation of the two leading orders of the gravitational self-force will enable one to construct highly accurate waveform templates, which are needed for the data analysis of gravitational-waves that are emitted from extreme mass-ratio binaries.
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.
Spacetime Encodings III - Second Order Killing Tensors
Jeandrew Brink
2009-11-09
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.
Slowly rotating scalar field wormholes: The second order approximation
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.
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.
Implementation of fitted second order ODE integrators
Gear, C.W.
1988-07-01
The fixed step size integration of a system of second-order ODES without first derivatives can most efficiently be implemented using backward differences (if variable step sizes are needed, modified backward differences appear to be the most efficient(2)). This note indicates how to modify these methods so that they are exact for solutions of the form e/sup /lambda/t/ for specified values of /lambda/. These appear to be particularly promising for the equations of planetary motion in which /lambda/ = i/omega/, where /omega//2/pi/ is the rotational frequency. 3 refs.
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…
Synchronization from Second Order Network Connectivity Statistics
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
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.
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.
Research Directions CharacterizationReaction Kinetics
the reaction time ·Reaction time dependent on polymer size, percentage of varying monomers, and solvent), standard (8.7 M) or dilute conditions (6.6 M) · Varying solvent amount changed reaction time and AVL conditions provided a good balance of reaction time to AVL incorporation · Dilute conditions are much slower
The surface reaction kinetics of salicylate on alumina
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.
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)
Second-order temporal modulation transfer functions.
Lorenzi, C; Soares, C; Vonner, T
2001-08-01
Detection thresholds were measured for a sinusoidal modulation applied to the modulation depth of a sinusoidally amplitude-modulated (SAM) white noise carrier as a function of the frequency of the modulation applied to the modulation depth (referred to as f'm). The SAM noise acted therefore as a "carrier" stimulus of frequency fm, and sinusoidal modulation of the SAM-noise modulation depth generated two additional components in the modulation spectrum: fm-f'm and fm+f'm. The tracking variable was the modulation depth of the sinusoidal variation applied to the "carrier" modulation depth. The resulting "second-order" temporal modulation transfer functions (TMTFs) measured on four listeners for "carrier" modulation frequencies fm of 16, 64, and 256 Hz display a low-pass segment followed by a plateau. This indicates that sensitivity to fluctuations in the strength of amplitude modulation is best for fluctuation rates f'm below about 2-4 Hz when using broadband noise carriers. Measurements of masked modulation detection thresholds for the lower and upper modulation sideband suggest that this capacity is possibly related to the detection of a beat in the sound's temporal envelope. The results appear qualitatively consistent with the predictions of an envelope detector model consisting of a low-pass filtering stage followed by a decision stage. Unlike listeners' performance, a modulation filterbank model using Q values > or = 2 should predict that second-order modulation detection thresholds should decrease at high values of f'm due to the spectral resolution of the modulation sidebands (in the modulation domain). This suggests that, if such modulation filters do exist, their selectivity is poor. In the latter case, the Q value of modulation filters would have to be less than 2. This estimate of modulation filter selectivity is consistent with the results of a previous study using a modulation-masking paradigm [S. D. Ewert and T. Dau, J. Acoust. Soc. Am. 108, 1181-1196 (2000)]. PMID:11519571
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…
Reaction kinetics of hydrothermal carbonization of loblolly pine.
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
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.
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.
Fluid flow and chemical reaction kinetics in metamorphic systems
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.
Reaction kinetics in a tight spot.
Biham, Ofer; Krug, Joachim; Lipshtat, Azi; Michely, Thomas
2005-05-01
The standard analysis of reaction networks based on deterministic rate equations fails in confined geometries, commonly encountered in fields such as astrochemistry, thin-film growth and cell biology. In these systems the small reactant population implies anomalous behavior of reaction rates, which can be accounted for only by following the full distribution of reactant numbers. PMID:17193475
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.
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)
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.
Reversibly Switching Silver Hierarchical Structures via Reaction Kinetics
NASA Astrophysics Data System (ADS)
Liu, Jianmei; Yang, Tao; Li, Chengxiang; Dai, Jinhui; Han, Yongsheng
2015-10-01
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.
Reversibly Switching Silver Hierarchical Structures via Reaction Kinetics
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
Second-Order Accurate Method for Solving Radiation-Hydrodynamics
Edwards, Jarrod Douglas
2013-11-12
Second-order discretization for radiation-hydrodynamics is currently an area of great interest. Second-order methods used to solve the respective single-physics problems often differ fundamentally, making it difficult to combine them in a second...
Reaction wheels for kinetic energy storage
NASA Technical Reports Server (NTRS)
Studer, P. A.
1984-01-01
In contrast to all existing reaction wheel implementations, an order of magnitude increase in speed can be obtained efficiently if power to the actuators can be recovered. This allows a combined attitude control-energy storage system to be developed with structure mounted reaction wheels. The feasibility of combining reaction wheels with energy storage wwheels is demonstrated. The power required for control torques is a function of wheel speed but this energy is not dissipated; it is stored in the wheel. The I(2)R loss resulting from a given torque is shown to be constant, independent of the design speed of the motor. What remains, in order to efficiently use high speed wheels (essential for energy storage) for control purposes, is to reduce rotational losses to acceptable levels. Progress was made in permanent magnet motor design for high speed operation. Variable field motors offer more control flexibility and efficiency over a broader speed range.
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.
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.
Chemistry 231 Fall 2013 Chemistry 231, Chemical Kinetics and Molecular Reaction Dynamics
Continetti, Robert E.
Chemistry 231 Fall 2013 Chemistry 231, Chemical Kinetics and Molecular Reaction Dynamics Dept chemical kinetics, the connection between chemical kinetics and molecular reaction dynamics as well as some and Hase, Prentice Hall (1999) 4. Chemical Kinetics, K.J. Laidler, McGraw Hill (1965) 5. Gas Phase Reaction
Kinetics and Mechanisms of Calcite Reactions with Saline Waters
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.
Interfacial kinetics of a model epoxy-amine addition reaction.
Hirai, Tomoyasu; Kawasaki, Kaoru; Tanaka, Keiji
2012-10-21
The kinetics of the addition reaction at a solid interface for a model epoxy-amine system composed of monofunctionalized phenyl glycidyl ether and hexylamine was examined. The chemical character for the reaction of this system at the interface was the same as that in the bulk, while the physical nature was significantly different. Slowing down of the diffusion for the reactants in close proximity to the solid interface was also addressed by interfacial selective spectroscopy. PMID:22968718
Microdroplet fusion mass spectrometry for fast reaction kinetics
Zare, Richard N.
Microdroplet fusion mass spectrometry for fast reaction kinetics Jae Kyoo Leea,b , Samuel Kima,b,1 94305; b Center for Plant Aging Research, Institute for Basic Science, Daegu 711-873, Republic of Korea the existence of two distinct popula- tions with fast and slow exchange rates. These studies demon- strated
REACTION KINETICS OF CA-BASED SORBENTS WITH HC1
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...
REACTION KINETICS OF CA-BASED SORBENTS WITH HC1
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...
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)
Basics of Chemical Kinetics -1 Rate of reaction = rate of disappearance of A =
Albert, RÃ©ka
Basics of Chemical Kinetics - 1 Rate of reaction = rate of disappearance of A = # of moles of Chemical Kinetics - 3 Elementary Reaction: Reaction order of each species is identical reactions: Forward Reaction Backward Reaction CBA + 2 CBA + 2 CBA + 2 CBA + 2 #12;Basics of Chemical
Yeung, Man-Chung
KINETICS, CATALYSIS, AND REACTION ENGINEERING Nonthermal Plasma Reactions of Dilute Nitrogen Oxide atom and N2(A) are found to control the conversion of nitrogen oxides and the evolution of byproducts for the conversion of nitrogen oxides,1,2,4-10 sulfur dioxide,11 and volatile organic car- bons.12 Despite its
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.
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.
Computation of kinetic isotope effects for enzymatic reactions
GAO, JiaLi
2013-01-01
We describe a computational approach, incorporating quantum mechanics into enzyme kinetics modeling with a special emphasis on computation of kinetic isotope effects. Two aspects are highlighted: (1) the potential energy surface is represented by a combined quantum mechanical and molecular mechanical (QM/MM) potential in which the bond forming and breaking processes are modeled by electronic structure theory, and (2) a free energy perturbation method in path integral simulation is used to determine both kinetic isotope effects (KIEs). In this approach, which is called the PI-FEP/UM method, a light (heavy) isotope is mutated into a heavy (light) counterpart in centroid path integral simulations. The method is illustrated in the study of primary and secondary KIEs in two enzyme systems. In the case of nitroalkane oxidase, the enzymatic reaction exhibits enhanced quantum tunneling over that of the uncatalyzed process in water. In the dopa delarboxylase reaction, there appears to be distinguishable primary carbon-13 and secondary deuterium KIEs when the internal proton tautomerism is in the N-protonated or in the O-protonated positions. These examples show that the incorporation of quantum mechanical effects in enzyme kinetics modeling offers an opportunity to accurately and reliably model the mechanisms and free energies of enzymatic reactions. PMID:23976893
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
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.
Autocatalysis-driven clock reaction II: kinetics of the pentathionate-periodate reaction.
Xu, Li; Horváth, Attila K
2014-10-23
The pentathionate-periodate reaction has been investigated by spectrophotometrically monitoring the total amount of iodine evolved in the presence of phosphoric acid/dihydrogen phosphate buffer at 468 nm. The majority of the main characteristics of the title system is very reminiscent of that found recently in the pentathionate-iodate reaction, a system that led us to classify generally the clock reactions. Along with the pentathionate-iodate reaction the title system is proposed to belong to the autocatalysis-driven clock reactions as well. The kinetic model of the pentathionate-iodate system published recently was implemented by the necessary reactions of periodate to compose a 24-step kinetic model in which the mechanisms of the pentathionate-iodine, pentathionate-iodate, bisulfite-periodate, bisulfite-iodate, iodide-periodate, and the well-known Dushman reactions are combined. A thorough analysis revealed that the direct pentathionate-periodate reaction plays a role only to produce iodide ion via a finite sequence of reactions, and once its concentration reaches a certain level, the reaction is almost exclusively governed by the pentathionate-iodine, the iodide-periodate, and the Dushman reactions. As expected strong catalytic effect of the buffer composition is also found that can readily be explained by its well-known catalytic influence on the Dushman reaction. PMID:25268333
Jester-Weinstein, Jack (Jack L.)
2013-01-01
The design process for an experimental platform measuring reaction kinetics in a chemical looping combustion (CLC) process is documented and justified. To enable an experiment designed to characterize the reaction kinetics ...
Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.
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
Portable centrifugal analyzer for the determination of rapid reaction kinetics
Bostick, W.D.; Bauer, M.L.; McCracken, R.; Mrochek, J.E.
1980-02-01
A portable centrifugal analyzer prototype is capable of rapidly initiating reactions and monitoring 17 optical channels as they rotate past a stationary photodetector. An advanced rotor drive permits transfer of discretely loaded sample and reagent into a cuvette within 60 ms. Various rotor designs have been employed to ensure effieicnt mixing concurrent with solution transfer, thus permitting absorbance or luminescence measurements to be made almost immediately after solution contract. Dye-dillution studies have been used to investigate transfer and mixing efficiencies. Rotor designs with parallel access for sample and reagent into the cuvette were found to promote efficient mixing during liquid transfer. The hypochlorite-luminol chemiluminescent reaction served to demonstrate the utility of the system for performing rapid kinetic analyses. Appropriate adjustment of reaction conditions allows first-order reaction half-lives as short as 0.04 s to be measured. 13 figures, 3 tables.
Interfacial Reactions: Mixed Order Kinetics and Segregation Effects
Ben O'Shaughnessy; Dimitrios Vavylonis
1999-11-02
We study A-B reaction kinetics at a fixed interface separating A and B bulks. Initially, the number of reactions ${\\cal R}_t \\sim t n_A^\\infty n_B^\\infty$ is 2nd order in the far-field densities $n_A^\\infty,n_B^\\infty$. First order kinetics, governed by diffusion from the dilute bulk, onset at long times: ${\\cal R}_t\\approx x_t n_A^\\infty$ where $x_t\\sim t^{1/z}$ is the rms molecular displacement. Below a critical dimension, $d
Electrochemically responsive heterogeneous catalysis for controlling reaction kinetics.
Mao, Xianwen; Tian, Wenda; Wu, Jie; Rutledge, Gregory C; Hatton, T Alan
2015-01-28
We report a method to control reaction kinetics using electrochemically responsive heterogeneous catalysis (ERHC). An ERHC system should possess a hybrid structure composed of an electron-conducting porous framework coated with redox-switchable catalysts. In contrast to other types of responsive catalysis, ERHC combines all the following desired characteristics for a catalysis control strategy: continuous variation of reaction rates as a function of the magnitude of external stimulus, easy integration into fixed-bed flow reactors, and precise spatial and temporal control of the catalyst activity. Herein we first demonstrate a facile approach to fabricating a model ERHC system that consists of carbon microfibers with conformal redox polymer coating. Second, using a Michael reaction whose kinetics depends on the redox state of the redox polymer catalyst, we show that use of different electrochemical potentials permits continuous adjustment of the reaction rates. The dependence of the reaction rate on the electrochemical potential generally agrees with the Nernstian prediction, with minor discrepancies due to the multilayer nature of the polymer film. Additionally, we show that the ERHC system can be employed to manipulate the shape of the reactant concentration-time profile in a batch reactor through applying customized potential-time programs. Furthermore, we perform COMSOL simulation for an ERHC-integrated flow reactor, demonstrating highly flexible manipulation of reactant concentrations as a function of both location and time. PMID:25563424
Weak lensing induced by second-order vector mode
NASA Astrophysics Data System (ADS)
Saga, Shohei; Yamauchi, Daisuke; Ichiki, Kiyotomo
2015-09-01
The vector mode of cosmological perturbation theory imprints characteristic signals on the weak lensing signals such as curl and B modes which are never imprinted by the scalar mode. However, the vector mode is neglected in the standard first-order cosmological perturbation theory since it only has a decaying mode. This situation changes if the cosmological perturbation theory is expanded up to second order. The second-order vector and tensor modes are inevitably induced by the product of the first-order scalar modes. We study the effect of the second-order vector mode on the weak lensing curl and B modes. We find that the curl mode induced by the second-order vector mode is comparable to that induced by the primordial gravitational waves with the tensor-to-scalar ratio r =0.1 at ??200 . In this case, the curl mode induced by the second-order vector mode dominates at ?>200 . Furthermore, the B-mode cosmic shear induced by the second-order vector mode dominates on almost all scales. However, we find that the observational signatures of the second-order vector and tensor modes cannot exceed the expected noise of ongoing and upcoming weak lensing measurements. We conclude that the curl and B modes induced by the second-order vector and tensor modes are unlikely to be detected in future experiments.
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…
Strong Logics of First and Second Order Peter Koellner
Koellner, Peter
Strong Logics of First and Second Order Peter Koellner Abstract In this paper we investigate strong-order logic is really set theory in sheep's clothing. This paper is concerned with strong logics of first logics of first and second order that have certain absoluteness properties. We begin
SECOND ORDER ENTROPY DIMINISHING SCHEME FOR THE EULER EQUATIONS
Coquel, Frédéric
]...), a general methodology has been developed to construct second order finite volume schemes for hyperbolic , P. HELLUY2 , J. SCHNEIDER2 Introduction In this paper, a methodology to build second order solver, a Godunov scheme. This terminology is developed in the review paper of Harten, Lax and Van Leer
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.
Microdroplet fusion mass spectrometry for fast reaction kinetics
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 ?m 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-?m 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 ?s. 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
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 ?-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 ?-methoxystyrenes by chloroacetic acid, but for the reactions of the parent and 4-NO2 substituted ?-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, ?Go ? 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 ?Go, along with a good correlation of Hammond shift in the transition state structure. PMID:19754046
Jung, Moon Chul; Weber, Stephen G.
2006-01-01
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-?m-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)33+ by analyte to the photoluminescent Os(bpy)32+) 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-hydroquinone. Kinetically controlled reactions of catechols, however, could be also completed in a reasonable time at increased reagent concentration. A satisfactory reactor, operating at 1.7 cm/s (2 ?L/min) velocity with solutes having diffusion coefficients in the 5 × 10?6 cm2/s range, can be constructed from 8.0 cm of 25-?m-radius capillary. Slower reactions require longer reaction times, but theoretical calculations expect that a CTR does not broaden a chromatographic peak (N = 14 000) from a 100-?m-capillary chromatography column by 10% if the pseudo-first-order rate constant is larger than 0.1 s?1. PMID:15858975
Kinetics and Mechanisms of Calcite Reactions with Saline Waters
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, pCO_{2}, 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 pCO_{2}, Ca^{2+}, 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 CO_{2} 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 growth mechanism was confirmed by grazing incidence X-ray diffraction, µ-Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and electron diffraction. Extended time studies out to 45 days confirmed the epitaxial relationship of the overgrowth layer with the substrate. Under NSW conditions, overgrowths were found to have ~0.4 to 0.8 nm / hr growth rates and accommodating 4 at% Mg, resulting in a highly strained overgrowth layer. Following the initial layer by layer growth mechanism, the growth changes to Stranski-Krastanov type after a critical thickness of approximately 100 nm.
Kinetic Studies on the Reaction between Dicyanocobinamide and Hypochlorous Acid
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
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.
Correction for instrument time constant in determination of reaction kinetics.
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.
Optimal second order sliding mode control for nonlinear uncertain systems.
Das, Madhulika; Mahanta, Chitralekha
2014-07-01
In this paper, a chattering free optimal second order sliding mode control (OSOSMC) method is proposed to stabilize nonlinear systems affected by uncertainties. The nonlinear optimal control strategy is based on the control Lyapunov function (CLF). For ensuring robustness of the optimal controller in the presence of parametric uncertainty and external disturbances, a sliding mode control scheme is realized by combining an integral and a terminal sliding surface. The resulting second order sliding mode can effectively reduce chattering in the control input. Simulation results confirm the supremacy of the proposed optimal second order sliding mode control over some existing sliding mode controllers in controlling nonlinear systems affected by uncertainty. PMID:24780159
Superposition rules and second-order differential equations
J. F. Cariñena; J. de Lucas
2011-07-14
The main purpose of this work is to introduce and analyse some generalizations of diverse superposition rules for first-order differential equations to the setting of second-order differential equations. As a result, we find a way to apply the theories of Lie and quasi-Lie systems to analyse second-order differential equations. In order to illustrate our results, several second-order differential equations appearing in the physics and mathematical literature are analysed and some superposition rules for these equations are derived by means of our methods.
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.
Canonical description of a second-order achromat
Kheifets, S.A.; Fieguth, T.H.; Ruth, R.D.
1988-03-01
Charged particle motion in second-order magnetic optical achromat is described using a canonical perturbation theory. Necessary and sufficient conditions for the existence of such a device are presented. Given these conditions, the second-order matrix elements at the end of the achromat are found explicity. It is shown that all geometric matrix elements are equal to zero and all chromatic matrix elements are either also equal to zero or proportional to the corresponding chromaticity. Thus all second-order matrix elements vanish simultaneously when the two chromaticities are made to be equal to zero 13 refs., 1 tab.
Method to render second order beam optics programs symplectic
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.
Redner, Sidney
Chapter 8 REACTION KINETICS In this chapter, we will discuss the time evolution of simple reactions-controlled limit. In contrast, in the reaction-controlled limit, reactants must meet many times before a reaction in reduced spatial dimension. Diffusion- limited reactions have played an important role in the development
Giménez, Domingo
Using hyperheuristics to improve the determination of the kinetic constants of a chemical reaction constants of a chemical reaction Kinetic parameters of a chemical reaction are determined with metaheuristic of a chemical reaction that occurs in heterogeneous phase involves the simulation of the processes occurring
Surface Reaction Kinetics of Ga 1x In x P Growth During Pulsed Chemical Beam Epitaxy
Surface Reaction Kinetics of Ga 1x In x P Growth During Pulsed Chemical Beam Epitaxy N. Dietz 1 growth has been a slow process because little is known about chemical reaction properties and reaction into the surface reaction kinetics during an organometallic deposition process. These insights will allow us
NO sub x -char reactions: Kinetics and transport aspects
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.
Simulation of the kinetics of precipitation reactions in ferritic steels
Schneider, A. . E-mail: schneider@mpie.de; Inden, G.
2005-01-10
Computer simulations of diffusion-controlled phase transformations in model alloys of Fe-Cr-C, Fe-Cr-W-C, Fe-Cr-Si-C, and Fe-Cr-Co-V-C are presented. The compositions considered are typical for ferritic steels. The simulations are performed using the software DICTRA and the thermodynamic calculations of phase equilibria are performed using Thermo-Calc. The thermodynamic driving forces and the kinetics of diffusion-controlled precipitation reactions of M{sub 23}C{sub 6}, M{sub 7}C{sub 3}, cementite and Laves-phase (Fe, Cr){sub 2}W are discussed. The simultaneous growth of stable and metastable phases is treated in a multi-cell approach. The results show remarkable effects on the growth kinetics due to the competition during simultaneous growth.
Best constants in a borderline case of second order
Tarsi, Cristina
Best constants in a borderline case of second order Moser type inequalities Daniele Cassani a borderline case of D.R. Adams' [1] generalization of Trudinger-Moser type inequalities to the case of higher
Maximum-principle-satisfying second order discontinuous Galerkin ...
2014-05-05
equations, the same scaling limiter coupled with second order DG methods ... step methods, which are convex combinations of Euler forward steps. ...... ume WENO schemes for convection-diffusion equations, SIAM Journal on Scientific.
On the state estimation of structures with second order observers
NASA Technical Reports Server (NTRS)
Belvin, W. Keith; Park, K. C.
1989-01-01
The use of Linear Quadratic Regulator (LQR) control synthesis techniques implies the availability of full state feedback. For vibration control of structures, usually only a limited number of states are measured from which an observer model reconstructs the full state. It is shown that using second order observers is a viable technique for reconstructing the unmeasured states of structures under mildly restrictive conditions. Moreover, the computational advantages of the second order observer as compared to a first order observer indicate that significantly larger observer models may be utilized. Numerical examples are used to demonstrate the performance of second order observers. The implications of second order observers in the development of Controls-Structures Interaction (CSI) technology is discussed.
Second-order nonlinear optical metamaterials: ABC-type nanolaminates
NASA Astrophysics Data System (ADS)
Alloatti, L.; Kieninger, C.; Froelich, A.; Lauermann, M.; Frenzel, T.; Köhnle, K.; Freude, W.; Leuthold, J.; Wegener, M.; Koos, C.
2015-09-01
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 = Al2O3, B = TiO2, and C = HfO2. 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.
Variational Principles for multisymplectic second-order classical field theories
Pedro Daniel Prieto-Martínez; Narciso Román-Roy
2015-03-31
We state a unified geometrical version of the variational principles for second-order classical field theories. The standard Lagrangian and Hamiltonian variational principles and the corresponding field equations are recovered from this unified framework.
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.
Universality of second order transport in Gauss-Bonnet gravity
Evgeny Shaverin; Amos Yarom
2012-11-08
We compute all the second order transport coefficients of a hydrodynamic theory with a gravity dual which includes a Gauss-Bonnet term. We find that a particular linear combination of the second order transport coefficients, which was found to vanish in generic two derivative gravity theories with matter, remains zero even in the presence of the Gauss-Bonnet term. We contrast this behavior with the shear viscosity to entropy density ratio.
Classic reaction kinetics can explain complex patterns of antibiotic action
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
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.
Kinetic Study of the Austempering Reactions in Ductile Irons
NASA Astrophysics Data System (ADS)
Pérez, M. J.; Cisneros, M. M.; Almanza, E.; Haro, S.
2012-11-01
Kinetics of the reaction that occur during the austempering heat treatment in unalloyed and alloyed ductile irons with 1Cu-0.25Mo, 1Ni-0.25Mo, and 0.7Cu-1Ni-0.25Mo, was studied. The austenitization and austempering cycles were achieved by isothermal dilatometry in cylindrical samples of 2 mm in diameter and 12 mm in length. The specimens were austenitized at 870 °C for 120 min, followed by isothermal holding for 300 min at temperatures between 270 and 420 °C. Kinetic parameters such as the order of reaction " n" and the rate of reaction " k" were calculated using the Johnson-Mehl equation while the empirical activation energy was calculated by means of the Arrhenius equation. It was found that the values of " k" decreased with the addition of Cu, Ni, and Mo as well as with the reduction of the isothermal temperature. The activation energy changes with the austempering temperature, in the range 30,348-58,250 J/mol when the heat treatment was carried out between 370 and 420 °C and 10,336-26,683 J/mol when the temperature varied from 270 to 350 °C. The microstructures in samples austempered at 370 and 315 °C were observed by transmission electron microscopy. No carbides precipitation was observed on samples heat treated at 370 °C for less than 120 min, while at 315 °C carbides of hexagonal structure ?(Fe2.4C) were found from the beginning of the transformation. The smallest value of activation energy and a slower kinetic transformation seem to be related with the presence of a carbide phase. Additionally, the time results obtained for transformation fractions of 0.05 and 0.95 by the dilatometry analysis were used to build the temperature-time-transformation diagrams for the irons.
Kinetics and mechanisms of reactions involving small aromatic reactive intermediates
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.
Python framework for kinetic modeling of electronically excited reaction pathways
NASA Astrophysics Data System (ADS)
Verboncoeur, John; Parsey, Guy; Guclu, Yaman; Christlieb, Andrew
2012-10-01
The use of plasma energy to enhance and control the chemical reactions during combustion, a technology referred to as ``plasma assisted combustion'' (PAC), can result in a variety of beneficial effects: e.g. stable lean operation, pollution reduction, and wider range of p-T operating conditions. While experimental evidence abounds, theoretical understanding of PAC is at best incomplete, and numerical tools still lack in reliable predictive capabilities. In the context of a joint experimental-numerical effort at Michigan State University, we present here an open-source modular Python framework dedicated to the dynamic optimization of non-equilibrium PAC systems. Multiple sources of experimental reaction data, e.g. reaction rates, cross-sections and oscillator strengths, are used in order to quantify the effect of data uncertainty and limiting assumptions. A collisional-radiative model (CRM) is implemented to organize reactions by importance and as a potential means of measuring a non-Maxwellian electron energy distribution function (EEDF), when coupled to optical emission spectroscopy data. Finally, we explore scaling laws in PAC parameter space using a kinetic global model (KGM) accelerated with CRM optimized reaction sequences and sparse stiff integrators.
Effects of nonproductive binding on the kinetics of enzymatic reactions with patterned substrates
Dinner, Aaron
Effects of nonproductive binding on the kinetics of enzymatic reactions with patterned substrates January 2007 Existing models of ligand-receptor binding kinetics suggest that clustering surface, can be used to probe the kinetics of binding and reaction in much greater detail.1013 However
Thermochemical Kinetics for Multireference Systems: Addition Reactions of Ozone
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 gives accurate forward barrier heights; however, it significantly underestimates reaction energies.
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.
Diffusion Controlled Reactions, Fluctuation Dominated Kinetics, and Living Cell Biochemistry
Konkoli, Zoran
2009-01-01
In recent years considerable portion of the computer science community has focused its attention on understanding living cell biochemistry and efforts to understand such complication reaction environment have spread over wide front, ranging from systems biology approaches, through network analysis (motif identification) towards developing language and simulators for low level biochemical processes. Apart from simulation work, much of the efforts are directed to using mean field equations (equivalent to the equations of classical chemical kinetics) to address various problems (stability, robustness, sensitivity analysis, etc.). Rarely is the use of mean field equations questioned. This review will provide a brief overview of the situations when mean field equations fail and should not be used. These equations can be derived from the theory of diffusion controlled reactions, and emerge when assumption of perfect mixing is used.
Optimal automatic reaction and species elimination in kinetic mechanisms
Mitsos, A.
2008-10-15
A known challenge for the simulation of reacting flow systems is that detailed chemical mechanisms contain hundreds to thousands of species and thousands of reactions, leading to high CPU requirements despite the use of state-of-the-art solvers. For specific conditions of interest (temperature, pressure, and composition), smaller mechanisms can predict the chemistry relatively accurately. One possibility for obtaining such mechanisms is species elimination from a detailed mechanism. Here, an automatic method for kinetic model reduction by simultaneous reaction and species elimination is proposed, based on an integer linear program (ILP) formulation. The solution of the ILP is an optimally reduced kinetic mechanism that reproduces the predictions of a reference mechanism within prespecified tolerances for finitely many reference points in the state space. The method is applied to generate optimally reduced models for isobaric, adiabatic homogeneous combustion. Case studies are presented for the combustion of n-heptane. Comparisons between the full and reduced models are shown and the tradeoff between species and reaction elimination is discussed. Tolerances in the ILP formulation control the error introduced by the model reduction. For increasing acceptable error, more species and/or reactions are eliminated. A method of quantifying this tradeoff between approximation error and reduction achieved is proposed, based on multiobjective optimization, and demonstrated in a case study. The effect of variable initial conditions is investigated. The mechanisms generated achieve significant reduction in the CPU requirement and can accurately predict the trajectories of the state variables (species mass fractions and temperature), as well as other metrics of interest, such as ignition time delay. (author)
TÃ³th, JÃ¡nos
Reaction Kinetics and Catalysis Letters, Vol. 1, No. 2/1974/209-213 STOCHASTIC SIMULATION OF CHEMICAL REACTIONS BY DIGITAL COMPUTER, H. APPLICATIONS T. Sipos1, J.TSth 2 and P. ~.rdi1 1. Danube Oil reactions/1/is described. Two applications of the program are given: (i) a reaction taking place
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…
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.
Spacecraft attitude determination using a second-order nonlinear filter
NASA Technical Reports Server (NTRS)
Vathsal, S.
1987-01-01
The stringent attitude determination accuracy and faster slew maneuver requirements demanded by present-day spacecraft control systems motivate the development of recursive nonlinear filters for attitude estimation. This paper presents the second-order filter development for the estimation of attitude quaternion using three-axis gyro and star tracker measurement data. Performance comparisons have been made by computer simulation of system models and filter mechanization. It is shown that the second-order filter consistently performs better than the extended Kalman filter when the performance index of the root sum square estimation error of the quaternion vector is compared. The second-order filter identifies the gyro drift rates faster than the extended Kalman filter. The uniqueness of this algorithm is the online generation of the time-varying process and measurement noise covariance matrices, derived as a function or the process and measurement nonlinearity, respectively.
Second-order axial color of thin lenses in air.
Nobis, Thomas
2015-10-01
In present research, the influence of higher-order aberrations on the correction of secondary axial color is under investigation. Analytical solutions have so far been restricted to special cases and simple optical systems. Common theories require the tracing of rays of different wavelengths. Such numerical approaches do not support the comprehension of the underlying physical effects. In this paper, a formula for second-order axial color contributions is derived which is based on paraxial ray data for the reference wavelength only. Therefore, it allows the determination of second-order axial color in early paraxial design stages without further numerical ray trace. For systems of thin lenses in air, three second-order effects are identified and discussed using simple examples. A quantitative comparison with intrinsic secondary axial color is given. PMID:26479939
Deflection of light to second order in conformal Weyl gravity
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 ?r in the Mannheim-Kazanas metric, yields again the paradoxical contribution ?R (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 ?r in the metric are again insignificant as reported in our earlier work.
Carborane tuning on iridium complexes: redox-switchable second-order NLO responses.
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 ? 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 ? 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
Gilli, L.; Lathouwers, D.; Kloosterman, J. L.; Van Der Hagen, T. H. J. J.
2012-07-01
In this paper a second-order perturbation technique for nonlinear time-dependent problems is presented and applied to a simplified multi-physics model. This method is developed by using the properties of the adjoint problem which allows calculating the set of first and second order coefficients by solving a number of linear systems. As an illustrative example the adjoint procedure is applied to a reference transient problem, represented by a coupled point-kinetic/lumped-parameters model, and used to calculate the sensitivity coefficients of a safety related response with respect to a set of input parameters. The results obtained are compared with the values given by a direct sampling of the forward nonlinear problem. A way to reduce the number of calculations required for the application of second order adjoint techniques is also discussed. Our first results show that the procedure provides good estimations in presence of higher order perturbation components, being able to reconstruct the responses of interest even in presence of non-Gaussian probability density functions. Furthermore, the use of reduced second order information decreases the computational requirements of the method, making it appealing for possible large scale applications. (authors)
Chen, Peng
reaction. For both nanocatalysts, the distributions of the microscopic reaction time from a single catalystSingle-Molecule Kinetics Reveals a Hidden Surface Reaction Intermediate in Single and characterizing reaction inter- mediates is not only important and powerful for elucidating reaction mechanisms
Second order coupling between excited atoms and surface polaritons
Sofia Ribeiro; Stefan Y. Buhmann; Stefan Scheel
2012-12-20
Casimir-Polder interactions between an atom and a macroscopic body are typically regarded as due to the exchange of virtual photons. This is strictly true only at zero temperature. At finite temperature, real-photon exchange can provide a significant contribution to the overall dispersion interaction. Here we describe a new resonant two-photon process between an atom and a planar interface. We derive a second order effective Hamiltonian to explain how atoms can couple resonantly to the surface polariton modes of the dielectric medium. This leads to second-order energy exchanges which we compare with the standard nonresonant Casimir-Polder energy.
Second order approximation of natural frequency constraints in structural synthesis
NASA Technical Reports Server (NTRS)
Miura, H.; Schmit, L. A., Jr.
1978-01-01
The paper is concerned with structural optimization problems in which the constraints consist of limits imposed on the natural frequencies of the structure. Improvements in the quality of approximations for the frequency constraints are sought by considering second-order Taylor series expansions. Analysis of the second-order sensitivity of natural frequencies is carried out. As an example, the design of a midplane symmetric aluminum beam of constant depth supporting three nonstructural masses is considered. Web thickness and chord member areas were determined so as to achieve minimum structural mass while maintaining the fundamental frequency at or above 30 Hz.
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
The Poisson equation at second order in relativistic cosmology
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.
Second order averaging for the nonlinear Schrodinger equation
2011-09-09
by the strong confinement operator with a nonlinear dynamics in the x plane, .... is a second order approximation of the solution ?? in C([0,T0];Bm), i.e., for some ...... here ? instead of ?0), and a system of linear equations for the excited modes.
Second-order accurate difference schemes on highly irregular meshes
Manteuffel, T.A.; White, A.B. Jr.
1988-01-01
In this paper compact-as-possible second-order accurate difference schemes will be constructed for boundary-value problems of arbitrary order on highly irregular meshes. It will be shown that for equations of order (K) these schemes will have truncation error of order (3/endash/K). This phenomena is known as supraconvergence. 7 refs.
Skyrme interaction to second order in nuclear matter
N. Kaiser
2015-05-26
Based on the phenomenological Skyrme interaction various density-dependent nuclear matter quantities are calculated up to second order in many-body perturbation theory. The spin-orbit term as well as two tensor terms contribute at second order to the energy per particle. The simultaneous calculation of the isotropic Fermi-liquid parameters provides a rigorous check through the validity of the Landau relations. It is found that published results for these second order contributions are incorrect in most cases. In particular, interference terms between $s$-wave and $p$-wave components of the interaction can contribute only to (isospin or spin) asymmetry energies. Even with nine adjustable parameters, one does not obtain a good description of the empirical nuclear matter saturation curve in the low density region $0<\\rho<2\\rho_0$. The reason for this feature is the too strong density-dependence $\\rho^{8/3}$ of several second-order contributions. The inclusion of the density-dependent term ${1\\over 6}t_3 \\rho^{1/6}$ is therefore indispensable for a realistic description of nuclear matter in the Skyrme framework.
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…
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…
The normalized second order renormalization group flow on closed surfaces
Volker Branding
2015-03-25
We study a normalized version of the second order renormalization group flow on closed Riemannian surfaces. We discuss some general properties of this flow and establish several basic formulas. In particular, we focus on surfaces with zero and positive Euler characteristic.
Skyrme interaction to second order in nuclear matter
NASA Astrophysics Data System (ADS)
Kaiser, N.
2015-09-01
Based on the phenomenological Skyrme interaction various density-dependent nuclear matter quantities are calculated up to second order in many-body perturbation theory. The spin-orbit term as well as two tensor terms contribute at second order to the energy per particle. The simultaneous calculation of the isotropic Fermi-liquid parameters provides a rigorous check through the validity of the Landau relations. It is found that published results for these second order contributions are incorrect in most cases. In particular, interference terms between s-wave and p-wave components of the interaction can contribute only to (isospin or spin) asymmetry energies. Even with nine adjustable parameters, one does not obtain a good description of the empirical nuclear matter saturation curve in the low density region 0\\lt ? \\lt 2{? }0. The reason for this feature is the too strong density-dependence {? }8/3 of several second-order contributions. The inclusion of the density-dependent term \\frac{1}{6}{t}3{? }1/6 is therefore indispensable for a realistic description of nuclear matter in the Skyrme framework.
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…
a Uniqueness Theorem for Second Order Elliptic Equations
NASA Astrophysics Data System (ADS)
Meshkov, V. Z.
1987-02-01
A uniqueness theorem for the solutions of second order elliptic equations is proved on the basis of a Carleman-type inequality. The author's theorem covers earlier results in this direction obtained by Cordes, Aronszajn, and Hörmander, and is definitive in a certain sense.Bibliography: 11 titles.
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.
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…
Ab initio correlation functionals from second-order perturbation theory.
Schweigert, Igor V; Lotrich, Victor F; Bartlett, Rodney J
2006-09-14
Orbital-dependent exchange-correlation functionals are not limited by the explicit dependence on the density and present an attractive alternative to conventional functionals. With the successful implementation of the exact orbital-dependent exchange functional, the challenge lies in developing orbital-dependent approximations for the correlation functional. Ab initio many-body methods can provide such approximations. In particular, perturbation theory with the Kohn-Sham model as the reference [Görling and Levy, Phys. Rev. A 50, 196 (1994)] defines the exact correlation functional via an infinite perturbation series. The second-order term of these series gives the lowest-order approximation to the correlation functional. However, it has been suggested [Bartlett et al., J. Chem. Phys. 122, 034104 (2005)] that the Kohn-Sham Hamiltonian is not the optimal choice for the perturbation expansion and a different reference Hamiltonian may lead to an improved perturbation series and more accurate second-order approximation. Here, we demonstrate explicitly that the modified series can be used to define superior functional and potential. We present results of atomic and molecular calculations with both second-order functionals. Our results demonstrate that the modified functional offers a significantly improved description of the correlation effects as it does not suffer from convergence problems and results in energies and densities that are more accurate than those obtained with second-order Møller-Plesset perturbation theory or generalized-gradient approximation functionals. PMID:16999516
Forward and backward second-order Pavlovian conditioning in honeybees
Menzel, Randolf - Institut für Biologie
, associative learning can be in- direct or of second-order, as in the case of Pavlov's dog (Pavlov 1927). A dog to CR). Then, in a separate event, the dog was presented with the tone of a bell (neutral stimulus, NS) followed by the light (CS, a secondary reinforcer). After several such combinations, the dog already
FIRST-ORDER SYSTEM LEAST SQUARES FOR SECOND-ORDER ...
second-order uniformly elliptic partial differential equations in n = 2 or 3 ... As an alternative to perturbation-based approaches, the least-squares ... unmodified form must be handled carefully because oscillatory divergence-free error ...... AND P. A. RAVIART, Finite Element Methods for Navier-Stokes Equations: Theory.
PREDICTIONS OF HIGHWAY EMISSIONS BY A SECOND ORDER CLOSURE MODEL
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...
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,…
Second-order bounds for linear recurrences with negative coefficients
NASA Astrophysics Data System (ADS)
Berenhaut, Kenneth S.; Morton, Daniel C.
2006-02-01
This paper introduces a generalization of Fibonacci and Pell polynomials in order to obtain optimal second-order bounds for general linear recurrences with negative coefficients. An important aspect of the derived bounds is that they are applicable and easily computable. The results imply bounds on all entries in inverses of triangular matrices as well as on coefficients of reciprocals of power series.
PID Control of Second-Order Systems with Hysteresis
Ryan, E.P.
PID Control of Second-Order Systems with Hysteresis Bayu Jayawardhana, Hartmut Logemann & Eugene P. Keywords. Hysteresis, Nonlinear systems, PID control, Tuning regulators. 1 Introduction With reference of form (2) exhibit hysteresis phenomena, a particular example of which is the "hysteric spring" model
Kinetics Of Isomerisation Reaction Of Oriented Polyacetylene Induced By Laser
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.
Nuclear quantum effects and kinetic isotope effects in enzyme reactions.
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
Shedd, Daniel C
2014-08-07
acid and calcite will allow for optimized treatment design. The kinetic model was also used to isolate the contributions of the transport of reactants, the surface reaction, and the transport of products to the overall resistance of the reaction...
TÃ³th, JÃ¡nos
Reaction Kinetics and Catalysis Letters, Vol. 1, No. 1, 113-117/1974/ STOCHASTIC SIMULATION OF CHEMICAL REACTION BY DIGITAL COMPUTER, I. THE MODEL T. Sipos, 1 j. T6th, 2 and P. l~rdi 1 1. Danube Oil Received November 9, 1972 A stochastic model of complex chemical reactions is outlined. A discrete
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.
Reaction sequence and kinetics of uranium nitride decomposition.
Silva, G W Chinthaka; Yeamans, Charles B; Sattelberger, Alfred P; Hartmann, Thomas; Cerefice, Gary S; Czerwinski, Kenneth R
2009-11-16
The reaction mechanism and kinetics of the thermal decomposition of uranium dinitride/uranium sesquinitride to uranium mononitride under inert atmosphere at elevated temperature were studied. An increase in the lattice parameter of the UN(2)/alpha-U(2)N(3) phase was observed as the reaction temperature increased, corresponding to a continuous removal of nitrogen. Electron density calculations for these two compounds using XRD powder patterns of the samples utilizing charge-flipping technique were performed for the first time to visualize the decrease in nitrogen level as a function of temperature. Complete decomposition of UN(2) into alpha-U(2)N(3) at 675 degrees C and the UN formation after a partial decomposition of alpha-U(2)N(3) at 975 degrees C were also identified in this study. The activation energy for the decomposition of the UN(2)/alpha-U(2)N(3) phase into UN, 423.8 +/- 0.3 kJ/mol (101.3 kcal/mol), was determined under an inert argon atmosphere and is reported here experimentally for the first time. PMID:19845318
A Biological Interpretation of Transient Anomalous Subdiffusion. II. Reaction Kinetics?
Saxton, Michael J.
2008-01-01
Abstract Reaction kinetics in a cell or cell membrane is modeled in terms of the first passage time for a random walker at a random initial position to reach an immobile target site in the presence of a hierarchy of nonreactive binding sites. Monte Carlo calculations are carried out for the triangular, square, and cubic lattices. The mean capture time is expressed as the product of three factors: the analytical expression of Montroll for the capture time in a system with a single target and no binding sites; an exact expression for the mean escape time from the set of lattice points; and a correction factor for the number of targets present. The correction factor, obtained from Monte Carlo calculations, is between one and two. Trapping may contribute significantly to noise in reaction rates. The statistical distribution of capture times is obtained from Monte Carlo calculations and shows a crossover from power-law to exponential behavior. The distribution is analyzed using probability generating functions; this analysis resolves the contributions of the different sources of randomness to the distribution of capture times. This analysis predicts the distribution function for a lattice with perfect mixing; deviations reflect imperfect mixing in an ordinary random walk. PMID:17905849
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)
Thin film reaction kinetics of niobium/aluminum multilayers
NASA Astrophysics Data System (ADS)
Coffey, K. R.; Barmak, K.; Rudman, D. A.; Foner, S.
1992-08-01
Phase formation kinetics in Nb/Al multilayered thin films having overall compositions of 25, 33, 50, and 75 at. % Al have been investigated using scanning calorimetry, x-ray diffraction, and cross-sectional transmission electron microscopy. The first phase to form upon annealing the Nb/Al layered structure of all samples is the NbAl3 intermetallic. Calorimetry clearly identifies the NbAl3 formation to be a two-stage process. The first stage is the formation of a planar layer by nucleation and growth to coalescence while the second stage is the thickening of the planar layer. The large amount of heat released (and hence large volume fraction of NbAl3 formed) during the first reaction stage is consistent with heterogeneous nucleation at well-isolated sites in the Nb/Al interface. This is surprising in light of the large thermodynamic driving force expected for nucleation and suggests that the local nonequilibrium nature of the Nb/Al interface greatly reduces the driving force for nucleation. The next phase observed in samples of 25 and 33 at. % Al is the A15 superconducting phase, Nb3Al. The Nb3Al growth completes a first reaction stage similar to the NbAl3, but the subsequent thickening reaction stage is not observed without simultaneous Nb2Al growth. The high interface velocities derived from the calorimetry for formation of both NbAl3 and the A15 Nb3Al indicate that atomic transport must be by grain boundary diffusion.
"Kinetics of Chemical Reactions in Environmental Systems: Research Needs and Challenges"
Sparks, Donald L.
"Kinetics of Chemical Reactions in Environmental Systems: Research Needs and Challenges" Donald(oid)s, nutrients, radionuclides, and organic chemicals have shown that reaction rates are initially rapid followed by a slow approach to a steady state. The rapid reaction has been ascribed to chemical reactions and film
of a population state at any time during the course of the reaction. II. THE REVERSIBLE BIMOLECULAR REACTION AAn analytical solution of the stochastic master equation for reversible bimolecular reaction The kinetics of the binding reaction A B C are solved exactly via the stochastic master equation, in which
Reaction kinetics of O(1D) with CF Mitsuhiko Kono and Yutaka Matsumi*
Kono, Mitsu
Reaction kinetics of O(1D) with CF 3 CN Mitsuhiko KonoÂ¤ and Yutaka Matsumi* Solar-T errestrialnd November 2000 The rate constant for removal of O(1D) by reaction with has been measured to be (1 was not observed as a primary product in the present reaction. 1. Introduction Reactions of electronically excited
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…
An oxocarbenium-ion intermediate of a ribozyme reaction indicated by kinetic isotope effects
Bartel, David
An oxocarbenium-ion intermediate of a ribozyme reaction indicated by kinetic isotope effects Peter the formation of a pyrimidine nucleotide. Primary and secondary kinetic isotope ef- fects indicate isotope effect of 1.002 0.003 indicates that the reaction is likely to be less concerted than
Optimal second order sliding mode control for linear uncertain systems.
Das, Madhulika; Mahanta, Chitralekha
2014-11-01
In this paper an optimal second order sliding mode controller (OSOSMC) is proposed to track a linear uncertain system. The optimal controller based on the linear quadratic regulator method is designed for the nominal system. An integral sliding mode controller is combined with the optimal controller to ensure robustness of the linear system which is affected by parametric uncertainties and external disturbances. To achieve finite time convergence of the sliding mode, a nonsingular terminal sliding surface is added with the integral sliding surface giving rise to a second order sliding mode controller. The main advantage of the proposed OSOSMC is that the control input is substantially reduced and it becomes chattering free. Simulation results confirm superiority of the proposed OSOSMC over some existing. PMID:25249166
Relativistic second-order dissipative hydrodynamics at finite chemical potential
Amaresh Jaiswal; Bengt Friman; Krzysztof Redlich
2015-11-17
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.
On Holographic Entanglement Entropy with Second Order Excitations
Song He; Jia-Rui Sun; Hai-Qing Zhang
2015-06-25
We study the low-energy quantum excitation corrections to the holographic entanglement entropy (HEE) of the boundary CFT from the bulk gravitational perturbations up to second order. By focusing on the case when the boundary subsystem is a strip, we show that the bulk minimal surface can be expanded in terms of the conserved charges such as the mass, angular momentum and electric charge of the bulk AdS black brane when the black brane is a slightly perturbed geometry deviates from the pure AdS spacetime. We also calculate the energy of the subsystem in the CFT and argue that the first law-like relation for the subsystem should be satisfied at second order when the bulk geometry is stable under fluctuations at the same order. Moreover, the HEE is naturally bounded at quadratic order perturbations when the cosmic censorship conjecture for the bulk black hole is held.
Second-order nonlinear optical metamaterials: ABC-type nanolaminates
Alloatti, Luca; Froelich, Andreas; Lauermann, Matthias; Frenzel, Tobias; Koehnle, Kira; Freude, Wolfgang; Leuthold, Juerg; Wegener, Martin; Koos, Christian
2015-01-01
Structuring optical materials on a nanometer scale can lead to artificial effective media, or metamaterials, with strongly altered optical behavior. Metamaterials can provide a wide range of linear optical properties such as negative refractive index, hyperbolic dispersion, or magnetic behavior at optical frequencies. Nonlinear optical properties, however, have only been demonstrated for patterned metallic films which suffer from high optical losses. Here we show that second-order nonlinear metamaterials can also be obtained from non-metallic centrosymmetric constituents with inherently low optical absorption. In our proof-of-principle experiments, we have iterated atomic-layer deposition (ALD) of three different constituents, A = Al$_2$O$_3$, B = TiO$_2$ and C = HfO$_2$. 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. To the best of our knowledge, this is the first realizati...
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.
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.
First- and second-order charged particle optics
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.
Transport equations with second-order differential collision operators
Cosner, C.; Lenhart, S.M.; Protopopescu, V.
1988-07-01
This paper discusses existence, uniqueness, and a priori estimates for time-dependent and time-independent transport equations with unbounded collision operators. These collision operators are described by second-order differential operators resulting from diffusion in the velocity space. The transport equations are degenerate parabolic-elliptic partial differential equations, that are treated by modifications of the Fichera-Oleinik-Radkevic Theory of second-order equations with nonnegative characteristic form. They consider weak solutions in spaces that are extensions of L/sup rho/ to include traces on certain parts of the boundary. This extension is necessary due to the nonclassical boundary conditions imposed by the transport problem, which requires a specific analysis of the behavior of our weak solutions.
A Second-Order Achromat Design Based on FODO Cell
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.
Second-order centrality correlation in scale-free networks
NASA Astrophysics Data System (ADS)
Lv, Meilei; Guo, Xinling; Chen, Jiaquan; Lu, Zhe-Ming; Nie, Tingyuan
2015-02-01
Scale-free networks in which the degree displays a power-law distribution can be classified into assortative, disassortative, and neutral networks according to their degree-degree correlation. The second-order centrality proposed in a distributed computation manner is quick-calculated and accurate to identify critical nodes. We explore the second-order centrality correlation (SOC) for each type of the scale-free networks. The SOC-SOC correlation in assortative network and neutral network behaves similarly to the degree-degree correlation, while it behaves an apparent difference in disassortative networks. Experiments show that the invulnerability of most of scale-free networks behaves similarly under the node removal ordering by SOC centrality and degree centrality, respectively. The netscience network and the Yeast network behave a little differently because they are native disconnecting networks.
Cosmological perturbations at second order and recombination perturbed
Senatore, Leonardo; Tassev, Svetlin; Zaldarriaga, Matias E-mail: stassev@cfa.harvard.edu
2009-08-01
We derive the full set of second-order equations governing the evolution of cosmological perturbations, including the effects of the first-order electron number density perturbations, ?{sub e}. We provide a detailed analysis of the perturbations to the recombination history of the universe and show that a perturbed version of the Peebles effective 3-level atom is sufficient for obtaining the evolution of ?{sub e} for comoving wavenumbers smaller than 1 Mpc{sup ?1}. We calculate rigorously the perturbations to the Ly? escape probability and show that to a good approximation it is governed by the local baryon velocity divergence. For modes longer than the photon diffusion scale, we find that ?{sub e} is enhanced during recombination by a factor of roughly 5 relative to other first-order quantities sourcing the CMB anisotropies at second order. Using these results, in a companion paper we calculate the CMB bispectrum generated during recombination.
Local conservation laws of second-order evolution equations
Roman O. Popovych; Anatoly M. Samoilenko
2008-08-06
Generalizing results by Bryant and Griffiths [Duke Math. J., 1995, V.78, 531-676], we completely describe local conservation laws of second-order (1+1)-dimensional evolution equations up to contact equivalence. The possible dimensions of spaces of conservation laws prove to be 0, 1, 2 and infinity. The canonical forms of equations with respect to contact equivalence are found for all nonzero dimensions of spaces of conservation laws.
Harmonic entanglement with second-order non-linearity
Nicolai B. Grosse; Warwick P. Bowen; Kirk McKenzie; Ping Koy Lam
2005-07-08
We investigate the second-order non-linear interaction as a means to generate entanglement between fields of differing wavelengths. And show that perfect entanglement can, in principle, be produced between the fundamental and second harmonic fields in these processes. Neither pure second harmonic generation, nor parametric oscillation optimally produce entanglement, such optimal entanglement is rather produced by an intermediate process. An experimental demonstration of these predictions should be imminently feasible.
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.
Gravitational waves from global second order phase transitions
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.
Asymptotic behavior for abstract evolution differential equations of second order
NASA Astrophysics Data System (ADS)
da Luz, Cleverson Roberto; Ikehata, Ryo; Charão, Ruy Coimbra
2015-11-01
Abstract evolution differential equations of second order in time are studied in order to get (almost) optimal decay estimates to the corresponding energy functional of the equations. The framework is supported by a special energy method in the associated Fourier space. The constructed abstract theory can be applied to several concrete evolutionary partial differential equations as is illustrated in the last section of the paper.
Reaction kinetics of dual setting ?-tricalcium phosphate cements.
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 ?-tricalcium phosphate (?-TCP) is a promising approach to improve the mechanical performance of ?-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 ?-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 ?-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, ?-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
Cr stable isotope fractionation and reaction kinetics in aqueous milieu
NASA Astrophysics Data System (ADS)
Zink, S.; Schoenberg, R.; Staubwasser, M.
2009-12-01
Mass-dependent stable Cr isotope variations show great potential to monitor the natural attenuation of anthropogenic chromate pollution as well as to investigate changes in environmental conditions in the present and the past. However, accurate interpretation of mass-dependent Cr isotope variations requires profound knowledge of the Cr isotope fractionation behaviour during redox transitions and the isotope exchange kinetics of the reactions involved. Here, we present a comprehensive dataset of stable Cr isotope fractionation and reaction kinetics during Cr(III) oxidation, Cr(VI) reduction and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous milieu. All experiments were carried out with both oxidation states (i.e. Cr(III) and Cr(VI)) in solution, using H2O2 as oxidising as well as reducing agent. The pH conditions were varied to investigate the influence of the different Cr(III) and Cr(VI) species on the Cr isotope fractionation and on the reaction mechanisms during the enforced redox transitions. All Cr stable isotope measurements were performed by high-resolution MC-ICP-MS [1]. The reduction of Cr(VI) to Cr(III) with H2O2 under strongly acidic conditions shows an equilibrium isotope fractionation of ?(53,52Cr)Cr(III)-Cr(VI) of -3.54 ± 0.35 ‰. This value is within uncertainty equal to that of -3.4 ± 0.1 ‰ reported by Ellis et al. [2], who used natural sediment and magnetite as reducing agents at pH 6 to 7. At pH = 7 our reduction experiments show a unidirectional, kinetic isotope fractionation ?(53,52Cr)Cr(III)-Cr(VI) of approximately -5 ‰ for reduction rates of up to 80 %, but a strong deviation from this Rayleigh-type process for higher reduction rates. However, at a pH value of 7 H2O2 supports the temporary formation and decomposition of Cr(V)-peroxo complexes that might explain this fractionation behaviour and deviation from a single Rayleigh type trend. The oxidation experiments of Cr(III) to Cr(VI) were carried out in alkaline media using H2O2 as reducing agent. The observed, small Cr isotope fractionation can not be explained by one, unidirectional oxidation process. The high energy needed to oxidise Cr(III) to Cr(VI), potential Cr(III) oligomerisation and the formation of Cr(IV) and/or Cr(V) intermediates make the oxidation of Cr(III) to Cr(VI) a very complex fractionation mechanism. Our best-fit modelling points to an overall isotope fractionation ?(53,52Cr)Cr(VI)-Cr(III) of +0.15 ‰ during the different oxidation steps, which is overprinted by a much larger isotope fractionation ?(53,52Cr)Cr(III)-Cr(VI) of -3.4 ‰ during the back reduction of approximately 15 % of the chromium. No isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed by our experiments over a timescale of 120 hours. This observation is in good agreement with the lack of isotope exchange between oxygen bound in dissolved chromate CrO42- and that of the surrounding water [3]. [1] Schoenberg, R. et al. (2008) Chemical Geology, 249, 294ff. [2] Ellis, A. et al. (2002) Science, 295, 2060ff. [3] Bullen, T. et al. (2009) Geochim. Cosmochim. Acta, 73 (13), Suppl. 1, A173
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.
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.
Constraints on general second-order scalar-tensor models from gravitational Cherenkov radiation
Kimura, Rampei; Yamamoto, Kazuhiro E-mail: kazuhiro@hiroshima-u.ac.jp
2012-07-01
We demonstrate that the general second-order scalar-tensor theories, which have attracted attention as possible modified gravity models to explain the late time cosmic acceleration, could be strongly constrained from the argument of the gravitational Cherenkov radiation. To this end, we consider the purely kinetic coupled gravity and the extended galileon model on a cosmological background. In these models, the propagation speed of tensor mode could be less than the speed of light, which puts very strong constraints from the gravitational Cherenkov radiation.
Soil solid materials affect the kinetics of extracellular enzymatic reactions
NASA Astrophysics Data System (ADS)
Lammirato, C.; Miltner, A.; Kästner, M.
2009-04-01
INTRODUCTION Soil solid materials affect the degradation processes of many organic compounds by decreasing the bioavailability of substrates and by interacting with degraders. The magnitude of this effect in the environment is shown by the fact that xenobiotics which are readily metabolized in aquatic environments can have long residence times in soil. Extracellular enzymatic hydrolysis of cellobiose (enzyme: beta-glucosidase from Aspergillus niger) was chosen as model degradation process since it is easier to control and more reproducible than a whole cell processes. Furthermore extracellular enzymes play an important role in the environment since they are responsible for the first steps in the degradation of organic macromolecules; beta-glucosidase is key enzyme in the degradation of cellulose and therefore it is fundamental in the carbon cycle and for soil in general. The aims of the project are: 1) quantification of solid material effect on degradation, 2) separation of the effects of minerals on enzyme (adsorption ?change in activity) and substrate (adsorption ?change in bioavailability). Our hypothesis is that a rate reduction in the enzymatic reaction in the presence of a solid phase results from the sum of decreased bioavailability of the substrate and decreased activity of enzyme molecules. The relative contribution of the two terms to the overall effect can vary widely depending on the chemical nature of the substrate, the properties of the enzyme and on the surface properties of the solid materials. Furthermore we hypothesize that by immobilizing the enzyme in an appropriate carrier the adsorption of enzymes to soil materials can be eliminated and that therefore immobilization can increase the overall reaction rate (activity loss caused by immobilization < activity loss caused by adsorption to soil minerals). MATERIALS AND METHODS Enzymatic kinetic experiments are carried out in homogeneous liquid systems and in heterogeneous systems where solid materials (bentonite, kaolinite, goethite, activated charcoal) are suspended in a mixed liquid (standard experimental conditions: 66 mM phosphate buffer, pH 5, 25°C, 20 mg solid/ml buffer). The enzyme in an immobilized form (covalent bonding to oxirane groups on the surfaces of macroporous Eupergit® C particles) is used to exclude a direct effect of soil solid materials on the enzyme without excluding their effect on the availability of the substrate.The progress of the reactions is determined by measuring the accumulation of the product (i.e. glucose) in the systems at different times (after destroying enzymatic activity by boiling the samples) with a coupled enzymatic assay and an automatic microplate spectrophotometer. A regression analysis on the data points is performed to calculate the initial reaction rates, which is the parameter that allows to compare the different systems. RESULTS AND DISCUSSION The results show that, under the standard experimental conditions, cellobiose is not adsorbed by the clay minerals bentonite and kaolinite and by the iron oxyhydroxide goethite. In the case of activated charcoal a rapid adsorption phase in the first 20' is followed by a much slower process; after 4h 30' approximately 98% of cellobiose was adsorbed. The results from the adsorption experiments of beta-glucosidase to bentonite, kaolinite, goethite and activated charcoal show that, under the standard experimental conditions, the adsorption process is rapid in all cases (more than 80% of the adsorption takes place in the first 20 minutes). After 1h 20min the following fractions of enzyme were adsorbed: 30 % to bentonite, 60% to kaolinite, 67% to goethite, 100% to activated charcoal. The effect of kaolinite on the reaction rate was quantified: under the standard experimental conditions the initial reaction rate in presence of the mineral was 22% less then in the control. The fraction of enzyme molecules which are adsorbed to kaolinite (60%) loses 37% of its activity. CONCLUSIONS The results from the adsorption experiments lead to the conclusion that, among the sol
Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II
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.
Ab initio study of the kinetics of hydrogen abstraction reactions on toluene and tetralin
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.
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…
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…
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.
A second order differential equation for a point charged particle
Torromé, Ricardo Gallego
2012-01-01
A model for the dynamical evolution of a point charged particle interacting with higher order fields is described by an ordinary second order implicit differential equation. We show that such equation is free of run-away and pre-accelerated solutions of Dirac's type. The theory is Lorentz invariant, causal, and compatible with Newton's first law and energy-momentum conservation. However, it is not a local theory in the usual sense. In our model for point charged particles, covariant uniform acceleration motion is unstable and must be understood as an approximation.
Second-order nonlinear optical effects of spin currents
NASA Astrophysics Data System (ADS)
Wang, Jing; Liu, Ren-Bao; Zhu, Bang-Fen
2011-12-01
Pure spin currents, which carry information via spins in lieu of charges, are a key element in spintronics and signify the quantum spin Hall effect. However, they are hardly traceable as they bear neither net magnetization nor net charge currents, notwithstanding many "smoking-gun" evidences. We show that a pure spin current has measurable second-order nonlinear optical effects by symmetry analysis and microscopic calculations. These findings may be exploited for directly "seeing" spin currents in real-time and real-space with standard nonlinear optical spectroscopy.
Galaxy number counts to second order and their bispectrum
Dio, Enea Di; Durrer, Ruth; Marozzi, Giovanni; Montanari, Francesco E-mail: Ruth.Durrer@unige.ch E-mail: Francesco.Montanari@unige.ch
2014-12-01
We determine the number counts to second order in cosmological perturbation theory in the Poisson gauge and allowing for anisotropic stress. The calculation is performed using an innovative approach based on the recently proposed ''geodesic light-cone'' gauge. This allows us to determine the number counts in a purely geometric way, without using Einstein's equation. The result is valid for general dark energy models and (most) modified gravity models. We then evaluate numerically some relevant contributions to the number counts bispectrum. In particular we consider the terms involving the density, redshift space distortion and lensing.
Finite difference schemes for second order systems describing black holes
Motamed, Mohammad; Kreiss, H-O.; Babiuc, M.; Winicour, J.; Szilagyi, B.
2006-06-15
In the harmonic description of general relativity, the principal part of Einstein's equations reduces to 10 curved space wave equations for the components of the space-time metric. We present theorems regarding the stability of several evolution-boundary algorithms for such equations when treated in second order differential form. The theorems apply to a model black hole space-time consisting of a spacelike inner boundary excising the singularity, a timelike outer boundary and a horizon in between. These algorithms are implemented as stable, convergent numerical codes and their performance is compared in a 2-dimensional excision problem.
Second-order electromagnetic eigenfrequencies of a triaxial ellipsoid
NASA Astrophysics Data System (ADS)
Mehl, James B.
2009-10-01
The dependence of the eigenvalues of the TM1n and TE1n electromagnetic triplet modes on the shape of a triaxial ellipsoid cavity resonator is investigated. For an ellipsoid with semi-axes proportional to 1 : (1 + epsilon1) : (1 + epsilon2) the fractional perturbations of the triplet components are found to second order in epsilon1 and epsilon2. The formulae are derived from the results of Kokkorakis and Roumeliotis (1997 J. Electromagn. Waves Appl. 11 279-92) for prolate and oblate spheroids. Finite-element calculations were carried out to confirm the accuracy of the formulae and to determine the next correction terms.
Results for second order hyperbolic systems with viscous dumping
NASA Astrophysics Data System (ADS)
Lasiecka, I.
1985-01-01
Results have been obtained for certain second order hyperbolic systems with viscous dumping which imply that one can increase at will the margin of stability of arbitrarily finite modes of the damped wave equation (those presumed dominant) by means of certain type of the boundary feedback, while the remaining new modes approach asymptotically the original ones from the left of the vertical axis Rez = -k. Numerical testing of the constructive procedure is in the process of being implemented by a Ph.D. student.
Bernstein, Dennis S.
A Nonlinear Observer for Semidetectable Chemical Reactions with Application to Kinetic]. For the class of polyno- mial systems that model the concentrations of species of a chemical reaction network that the reactions of chemical networks are semistable, that is, the concentrations converge to nonzero values
A constant-time kinetic Monte Carlo algorithm for simulation of large biochemical reaction networks
Li, Tiejun
A constant-time kinetic Monte Carlo algorithm for simulation of large biochemical reaction networks The time evolution of species concentrations in biochemical reaction networks is often modeled using simulation. We present here a constant-time algorithm, whose cost is independent of the number of reactions
Sontag, Eduardo
On persistence of chemical reaction networks with time-dependent kinetics and no global work. The new results allow the consideration of reaction rates which are time-varying, thus for persistence of chemical reaction networks are proposed, which extend those obtained by the authors in previous
Kinetics of Radical-Radical Reactions of Hydrocarbon-Based Radicals Vadim D. Knyazev,*
Knyazev, Vadim D.
as chain termination pathways. In addition, radical-radical reactions represent pathways of molecular mass1 Kinetics of Radical-Radical Reactions of Hydrocarbon-Based Radicals Vadim D. Knyazev,* Irene R-radical reactions are among the very important elementary processes occurring in the oxidation and pyrolysis
Appendix C Kinetic MonteCarlo algorithm to simulate deuterium reaction
Goddard III, William A.
152 Appendix C Kinetic MonteCarlo algorithm to simulate deuterium reaction with diamond (100) (2\\Theta1) C.1 Reaction mechanism The interaction of gasphase deuterium with the diamond surface is modeled via an abridged version of the reaction mechanism of Dawnkaski et al. [1], table C.1
On the universal identity in second order hydrodynamics
Sašo Grozdanov; Andrei O. Starinets
2014-12-29
We compute the 't Hooft coupling correction to the infinite coupling expression for the second order transport coefficient $\\lambda_2$ in ${\\cal N}=4$ $SU(N_c)$ supersymmetric Yang-Mills theory at finite temperature in the limit of infinite $N_c$, which originates from the $R^4$ terms in the low energy effective action of the dual type IIB string theory. Using this result, we show that the identity involving the three second order transport coefficients, $2 \\eta \\tau_\\Pi - 4 \\lambda_1 - \\lambda_2 =0$, previously shown by Haack and Yarom to hold universally in relativistic conformal field theories with string dual descriptions to leading order in supergravity approximation, holds also at next to leading order in this theory. We also compute corrections to transport coefficients in a (hypothetical) strongly interacting conformal fluid arising from the generic curvature squared terms in the corresponding dual gravity action (in particular, Gauss-Bonnet action), and show that the identity holds to linear order in the higher-derivative couplings. We discuss potential implications of these results for the near-equilibrium entropy production rate at strong coupling.
Meyer, T E; Tollin, G; Cusanovich, M A; Freeman, J C; Blankenship, R E
1989-07-01
The photochemical reaction center in the green bacterium Chloroflexus aurantiacus is similar to that found in purple phototrophic bacteria and interacts with a multiheme membrane-bound cytochrome. We have examined the kinetics of reduction of the pure solubilized reaction center cytochrome by laser flash photolysis of solutions containing lumiflavin or FMN. Reduction by lumiflavin semiquinone followed single exponential kinetics and the observed rate constant (kobs) was linearly dependent on protein concentration (k = 1.8 X 10(7) M-1s-1 heme-1). This result suggests either that the four hemes have similar reduction rate constants which cannot be resolved or that there are large differences in rate constant and only the most reactive heme (or hemes) was observed under these conditions. To determine the relative reactivities of the four hemes, we varied the extent of heme reduction at a single total protein concentration. As the hemes were progressively reduced by steady-state illumination prior to laser flash photolysis, kobs for the reaction with fully reduced lumiflavin decreased nonlinearly. Second-order rate constants for the four hemes were assigned by nonlinear least-squares analysis of kobs vs oxidized heme concentration data. The second-order rate constants obtained in this way for the highest and lowest potential hemes differed by a factor of about 20, which is larger than expected for c-type cytochromes based on redox potential alone (a factor of about 3 would be expected). This is interpreted as being due to differences in steric accessibility. Relative to the highest potential heme, which is as reactive as a typical c-type cytochrome, we estimated a steric effect of approximately twofold for heme 2, and steric effects of approximately fivefold for hemes 3 and 4. Using fully reduced FMN as reductant of oxidized cytochrome, ionic strength effects indicate a minus-minus interaction, with approximately a -2 charge near the site of reduction of the highest potential heme. PMID:2544143
A Pore Scale Evaluation of the Kinetics of Mineral Dissolution and Precipitation Reactions (EMSI)
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.
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.
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 magnetic shields. In the quadrupole and 12-pole traps, the potentials are produced by RF voltages applied to even numbers (4 and 12, respectively) of parallel rods equally spaced around a circle. The polarity of the voltage on each rod is opposite that of the voltage on the adjacent rod. As a result, the amplitude of the RF trapping field is zero along the centerline and increases, with radius, to a maximum value near the rods.
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.
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.
Cai, Yun
2010-01-14
and chemical information of catalysts from UHV to elevated pressure conditions; 2) explore reaction mechanisms by in situ monitoring surface species with concurrent kinetic measurements. In this dissertation, NO adsorption and dissociation on Rh(111) have been...
Cavity enhanced second-order nonlinear quantum photonic logic circuits
Trivedi, Rahul; Majumdar, Arka
2015-01-01
A large obstacle for realizing quantum photonic logic is the weak optical nonlinearity of available materials, which results in large power consumption. In this paper, we argue that second order ($\\chi^{(2)}$) nonlinear optical devices are more suitable for achieving low power photonic logic. We present the theoretical design of all-optical logic with $\\chi^{(2)}$ nonlinear bimodal cavities and their networks. Using semiclassical models derived from the Wigner quasi-probability distribution function, we analyze the power consumption of networks implementing an optical AND gate and an optical latch. Comparison between the second and third order $(\\chi^{(3)})$ optical logic reveals that the $\\chi^{(2)}$ design outperforms the corresponding $\\chi^{(3)}$ design in terms of the gate power consumption at high quality factors. Specifically, using realistic estimates for the $\\chi^{(2)}$ and $\\chi^{(3)}$ susceptibilities of available materials we show that at cavity quality factors $\\sim 10^4$, optical logic designed...
Second order chromaticity of the interaction regions in the collider
Sen, T.; Syphers, M.
1993-05-01
The collider in the SSC has large second order chromaticity ({xi}{sub 2}) with the interaction regions (IRs) contributing substantially to it. We calculate the general expression for {xi}{sub 2} in a storage ring and find that it is driven by the first order chromatic beta wave. Specializing to the interaction regions, we show that {xi}{sub 2} is a minimum when the phase advance ({Delta}{mu}{sub IP-IP}) between adjacent interaction points is an odd multiple of {pi}/2 and both IRs are identical. In this case the first order chromatic beta wave is confined within the IRs. Conversely, {xi}{sub 2} is large either if {Delta}{mu}{sub IP-IP} = (2n + 1){pi}/2 and the two IRs are very far from equality or if the two IRs are equal but {Delta}{mu}{sub IP-IP} = n{pi}.
Second order chromaticity of the interaction regions in the collider
Sen, T.; Syphers, M.
1993-05-01
The collider in the SSC has large second order chromaticity ([xi][sub 2]) with the interaction regions (IRs) contributing substantially to it. We calculate the general expression for [xi][sub 2] in a storage ring and find that it is driven by the first order chromatic beta wave. Specializing to the interaction regions, we show that [xi][sub 2] is a minimum when the phase advance ([Delta][mu][sub IP-IP]) between adjacent interaction points is an odd multiple of [pi]/2 and both IRs are identical. In this case the first order chromatic beta wave is confined within the IRs. Conversely, [xi][sub 2] is large either if [Delta][mu][sub IP-IP] = (2n + 1)[pi]/2 and the two IRs are very far from equality or if the two IRs are equal but [Delta][mu][sub IP-IP] = n[pi].
Reconstructing the inflaton potential: Perturbative reconstruction to second order
Copeland, Edmund J.; Kolb, Edward W.; Liddle, Andrew R.; Lidsey, James E.
1993-08-01
One method to reconstruct the scalar field potential of inflation is a perturbative approach, where the values of the potential and its derivatives are calculated as an expansion in departures from the slow-roll approximation. They can then be expressed in terms of observable quantities, such as the square of the ratio of the gravitational wave amplitude to the density perturbation amplitude, the deviation of the spectral index from the Harrison--Zel'dovich value, etc. Here, we calculate complete expressions for the second-order contributions to the coefficients of the expansion by including for the first time corrections to the standard expressions for the perturbation spectra. As well as offering an improved result, these corrections indicate the expected accuracy of the reconstruction. Typically the corrections are only a few percent.
Relativistic second-order dissipative hydrodynamics at finite chemical potential
Jaiswal, Amaresh; Redlich, Krzysztof
2015-01-01
Starting from the Boltzmann equation in the relaxation time approximation and employing Chapman-Enskog like expansion for the distribution function close to equilibrium, we derive second-order evolution equations for shear stress tensor and 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 evolution equations for shear stress tensor and dissipative charge current could 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.
New Implicitly Solvable Potential Produced by Second Order Shape Invariance
Cannata, F; Kolevatova, E V; Nishnianidze, D N
2015-01-01
The procedure proposed recently by J.Bougie, A.Gangopadhyaya and J.V.Mallow 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 Schr\\"odinger 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.
K-inflationary power spectra at second order
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.
Second-order phase transitions, L. Landau and his successors
Mnyukh, Y
2011-01-01
There are only two ways for solid-state phase transitions to be compliant with thermodynamics: emerging of infinitesimal quantity of the new phase, or infinitesimal "qualitative" change occurring uniformly throughout the bulk at a time. The suggested theories of phase transitions are checked here for that compliance and in historical perspective. While introducing the theory of "continuous" second-order phase transitions, L. Landau claimed that they "may also exist" along with the majority of first order phase transitions, the latter being "discontinuous", displaying "jumps" of their physical properties; the fundamental differences between the two types were specified. But his theoretical successors disregarded these irreconcilable differences, incorrectly presenting all phase transitions as a cooperative phenomenon treatable by statistical mechanics. In the meantime, evidence has been mounted that all phase transitions have a nucleation-and-growth mechanism, thus making the above classification unneeded.
Relativistic quantum transport coefficients for second-order viscous hydrodynamics
Wojciech Florkowski; Amaresh Jaiswal; Ewa Maksymiuk; Radoslaw Ryblewski; Michael Strickland
2015-05-19
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 non-equilibrium part. Specializing to 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+1d 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 leads to better agreement with the exact solution of the relativistic Boltzmann equation.
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.
Model for reaction kinetics in pyrolysis of wood
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.
WEAK GALERKIN METHODS FOR SECOND ORDER ELLIPTIC INTERFACE PROBLEMS
MU, LIN; WANG, JUNPING; WEI, GUOWEI; YE, XIU; ZHAO, SHAN
2013-01-01
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 L2 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 O(h) to O(h1.5) 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 O(h1.75) to O(h2) in the L? norm for C1 or Lipschitz continuous interfaces associated with a C1 or H2 continuous solution. PMID:24072935
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)
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…
Li, Lingling
2012-07-16
PROPERTIES AND REACTION KINETICS OF AMIDOAMINE OXIDE SURFACTANT-BASED ACIDS WITH CALCITE A Dissertation by LINGLING LI Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements... for the degree of DOCTOR OF PHILOSOPHY May 2011 Major Subject: Petroleum Engineering Rheological Properties and Reaction Kinetics of Amidoamine Oxide Surfactant-based Acids with Calcite Copyright 2011...
Pedersen; Jensen; Humble; Rein; Tanner; Bodmann; Reiser
2000-02-24
[reaction: see text] A racemic aldehyde can undergo parallel kinetic resolution (PKR) by simultaneous reaction with two different chiral phosphonates, differing either in the structure of the chiral auxiliary or in the structure of the phosphoryl group (i.e., one (E)- and one (Z)-selective reagent). This strategy allows conversion of a racemic aldehyde to two different, synthetically useful chiral products with essentially doubled material throughput and similar or improved selectivities as compared to conventional kinetic resolution. PMID:10814370
Hot atom kinetic theory: Changes in average reaction energy
NASA Astrophysics Data System (ADS)
Knierim, K. D.
1990-10-01
Average gas phase hot atom reaction energy is determined using the two-temperature moment method of solving the Boltzmann equation. Factors which can alter the average reaction energy are discussed. A model system based on the 18F + H 2 reactive cross section is used to illustrate changes in reaction energy resulting from addition of a moderator or a competing reactant.
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.
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
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.
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.
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...
Accelerated Search Kinetics Mediated by Redox Reactions of DNA Repair Enzymes
Levine, Alex J.
Accelerated Search Kinetics Mediated by Redox Reactions of DNA Repair Enzymes Pak-Wing Fok and Tom to explain the localization of base excision repair (BER) enzymes to lesions on DNA. The CT mechanism relies on redox reactions of iron-sulfur cofactors that modify the enzyme's binding affinity. These redox
KINETICS OF GAS-GRAIN REACTIONS IN THE SOLAR NEBULA BRUCE FEGLEY, JR.
KINETICS OF GAS-GRAIN REACTIONS IN THE SOLAR NEBULA BRUCE FEGLEY, JR. Planetary Chemistry nebula. However, chemical reactions proceed at different rates, which generally decrease exponentially the local en- vironment cooled significantly or before the gaseous solar nebula was dispersed
Paper Number 15736-PA Title Reaction Kinetics of Fuel Formation for In-Situ Combustion
Abu-Khamsin, Sidqi
the approach of a combustion front. Analysis of gases produced from the reaction cell revealed that pyrolysisPaper Number 15736-PA Title Reaction Kinetics of Fuel Formation for In-Situ Combustion Authors Abu believed to cause fuel formation for in-situ combustion have been studied and modeled. A thin, packed bed
Truong, Thanh N.
Kinetics of Hydrogen Abstraction Reactions from Polycyclic Aromatic Hydrocarbons by H Atoms Angela of being a major intermediate leading to soot formation, and existing kinetic models give poor predictions is the availability of accurate kinetic parameters. Hence, an accurate analysis of the reaction rates is required
Second-order electromagnetic eigenfrequencies of a triaxial ellipsoid II
NASA Astrophysics Data System (ADS)
Mehl, James B.
2015-10-01
Finite-element calculations of electromagnetic eigenvalues are known to converge to the exact solutions in the limit of vanishing element sizes. In an extension of previous work (Mehl 2009 Metrologia 46 554-9) the eigenfrequencies of the TM1n and TE1n (n??=??1, 2, ··· 6) modes of triaxial ellipsoids were calculated as a function of mesh size. Higher-accuracy eigenvalues were obtained through a limiting process as the mesh size was reduced; the extrapolation was based on the theoretical convergence rate. The difference between the finite-element eigenfrequencies and the eigenfrequencies predicted by shape perturbation theory is found to be proportional to the cube of the fractional deformation parameter ? for all investigated modes. For ellipsoids with axes proportional to 1?:?1.0005?:?1.0010, the cubic term represents a fractional perturbation of the average TM16 eigenvalue k2 by??-0.16??× 10??-??6 and the average TE16 eigenvalue by??-0.22??× 10??-??6. This work adds support to the correctness of the analytic second-order formula derived in the previous work, and also demonstrates the usefulness of finite-element methods for investigating the quasi-spherical resonators (QSRs) used in measurements of the Boltzmann constant. In principle, the method can be extended to QSRs whose shape differs from triaxial ellipsoids.
Second order sliding mode control for a quadrotor UAV.
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
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.
Second-order perturbation theory: problems on large scales
Pound, Adam
2015-01-01
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 timescales. 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 ef...
On computing first and second order derivative spectra
NASA Astrophysics Data System (ADS)
Roy, Indrajit G.
2015-08-01
Enhancing resolution in spectral response and an ability to differentiate spectral mixing in delineating the endmembers from the spectral response are central to the spectral data analysis. First and higher order derivatives analysis of absorbance and reflectance spectral data is commonly used techniques in differentiating the spectral mixing. But high sensitivity of derivative to the noise in data is a major problem in the robust estimation of derivative of spectral data. An algorithm of robust estimation of first and second order derivative spectra from evenly spaced noisy normal spectral data is proposed. The algorithm is formalized in the framework of an inverse problem, where based on the fundamental theorem of calculus a matrix equation is formed using a Volterra type integral equation of first kind. A regularization technique, where the balancing principle is used in selecting a posteriori optimal regularization parameter is designed to solve the inverse problem for robust estimation of first order derivative spectra. The higher order derivative spectra are obtained while using the algorithm in sequel. The algorithm is tested successfully with synthetically generated spectral data contaminated with additive white Gaussian noise, and also with real absorbance and reflectance spectral data for fresh and sea water respectively.
Holographic dark matter and dark energy with second order invariants
Alejandro Aviles; Luca Bonanno; Orlando Luongo; Hernando Quevedo
2011-11-25
One of the main goals of modern cosmology remains to summon up a self consistent policy, able to explain, in the framework of the Einstein's theory, the cosmic speed up and the presence of Dark Matter in the Universe. Accordingly to the Holographic principle, which postulates the existence of a minimal size of a physical region, we argue, in this paper, that if this size exists for the Universe and it is accrued from the independent geometrical second order invariants, it would be possible to ensure a surprising source for Dark Matter and a viable candidate for explaining the late acceleration of the Universe. Along the work, we develop low redshift tests, such as Supernovae Ia and kinematical analysis complied by the use of Cosmography and we compare the outcomes with higher redshift tests, such as CMB peak and anisotropy of the cosmic power spectrum. All the results indicate that the models presented here can be interpreted as unified models that are capable to describe both the dark matter and the dark energy.
PHD filters of second order in target number
NASA Astrophysics Data System (ADS)
Mahler, Ronald
2006-05-01
The multitarget recursive Bayes nonlinear filter is the theoretically optimal approach to multisensor-multitarget detection, tracking, and identification. For applications in which this filter is appropriate, it is likely to be tractable for only a small number of targets. In earlier papers we derived closed-form equations for an approximation of this filter based on propagation of a first-order multitarget moment called the probability hypothesis density (PHD). In a recent paper, Erdinc, Willett, and Bar-Shalom argued for the need for a PHD-type filter which remains first-order in the states of individual targets, but which is higher-order in target number. In an earlier paper at this conference we derived a closed-form cardinalized PHD CPHD), filter, which propagates not only the PHD but also the entire probability distribution on target number. Since the CPHD filter has computational complexity O(m 3) in the number m of measurements, additional approximation is desirable. In this paper we discuss a second-order approximation called the "binomial filter."
Correction of the Chromaticity up to Second Order for MEIC
H. K. Sayed, S.A. Bogacz, P. Chevtsov
2010-03-01
The proposed electron collider lattice exhibits low ?- functions at the Interaction Point (IP) (?x?100mm ? ?y? 20 mm) and rather large equilibrium momentum spread of the collider ring (?p/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.
Incorporation of aqueous reaction and sorption kinetics andbiodegradation into TOUGHREACT
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.
Kinetic and mechanistic studies of free-radical reactions in combustion
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.
Comparison of kinetic and equilibrium reaction models insimulating the behavior of porous media
Kowalsky, Michael B.; Moridis, George J.
2006-11-29
In this study we compare the use of kinetic and equilibriumreaction models in the simulation of gas (methane) hydrate behavior inporous media. Our objective is to evaluate through numerical simulationthe importance of employing kinetic versus equilibrium reaction modelsfor predicting the response of hydrate-bearing systems to externalstimuli, such as changes in pressure and temperature. Specifically, we(1) analyze and compare the responses simulated using both reactionmodels for natural gas production from hydrates in various settings andfor the case of depressurization in a hydrate-bearing core duringextraction; and (2) examine the sensitivity to factors such as initialhydrate saturation, hydrate reaction surface area, and numericaldiscretization. We find that for large-scale systems undergoing thermalstimulation and depressurization, the calculated responses for bothreaction models are remarkably similar, though some differences areobserved at early times. However, for modeling short-term processes, suchas the rapid recovery of a hydrate-bearing core, kinetic limitations canbe important, and neglecting them may lead to significantunder-prediction of recoverable hydrate. Assuming validity of the mostaccurate kinetic reaction model that is currently available, the use ofthe equilibrium reaction model often appears to be justified andpreferred for simulating the behavior of gas hydrates, given that thecomputational demands for the kinetic reaction model far exceed those forthe equilibrium reaction model.
Graphene liquid marbles as photothermal miniature reactors for reaction kinetics modulation.
Gao, Wei; Lee, Hiang Kwee; Hobley, Jonathan; Liu, Tianxi; Phang, In Yee; Ling, Xing Yi
2015-03-23
We demonstrate the fabrication of graphene liquid marbles as photothermal miniature reactors with precise temperature control for reaction kinetics modulation. Graphene liquid marbles show rapid and highly reproducible photothermal behavior while maintaining their excellent mechanical robustness. By tuning the applied laser power, swift regulation of graphene liquid marble's surface temperature between 21-135?°C and its encapsulated water temperature between 21-74?°C are demonstrated. The temperature regulation modulates the reaction kinetics in our graphene liquid marble, achieving a 12-fold superior reaction rate constant for methylene blue degradation than at room temperature. PMID:25650763
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.
NASA Astrophysics Data System (ADS)
Markovic, Bojan; Vladimirov, Sote; Cudina, Olivera; Savic, Vladimir; Karljikovic-Rajic, Katarina
2010-02-01
A novel topical corticosteroid FA-21-PhP, 2-phenoxypropionate ester of fluocinolone acetonide, has been synthesized in order to investigate the possibility of decreasing systemic side effects. In this study model system for in vitro solvolytic reaction of FA-21-PhP has been analyzed in ethanol/water (90:10, v/v) with excess of sodium hydrogen carbonate. The selected conditions have been used as in vitro model for activation of corticosteroid C-21 ester prodrug. The second-order derivative spectrophotometric method (DS) using zero-crossing technique was developed for monitoring ternary mixture of solvolysis. Fluocinolone acetonide (FA) as a solvolyte was determined in the mixture in the concentration range 0.062-0.312 mM using amplitude 2D 274.96. Experimentally determined LOD value was 0.0295 mM. The accuracy of proposed DS method was confirmed with HPLC referent method. Peak area of parent ester FA-21-PhP was used for solvolysis monitoring to ensure the initial stage of changes. Linear relationship in HPLC assay for parent ester was obtained in the concentration range 0.054-0.54 mM, with experimentally determined LOD value of 0.0041 mM. Investigated solvolytic reaction in the presence of excess of NaHCO 3 proceeded via a pseudo-first-order kinetic with significant correlation coefficients 0.9891 and 0.9997 for DS and HPLC, respectively. The values of solvolysis rate constant calculated according to DS and HPLC methods are in good accordance 0.038 and 0.043 h -1, respectively.
General theory of multistage geminate reactions of isolated pairs of reactants. I. Kinetic equations
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.
Redner, Sidney
Chapter 8 REACTION KINETICS In this chapter, we will discuss the time evolution of simple reactions#usionÂcontrolled limit. In contrast, in the reactionÂcontrolled limit, reactants must meet many times before a reaction in reduced spatial dimension. Di#usionÂ limited reactions have played an important role in the development
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.…
Further development and testing of a second-order bulk boundary layer model. Master's thesis
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.
Coherent chemical kinetics as quantum walks I: Reaction operators for radical pairs
A. Chia; A. Gorecka; K. C. Tan; L. Pawela; P. Kurzynski; T. Paterek; D. Kaszlikowski
2015-08-20
Classical chemical kinetics use 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, or in other words, a reaction which contain only incoherent transitions. A prominent example reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator which 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 a recombination dephasing rate consistent with recent experiments [J. Chem. Phys. {\\bf 139}, 234309 (2013)], in contrast to previous work by Jones and Hore [Chem. Phys. Lett. {\\bf 488}, 90 (2010)]. The standard radical-pair reaction has conventionally been described by either a normalised density operator incorporating both the radical pair and reaction products, or by a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalised and refers only to radical-pair states. Generalisations to include additional dephasing processes and an arbitrary number of sites are also discussed.
Second order multidimensional sign-preserving remapping for ALE methods
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 for single material problems. The results demonstrate that the MPDATA gauge option is suitable for providing accurate ALE remapping and preserves the multidimensionality and sign of both scalar and vector fields.
Xu, Li; Horváth, Attila K
2014-08-14
The pentathionate-iodate reaction has been investigated by spectrophotometrically monitoring the formation of the total amount of iodine at 468 nm in the presence of phosphoric acid/dihydrogen phosphate buffer. We noticed that iodine forms only after a fairly long time lag, and the inverse of time necessary to produce a certain amount of iodine is linearly proportional to the initial concentration of iodate ion and the square of the hydrogen ion concentration, while depending complexly on the concentration of substrate pentathionate. This reaction can therefore be treated as a clock reaction but differs from the original Landolt reaction in the sense that substrate pentathionate and the clock species iodine coexist for a relatively long time--due to their relatively slow direct reaction--depending on the experimental circumstances. Furthermore, we also provided experimental evidence that iodide ion acts as an autocatalyst of the system. A 14-step kinetic model is proposed in which the mechanisms of the pentathionate-iodine, bisulfite-iodate, and the well-known Dushman reactions are combined. A thorough analysis revealed that the direct pentathionate-iodate reaction plays a role only to produce iodide ions via a finite sequence of reactions, and once its concentration reaches a certain level, the reaction is almost exclusively governed by the pentathionate-iodine and the Dushman reactions. As expected, a strong catalytic effect of the buffer composition is also found that can readily be explained by its well-known catalytic influence on the original Dushman reaction. PMID:25068832
Minnesota, University of
1 Hybrid Quantum and Classical Methods for Computing Kinetic Isotope Effects of Chemical Reactions for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble that enzymes accelerate the rates of chemical reactions has fascinated chemists and biochemists for nearly
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.
Kinetics of the reaction of hydrogen sulfide and sulfur dioxide in organic solvents
Neumann, D.W.; Lynn, S.
1986-01-01
Calorimetry was used to study the kinetics of the irreversible reaction between hydrogen sulfide and sulfur dioxide in mixtures of N,N-dimethylaniline (DMA) and diethylene glycol monomethyl ether (DGM) and of DMA and triethylene glycol dimethyl ether (triglyne). The reaction was found to be first order in both H/sub 2/S and SO/sub 2/ in the presence of DMA. The approximate heat of reaction is 28 kcal/mol of sulfur dioxide. The addition of DMA accelerates the reaction by an order of magnitude over that obtained in the glycol ethers alone. Rate constants are in the range of 1-20 L/(mol s). Hydroxylated species such as water, methanol, and other alcohols increase the rate still more dramatically when added to the DMA/ether mixtures. The results of these experiments show some of the effects of solvent composition on the kinetics of the reaction.
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)
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
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.
A Note on the Kinetics of Diffusion-mediated Reactions
Naqvi, K Razi
2014-01-01
The prevalent scheme of a diffusion-mediated bimolecular reaction $A+B\\rightarrow P$ is an adaptation of that proposed by Briggs and Haldane for enzyme action [{\\em Biochem J.\\/}, 19:338--339, 1925]. The purpose of this Note is to explain, {\\em by using an argument involving no mathematics\\/}, why the breakup of the encounter complex cannot be described, except in special circumstances, in terms of a first-order process $\\{AB\\}\\rightarrow A+B$. Briefly, such a description neglects the occurrence of re-encounters, which lie at the heart of Noyes's theory of diffusion-mediated reactions. The relation $k=\\alpha k_{\\mbox{\\scriptsize e}}$ becomes valid only when $\\alpha$ (the reaction probability per encounter) is very much smaller than unity (activation-controlled reactions), or when $\\beta$ (the re-encounter probability) is negligible (as happens in a gas-phase reaction). References to some works (by the author and his collaborators) which propound the correct approach for finding $k$ are also supplied.
Seismic implications of the kinetics of the reaction perovskite + ferropericlase = ringwoodite
NASA Astrophysics Data System (ADS)
Lessing, Stephan; Dobson, David P.; Cobden, Laura; Sebastian, Rost; Thomas, Christine
2014-05-01
Kinetics of the mantle transition zone phase transitions/mineral reactions may give insights into the density structure and rheology of subducting slabs or mantle plume regions. The effect of kinetics in mantle up- and downwellings on the seismic structure has not been investigated in detail and would add further constraints on mantle dynamics. Here we study whether and how the effects of reaction kinetics can be resolved with PP and SS precursors in mantle upwellings. PP or SS precursors are underside reflections of P- or S-waves off the discontinuities, halfway between the source and the receivers. We use data from kinetic experiments of the reaction of perovskite and ferropericlase to ringwoodite and combine them with thermodynamic calculations of phase assemblages to obtain the seismic structure of kinetically inhibited mineral assemblages. The kinetic data show sensitivity to grain size and upwelling rate. From the profiles of density, P wave and S wave velocity, we calculate 1D synthetic seismograms for a range of dominant frequencies. We analyse the frequency dependence of the amplitudes and traveltime residuals of the reflected waves. The synthetic modelling shows that kinetic inhibition of the backward reaction of ringwoodite, i.e. the recombination of perovskite + ferropericlase to ringwoodite, affects the amplitudes of PP and SS underside reflections, showing larger amplitudes for shorter periods due to the finite depth interval where the kinetic inhibition occurs. Thus the frequency dependency of PP and SS precursor amplitudes can be a probe to investigate regions of mantle upwellings and to further constrain grain size in the mantle.
Second-order susceptibility from a tight-binding Hamiltonian
Dumitrica, T.; Graves, JS; Allen, Roland E.
1998-01-01
to the tight-binding form, an effective momentum operator P and a kinetic energy opera- tor T can be defined.12 In matrix form these operators are pn ,n 8 ~ k!5 m0 \\ C? ~ nk!?kH~k!C~n8k!, ~4! m0 ? 15 340 ?1998 The American Physical Society t a 8... y e T ~ k!5 C ~nk!? ? H~k!C~n 8 k!. ~5! PHYSICAL REVIEW B 15 DECEMBER 1998-IVOLUME 58, NUMBER 23 II of this paper we summarize the essential features of their formalism. In Sec. III we then extend it to obtain an analyti- cal expression...
Second-order truncated functional expansions of energy density functionals
NASA Astrophysics Data System (ADS)
Joubert, Daniel
2001-11-01
Parr and Liu [Chem. Phys. Lett., 276, 164 (1997)], showed that the electron-electron repulsion functional Vee[?] can be expressed in terms of its first and second functional derivatives under certain assumptions. Starting from this expansion it is shown that with the same assumptions, the density-functional exchange energy Ex[?], correlation energy Ec[?], and the kinetic contribution to the correlation energy Tc[?], can each be expressed in terms of their first and second functional derivatives only. It is pointed out that some expansions of density functionals proposed in the literature are not compatible with the expressions derived.
On the potential failure of reduced reaction kinetics
NASA Astrophysics Data System (ADS)
Powers, Joseph; Paolucci, Samuel
2013-11-01
Severe stiffness of equations modeling advection, reaction, and diffusion in combustion systems has motivated many efforts to filter the primary mechanism inducing the stiffness: the simultaneous presence of fast and slow reaction dynamics. Here, it is demonstrated that a common filtering technique for construction of low dimensional reaction manifolds, connection of equilibria by heteroclinic orbits, can fail. While the method is guaranteed to generate an invariant manifold, the local dynamics far from equilibrium may be such that nearby trajectories are in fact carried away from the identified invariant manifold, thus rendering it to be of limited utility in capturing slow dynamics far from equilibrium. An eigenvalue-based method is described to characterize the local behavior of such invariant manifolds. The method provides a diagnostic tool for evaluating whether a candidate manifold has the desirable properties of being both slow and attractive. A simple model system and a realistic hydrogen-air system are examined; method success and failure are demonstrated.
Kinetics and Mechanism of the Chlorate-Bromide Reaction.
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
WELL POSEDNESS FOR DAMPED SECOND ORDER SYSTEMS WITH UNBOUNDED INPUT OPERATORS*
WELL POSEDNESS FOR DAMPED SECOND ORDER SYSTEMS WITH UNBOUNDED INPUT OPERATORS* H.T. Banks, K. Ito9015007. #12; Well Posedness for Damped Second Order Systems with Unbounded Input Operators H.T. Banks, K. Ito and Y. Wang Abstract: We consider damped second order in time systems such as those arising
Binocular summation of second-order global motion signals in human vision Claire V. Hutchinson a,
Nottingham, University of
Binocular summation of second-order global motion signals in human vision Claire V. Hutchinson a 2013 Keywords: Global motion Binocular summation Second-order First-order a b s t r a c t Although many, nature and extent of the binocular advantage for encoding second-order (contrast- defined) global motion
Kinetics Feasibility Study of Alcohol Sulfate Esterification Reactions in
Elrod, Matthew J.
on sulfuric acid films, Iraci and co-workers have asserted that reaction 1 is too slow to lead to appreciable and sulfuric acid to form sulfate esters in aerosol particles is explored. Nuclear magnetic resonance methods of simple alcohols. The experiments were carried out at various sulfuric acid concentrations and a range
Chang, M. H.; Cho, S.; Lee, E. S.; Ahn, M. Y.; Kim, D. H.; Jung, J. J.; Chung, H.; Shim, M.; Song, K. M.; Kim, D.; Yoshida, H.
2008-07-15
The de-hydriding reaction between ZrCo and hydrogen is the most important role of delivering hydrogen isotopes for fusion energies. Many researchers experimented in various conditions and estimated the relationship between ZrCo and hydrogen. In this study the kinetic approaches are performed using numerical simulations between ZrCo and hydrogen. Two kinds of parameter estimations are performed for the equilibrium pressure and the kinetics modeling and those are validated by the good agreement between predicted and experimental data. Based on the numerical simulation with obtained parameters, more rapid rates of de-hydriding reaction can be achieved with lower pressure and higher temperature. (authors)
On the complexity of kinetics and the mechanism of the thiosulfate-periodate reaction.
Rauscher, Evelin; Cseko, György; Horváth, Attila K
2011-06-20
The thiosulfate-periodate reaction has been studied spectrophotometrically in a slightly acidic medium at 25.0 ± 0.1 °C in an acetate/acetic acid buffer by monitoring the absorbance in the 250-600 nm wavelength range at a constant ionic strength adjusted by the buffer component sodium acetate. In agreement with a previous study, we found that the reaction cannot be described by a single stoichiometric equation, tetrathionate and sulfate are simultaneously formed, and its ratio strongly depends on the pH. As expected at certain initial concentration ratios of the reactants, the reaction behaves as a clock reaction, but after its appearance, iodine is slowly consumed mainly because of the moderate tetrathionate-iodine reaction. It is also enlightened that the initial rate of the reaction is completely independent of the pH, which apparently contradicts a previous study, which postulates a "supercatalytic" behavior of the hydrogen ion on the title reaction. Significant buffer assistance that may change the absorbance-time profiles was also observed. On the basis of the kinetic data, a robust 28-step kinetic model with 22 fitted parameters is proposed and discussed to explain adequately all of the important characteristics of the kinetic curves. PMID:21612189
Truong, Thanh N.
the first step. In such a case, theory can play an important role in providing necessary kinetic informationKinetics of Hydrogen Abstraction Reaction Class H + H-C(sp3): First-Principles Predictions Using the Reaction Class Transition State Theory Shaowen Zhang and Thanh N. Truong* Henry Eyring Center
Computer-assisted study of the kinetics of H/sub 2/O/sub 2/-S(IV) reaction in precipitation samples
Shen, J.; Lee, Y.N.
1986-07-01
A computer-assisted data acquisition and analysis method for the study of the kinetics of H/sub 2/O/sub 2/-S(IV) reaction in precipitation samples has been developed. The extent of reaction was followed by continuous amperometric measurement of the concentrations of the reagents. The analog output signal of the amperometric device was acquired, digitized, and processed by a Keithley DAS Series 500 data acquisition system connected to an IBM-PC/XT computer. The apparent second-order rate constant of the reaction, as defined -d(H/sub 2/O/sub 2/)/dt = k/sup (2)/(H/sub 2/O/sub 2/)(S(IV)), was calculated by the computer using a least-squares fitting routine. This technique was found to be applicable for a wide range of pH and concentrations of H/sub 2/O/sub 2/ and S(IV) as exhibited by precipitation samples. A comparison of the results obtained by this method and a manual method revealed that the computer-assisted method not only was more time efficient but also yielded data with higher precision.
Reactions of Cl atoms with alkyl esters: kinetic, mechanism and atmospheric implications.
Ifang, Stefanie; Benter, Thorsten; Barnes, Ian
2015-04-01
Rate coefficients have been measured for the reaction of Cl atoms with a series of alkyl esters at 298?±?2 K and atmospheric pressure in a large volume photoreactor using the relative kinetic technique. The kinetic data have been used in conjunction with other literature studies on the reactions of Cl atoms with esters to revise the existing values for ester substituent factors in a structure activity relationship (SAR) for Cl reactions. Product studies are reported for the reactions of Cl atoms with isopropyl ethanoate and methyl-2-methyl-propanoate under NO x -free conditions. These studies highlight the types of products that can be expected when oxidation occurs at R groups on the acyl (-C(O)OR) and oxy (RC(O)O-) sides of the ester functionality where R is a straight or branched chain alkyl entity. Possible atmospheric repercussions of the atmospheric chemistry of esters are considered. PMID:24809490
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.
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.
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.
NASA Astrophysics Data System (ADS)
Suzuki, Hiroyuki; Brown, Eric; Sterling, Ray
2015-09-01
Second-order sideband generation in a coherent-mechanical pumped optomechanical system is discussed, and the features of the coherent mechanical pump induced enhancement of second-order sideband generation are identified. We show that the coherent mechanical pump induced enhancement of second-order sideband generation exhibits an essential difference between the case of a weak control field and a strong control field. In the weak control field case, the efficiency of second-order sideband generation increases as the amplitude of the mechanical pump increases. In the strong control field case, the effect of optomechanically induced transparency occurs and increasing the amplitude of the mechanical pump does not always bring an enhancement of second-order sideband generation. The phase-dependent effect of the second-order sideband generation with a coherent mechanical pump is also discussed, and it is shown that the phase difference ? plays an important role in the process of second-order sideband generation.
Yancey, Benjamin; Vyazovkin, Sergey
2015-04-21
This study highlights the effect of the aggregate state of a reactant on the reaction kinetics under the conditions of nanoconfinement. Our previous work (Phys. Chem. Chem. Phys., 2014, 16, 11409) has demonstrated considerable deceleration of the solid state trimerization of sodium dicyanamide in organically modified silica nanopores. In the present study we use FTIR, NMR, pXRD, TGA and DSC to analyze the kinetics and mechanism of the liquid state trimerization of potassium and rubidium dicyanamide under similar conditions of nanoconfinement. It is found that nanoconfinement accelerates dramatically the kinetics of the liquid state trimerization, whereas it does not appear to affect the reaction mechanism. Kinetic analysis indicates that the acceleration is associated with an increase in the preexponential factor. Although nanoconfinement has the opposite effects on the respective kinetics of solid and liquid state trimerization, both effects are linked to a change in the preexponential factor. The results obtained are consistent with our hypothesis that the effects differ because nanoconfinement may promote disordering of the solid and ordering of the liquid reaction media. PMID:25796991
Ma, Teng-Ying; Ma, Na-Na; Yan, Li-Kai; Guan, Wei; Su, Zhong-Min
2013-03-01
The switchable second-order nonlinear optical (NLO) responses of the photoisomerized chromophore dithienylperfluorocyclopentene (DTE) derivatives, organic-inorganic systems of Lindqvist-type [Mo?O??]²?, have been investigated by tuning open-ring and the closed-ring form. In the present paper, we performed density functional theory (DFT) combined with finite field (FF) methods to calculate the second-order NLO coefficients for these organic-inorganic compounds. The calculations with three functionals (B3LYP/CAM-B3LYP/LC-BLYP) confirm the switching behavior on NLO properties by the photoisomerization reaction. The ?(tot) value of system 2c (closed-ring form) is 10 times larger than that of its open-ring form (system 2o). And the other two pairs of systems also show good tuning properties. The ampliative ratio on second-order NLO coefficients between systems 2o and 2c (?(2c)/?(2o)) is 13 times as large as that of DTE (?(DTEc)/?(DTEo)). It suggests that introduction of [Mo?O??]²? and organic groups to the DTE monomer effectively improve the conversion ratio of second-order NLO coefficients between the open-ring and closed-ring forms. PMID:23419765
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.
Control of Mass Transport and Chemical Reaction Kinetics in Ultrasmall Volumes
NASA Astrophysics Data System (ADS)
Collier, Charles
2012-02-01
This talk will describe means for triggering chemical reactions for studying reaction kinetics under extreme confinement with sub-millisecond temporal resolution, including on-demand generation and fusion of femtoliter (10-15 L) volume water-in-oil droplets, and triggering reactions in femtoliter chambers microfabricated in poly(dimethylsiloxane) (PDMS). We demonstrated a reversible chemical toggle switch, which lays the groundwork for exploring more complex chemical and biochemical reaction sequences triggered and monitored in real time in discrete ultrasmall reactors, such as sequential and coupled enzymatic reactions. We are also developing methods to vary confinement and macromolecular crowding in ultrasmall, water-in-oil droplets and chambers micromolded in PDMS as biomimetic reaction vessels containing minimal synthetic gene circuits, in order to better understand how confinement, reduced dimensionality and macromolecular crowding affect molecular mechanisms involved in the operation and regulation of genetic circuits in living cells.
SurfKin: an ab initio kinetic code for modeling surface reactions.
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
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…
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.
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…
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…
Bechhoefer, John
Control of DNA Replication by Anomalous Reaction-Diffusion Kinetics Michel G. Gauthier and John replication in which the rate of initiation of replication origins is controlled by protein-DNA interactions nearly the end of replication, when it becomes diffusion limited. Initiation of origins is suppressed
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.
Kinetics of the reaction of diethylene glycol bis-chloroformate with allyl alcohol
Alekseev, N.N.; Shtoda, N.F.; Dzumedzei, N.V.
1988-10-01
The kinetics of diethylene glycol bis-chloroformate solvolysis by excess allyl alcohol in toluene and carbon tetrachloride has been studied. Under conditions of a pseudofirst order reaction with respect to diethylene glycol bis-chloroformate the activation parameters confirm an addition-detachment mechanism.
Andujar-De Sanctis, Ivonne L; Singleton, Daniel A
2012-10-19
Intramolecular (13)C kinetic isotope effects were determined for the dimerization of methacrolein. Trajectory studies accurately predict the isotope effects and support an origin in Newton's second law of motion, with no involvement of zero-point energy or transition state recrossing. Atomic motion reaction coordinate diagrams are introduced as a way to qualitatively understand the selectivity. PMID:23025278
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…
Autocatalysis and Self-Inhibition: Coupled Kinetic Phenomena in the Chlorite-Tetrathionate Reaction
Epstein, Irving R.
of the parent reaction have been investigated. The kinetics and mechanism of the chlorite-hypochlorous acid,5 thiosulfate-chlorine dioxide,6 tetrathionate-hypochlorous acid,7 chlorine dioxide-hypochlorite,8 and chlorine is "supercatalytic". This feature plays a key role in the diffusion-driven instabilities,10 cellular acidity fronts
Agmon, Noam
2003 Several recent theories of the kinetics of diffusion influenced excited-state association and the so-called kinetic theory. In the irreversible limit, none of these theories reduce, this new theory has been compared14 with simulated ground-state kinetics for the A B C reaction,15 and more
Bench-scale Kinetics Study of Mercury Reactions in FGD Liquors
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.
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.
Macroscopic Kinetic Effect of Cell-to-Cell Variation in Biochemical Reactions
Pan-Jun Kim; Nathan D. Price
2010-04-08
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.
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…
Kinetics of hydration-dehydration reactions considered as solid transformations
Stanish, M.A.; Perlmutter, D.D.
1982-01-01
A mechanism is proposed for the dehydration-rehydration process in solid inorganic salts and model rate equations are derived and applied to the observed behavior of potassium carbonate. Quantitative expressions for the effect of pressure on the reaction rates are derived using basic principles from nucleation and heterogeneous phase transformation theory. Model equation predictions agree with experimental dehydration and rehydration rate data at all but extreme pressures. The basic rate equation is also used to interpret the data of Eckhardt and Flanagan (1964) for the effect of pressure on the dehydration of manganous formate dihydrate. The mechanism on which the model equations are based is also consistent with the observed effects of cycling and of high temperatur pretreatment on the K/sub 2/CO/sub 3/ rehydration rate.
Kinetics of SiC Formation During High P-T Reaction Between Diamond and Silicon
Pantea,C.; Voronin, G.; Zerda, T.; Wang, L.; Zhao, Y.
2005-01-01
Time-resolved in situ X-ray diffraction at simultaneous high pressures (P) and high temperatures (T) was used to monitor kinetics of the reaction between diamond and silicon. Analysis of the data indicated that the reaction was diffusion controlled, and the diffusion was taking place through grain boundaries. For the nm size diamond the activation energy (170 kJ/mol) was smaller than that for {mu}m size diamond (260 kJ/mol), and the reaction started at a temperature below the melting point of silicon. These effects are attributed to nanocrystalline structure and strained bonds within grain boundaries.
NASA Astrophysics Data System (ADS)
Wang, Quan-De; Wang, Xing-Jian; Liu, Zi-Wu; Kang, Guo-Jun
2014-11-01
Ab initio and chemical kinetic study of the hydrogen abstraction reactions by the hydrogen radical on ethyl formate, ethyl acetate, ethyl propanoate, and ethyl butanoate have been performed at the CCSD(T)/CBS//B3LYP/6-311G(d, p) level of theory. High-pressure limit rate constants at temperatures from 300 to 2500 K have been calculated for all of the reaction channels using transition state theory with Eckart tunneling corrections, and the data are fitted to the modified three parameters Arrhenius expression using least-squares regression. A branching ratio analysis for each reaction site has also been investigated for all of the ethyl esters.
Kinetics of the reaction between OH radicals and monochlorodimethylsulphide (CH 3SCH 2Cl)
NASA Astrophysics Data System (ADS)
Shallcross, Dudley E.; Vaughan, Stewart; Trease, David R.; Canosa-Mas, Carlos E.; Ghosh, Mariana V.; Dyke, John M.; Wayne, Richard P.
The gas-phase rate coefficient for the reaction between OH radicals and CH 3SCH 2Cl (MCDMS) was determined to be (2.5±1.3)×10 -12 cm 3 molecule -1 s -1 using the discharge-flow kinetic technique. An estimate of ?10 -10 cm 3 molecule -1 s -1 was obtained for the rate coefficient for reaction of Cl with MCDMS. It would appear that the reaction with OH is not the main loss process for CH 3SCH 2Cl in the marine boundary layer. The possible implications for the MBL of halogen-promoted oxidation of dimethylsulphide are considered.
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).
Kinetic parameters of radical reactions of 2-mercaptobenzothiazole with quinone imines
NASA Astrophysics Data System (ADS)
Varlamov, V. T.; Gadomska, A. V.
2014-09-01
The chain reaction of N, N'-diphenyl-1,4-benzoquinone diimine with 2-mercaptobenzothiazole was studied by two methods developed earlier for the nonchain reaction of N-phenyl-1,4-benzoquinone monoimine with 2-mercaptobenzothiazole. In the methods used, the kinetic scheme of the reaction is simplified by creating conditions under which the rates of all stages except radical generation and decay can be neglected. One of the methods was updated. For the nonchain reaction of N-phenyl-1,4-benzoquinone monoimine with 2-mercaptobenzothiazole, both methods gave close results; for the chain reaction of N, N'-diphenyl-1,4-phenylenediamine with 2-mercaptobenzothiazole, the results differed by approximately one order of magnitude.
Kowalsky, Michael B.; Moridis, George J.
2006-11-29
In this study we compare the use of kinetic and equilibriumreaction models in the simulation of gas (methane) hydrate behavior inporous media. Our objective is to evaluate through numerical simulationthe importance of employing kinetic versus equilibrium reaction modelsfor predicting the response of hydrate-bearing systems to externalstimuli, such as changes in pressure and temperature. Specifically, we(1) analyze and compare the responses simulated using both reactionmodels for natural gas production from hydrates in various settings andfor the case of depressurization in a hydrate-bearing core duringextraction; and (2) examine the sensitivity to factors such as initialhydrate saturation, hydrate reaction surface area, and numericaldiscretization. We find that for large-scale systems undergoing thermalstimulation and depressurization, the calculated responses for bothreaction models are remarkably similar, though some differences areobserved at early times. However, for modeling short-term processes, suchas the rapid recovery of a hydrate-bearing core, kinetic limitations canbe important, and neglecting them may lead to significantunder-prediction of recoverable hydrate. The use of the equilibriumreaction model often appears to be justified and preferred for simulatingthe behavior of gas hydrates, given that the computational demands forthe kinetic reaction model far exceed those for the equilibrium reactionmodel.
Using Single-Turnover Kinetics with Osmotic Stress to Characterize the EcoRV Cleavage Reaction
Ferrandino, Rocco; Sidorova, Nina; Rau, Donald
2014-01-01
Type II restriction endonucleases require metal ions to specifically cleave DNA at canonical sites. Despite the wealth of structural and biochemical information, the number of Mg2+ ions used for cleavage by EcoRV, in particular, at physiological divalent ion concentrations is still not established. In this work we employ a single-turnover technique that uses osmotic stress in order to probe reaction kinetics between an initial specific EcoRV-DNA complex formed in the absence of Mg2+ and the final cleavage step. With osmotic stress, complex dissociation before cleavage is minimized and the reaction rates are slowed to a convenient timescale of minutes to hours. We find that cleavage occurs by a two-step mechanism that can be characterized by two rate constants. The dependence of these rate constants on Mg2+ concentration and osmotic pressure gives the number of Mg2+ ions and water molecules coupled to each kinetic step of the EcoRV cleavage reaction. Each kinetic step is coupled to the binding 1.5 – 2.5 Mg2+ ions, the uptake of ~30 water molecules, and the cleavage of a DNA single strand. We suggest that each kinetic step reflects an independent, rate limiting conformational change of each monomer of the dimeric enzyme that allows Mg2+ ion binding. This modified single turnover protocol has general applicability for metalloenzymes. PMID:24328115
Deriving reaction mechanisms from kinetic spectroscopy. Application to late rhodopsin intermediates.
Szundi, I; Lewis, J W; Kliger, D S
1997-01-01
A general algebraic approach to the kinetic analysis of time-dependent absorption data is presented that allows the calculation of possible kinetic schemes. The kinetic matrices of all possible reaction mechanisms are calculated from experimental eigenvalues and eigenvectors derived from the decay constants and amplitude spectra (b-spectra) of the global exponential fit to the time-dependence of the absorption data. The eigenvalues are directly related to the decay constants, and the eigenvectors are obtained by decomposing the b-spectra into spectral components representing the intermediates. The analysis method is applied to the late intermediates (lumi, meta I, meta I-380, and meta II) of the rhodopsin photoreaction. The b-spectra are decomposed into lumi, meta I, meta-380, and rhodopsin spectra. The meta-380 component is partitioned into isospectral meta I-380 and meta II components based on physical criteria. The calculated kinetic matrices yield a number of reaction mechanisms (linear scheme with back reactions, branched schemes with equilibrium steps, and a variety of square models) consistent with the photolysis data at 25 degrees C. The problems associated with isospectral intermediates (meta I-380 and meta II) are treated successfully with this method. PMID:9251787
Reduction of soliton interactions by sliding-frequency second-order Butterworth filters
NASA Astrophysics Data System (ADS)
Dung, Jeng-Cherng; Chi, Sien; Wen, Senfar
1996-03-01
The reduction of the soliton interaction by use of optical sliding-frequency second-order Butterworth filters is studied numerically. It is found that the second-order Butterworth filters can reduce the soliton interaction more effectively than Fabry-Perot filters or third-order Butterworth filters because the second-order Butterworth filter induces larger frequency chirping on the soliton, compressing it as it propagates in the fiber after the filter.
Wille, Christa; Lenhart, Rachel; Wang, Sijian; Thelen, Darryl; Heiderscheit, Bryan
2015-01-01
Study Design Controlled laboratory study, cross sectional design. Objective To determine if sagittal kinematic variables can be used to estimate select running kinetics. Background Excessive loading during running has been implicated in a variety of injuries, yet this information is typically not assessed during a standard clinical examination. Developing a clinically feasible strategy to estimate ground reaction forces and joint kinetics may improve the ability to identify those at an increased risk of injury. Methods Three-dimensional kinematics and ground reaction forces of 45 participants were recorded during treadmill running at self-selected speed. Kinematic variables used to estimate specific kinetic metrics included: vertical excursion of the center of mass, foot inclination angle at initial contact, horizontal distance between the center of mass and heel at initial contact, knee flexion angle at initial contact, and peak knee flexion angle during stance. Linear mixed effects models were fitted to explore the association between the kinetic and kinematic measures, including step rate and gender, with final models created using backward variable selection. Results Models were developed to estimate peak knee extensor moment (R2=0.43), energy absorbed at the knee during loading response (R2=0.58), peak patellofemoral joint reaction force (R2=0.55), peak vertical ground reaction force (R2=0.48), braking impulse (R2=0.50), and average vertical loading rate (R2=0.04). Conclusions Our findings suggest that insights into important running kinetics can be obtained from a subset of sagittal plane kinematics common to a clinical running analysis. Of note, the limb posture at initial contact influenced subsequent loading patterns in stance. PMID:25156183
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.
NASA Astrophysics Data System (ADS)
Lin, N. Y.
1996-02-01
Laser induced acetone-sensitized excitation of DNA components offered, for the first time, T-T absorption spectra and direct measurement of triplet states kinetics of cytosine, cytidine, and dCMP, adenine, adenosine and dAMP and guanosine. Mechanisms and kinetics of electron transfer reactions between triplet acetone and purine bases and triplet thymine and electrophilic modifiers have been elucidated. Rapid electron transfer from hydroxycinnamic acid derivatives to oxidizing OH adducts of pyrimidines have been performed. Fast reduction and repair of oxidizing damage of pyrimidines have been achieved using pulse radiolysis techniques.
CHLORINE DEMAND AND TTHM FORMATION KINETICS: A SECOND-ORDER MODEL
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...
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
Linear matrix inequalities for analysis and control of linear vector second-order systems
Adegas, Fabiano D.; Stoustrup, Jakob
2015-11-10
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.
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 with acetate concentrations and the energy available in the environment, and how M. acetivorans regulate the enzymes of methanogenesis under different biogeochemical conditions.
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, ?rH° and ?rS°, from the measured equilibrium constants. The values obtained from the Second Law analysis (?rH° = - 80.8 ± 2.2 kJ mol-1; ?rS° = - 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. Müller, F. Stroh, Atmospheric Chemistry and Physics, 2007, 7, 3055 2. S. L. Nickolaisen, R. R. Friedl, S. P. Sander, Journal of Physical Chemistry, 1994, 98, 155 3. S. P. Sander, R. R. Friedl, D. M. Golden, M. J. Kurylo, R. E. Huie, V. L. Orkin, G. K. Moortgat, A. R. Ravishankara, C. E. Kolb, M. J. Molina, B. J. Finlayson-Pitts, Chemical Kinetics and Photochemical Data for use in Atmospheric Studies, Evaluation No. 14, JPL Publication 02-25, NASA Jet Propulsion Laboratory, Pasadena CA, 2003
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.
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.
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.
Moxley, Michael A; Becker, Donald F
2012-01-10
The multifunctional proline utilization A (PutA) flavoenzyme from Escherichia coli catalyzes the oxidation of proline to glutamate in two reaction steps using separate proline dehydrogenase (PRODH) and ?(1)-pyrroline-5-carboxylate (P5C) dehydrogenase domains. Here, the kinetic mechanism of PRODH in PutA is studied by stopped-flow kinetics to determine microscopic rate constants for the proline:ubiquinone oxidoreductase mechanism. Stopped-flow data for proline reduction of the flavin cofactor (reductive half-reaction) and oxidation of reduced flavin by CoQ(1) (oxidative half-reaction) were best-fit by a double exponential from which maximum observable rate constants and apparent equilibrium dissociation constants were determined. Flavin semiquinone was not observed in the reductive or oxidative reactions. Microscopic rate constants for steps in the reductive and oxidative half-reactions were obtained by globally fitting the stopped-flow data to a simulated mechanism that includes a chemical step followed by an isomerization event. A microscopic rate constant of 27.5 s(-1) was determined for proline reduction of the flavin cofactor followed by an isomerization step of 2.2 s(-1). The isomerization step is proposed to report on a previously identified flavin-dependent conformational change [Zhang, W. et al. (2007) Biochemistry 46, 483-491] that is important for PutA functional switching but is not kinetically relevant to the in vitro mechanism. Using CoQ(1), a soluble analogue of ubiquinone, a rate constant of 5.4 s(-1) was obtained for the oxidation of flavin, thus indicating that this oxidative step is rate-limiting for k(cat) during catalytic turnover. Steady-state kinetic constants calculated from the microscopic rate constants agree with the experimental k(cat) and k(cat)/K(m) parameters. PMID:22148640
Reaction-kinetic parameters of glycidamide as determinants of mutagenic potency.
Silvari, V; Haglund, J; Jenssen, D; Golding, B T; Ehrenberg, L; Törnqvist, M
2005-02-01
Values for reaction-kinetic parameters of electrophiles can be used to predict mutagenic potency. One approach employs the Swain-Scott relationship for comparative kinetic studies of electrophilic agents reacting with nucleophiles. In this way glycidamide (GA), the putatively mutagenic/carcinogenic metabolite of acrylamide, was assessed by determining the rates of reaction with different nucleophiles. The rate constants (kNu) were determined using the "supernucleophile" cob(I)alamin [Cbl(I)] as an analytical tool. The Swain-Scott parameters for GA were compared with those of ethylene oxide (EO). The substrate constants, s values, for GA and for EO were found to be 1.0 and 0.93, respectively. The reaction rates at low values of nucleophilic strength (n=1-3), corresponding to oxygens in DNA, were determined to be 2-3.5 times higher for GA compared to EO. GA was also more reactive than EO towards other nucleophiles (n=0-6.4). The mutagenic potency of GA was determined in Chinese hamster ovary cells (hprt mutations in CHO-AA8 cells per dose unit with gamma-radiation as reference standard). The potency of GA was estimated to be about three mutations per 10(5) cells and mMh corresponding to about 40 rad-equ./mMh. A preliminary comparison of the mutagenic potency (per mMh and as rad-equivalents) of GA and EO shows an approximately seven times higher potency for GA. A higher mutagenic potency of GA compared to EO is compatible with expectation from reaction-kinetic data of the two compounds. The data confirmed that GA is not a strong mutagen, which is in line with what is expected for simple oxiranes. The present study shows the value of cob(I)alamin for the determination of reaction-kinetic parameters and their use for prediction of mutagenic potency. PMID:15668111
Ben O'Shaughnessy; Dimitrios Vavylonis
1998-12-21
We study reactions between end-functionalized chains at a polymer-polymer interface. For small chemical reactivities (the typical case) the number of diblocks formed, $R_t$, obeys 2nd order chemically controlled kinetics, $R_t \\sim t$, until interfacial saturation. For high reactivities (e.g. radicals) a transition occurs at short times to 2nd order diffusion-controlled kinetics, with $R_t \\sim t/\\ln t$ for unentangled chains while $t/\\ln t$ and $t^{1/2}$ regimes occur for entangled chains. Long time kinetics are 1st order and controlled by diffusion of the more dilute species to the interface: $R_t \\sim t^{1/4}$ for unentangled cases, while $R_t \\sim t^{1/4}$ and $t^{1/8}$ regimes arise for entangled systems. The final 1st order regime is governed by center of gravity diffusion, $R_t \\sim t^{1/2}$.
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.
Reaction kinetics of Cl atoms with limonene: An experimental and theoretical study
NASA Astrophysics Data System (ADS)
Dash, Manas Ranjan; Rajakumar, B.
2014-12-01
Rate coefficients for the reaction of Cl atoms with limonene (C10H16) were measured between 278-350 K and 800 Torr of N2, using the relative rate technique, with 1,3-butadiene (C4H6), n-nonane (C9H20), and 1-pentene (C5H10) as reference compounds. Cl atoms were generated by UV photolysis of oxalyl chloride ((COCl)2) at 254 nm. A gas chromatograph equipped with a flame ionization detector (GC-FID) was used for quantitative analysis of the organics. The rate coefficient for the reaction of Cl atoms with limonene at 298 K was measured to be (8.65 ± 2.44) × 10-10 cm3 molecule-1 s-1. The rate coefficient is an average value of the measurements, with two standard deviations as the quoted error, including uncertainties in the reference rate coefficients. The kinetic data obtained over the temperature range of 278-350 K were used to derive the following Arrhenius expression: k(T) = (9.75 ± 4.1) × 10-11 exp[(655 ± 133)/T] cm3 molecule-1 s-1. Theoretical kinetic calculations were also performed for the title reaction using conventional transition state theory (CTST) in combination with G3(MP2) theory between 275 and 400 K. The kinetic data obtained over the temperature range of 275-400 K were used to derive an Arrhenius expression: k(T) = (7.92 ± 0.82) × 10-13 exp[(2310 ± 34)/T] cm3 molecule-1 s-1. The addition channels contributes maximum to the total reaction and H-abstraction channels can be neglected in the range of studied pressures. The Atmospheric lifetime (?) of limonene due to its reaction with Cl atoms was estimated and concluded that the reaction with chlorine atoms can be an effective tropospheric loss pathway in the marine boundary layer and in coastal urban areas.
Mesoscopic modeling of stochastic reaction-diffusion kinetics in the subdiffusive regime
Emilie Blanc; Stefan Engblom; Andreas Hellander; Per Lötstedt
2015-03-24
Subdiffusion has been proposed as an explanation of various kinetic phenomena inside living cells. In order to fascilitate large-scale computational studies of subdiffusive chemical processes, we extend a recently suggested mesoscopic model of subdiffusion into an accurate and consistent reaction-subdiffusion computational framework. Two different possible models of chemical reaction are revealed and some basic dynamic properties are derived. In certain cases those mesoscopic models have a direct interpretation at the macroscopic level as fractional partial differential equations in a bounded time interval. Through analysis and numerical experiments we estimate the macroscopic effects of reactions under subdiffusive mixing. The models display properties observed also in experiments: for a short time interval the behavior of the diffusion and the reaction is ordinary, in an intermediate interval the behavior is anomalous, and at long times the behavior is ordinary again.
de Anna, Pietro; Dentz, Marco; Tartakovsky, Alexandre M.; Le Borgne, Tanguy
2014-07-08
We investigate the effective kinetics of a reaction front for mixing limited bimolecular reaction $A+B\\rightarrow C$ in a porous medium. While Fickian diffusion predicts a scaling of the cumulative mass produced as $M_C \\propto t^{1/2}$, we observe two time regimes in which the total product mass evolves faster then $t^{1/2}$. At early times the invading solute is organized in fingers of high velocity. Reactions take place only at the fingers boundaries whose surface grows linearly in time. We show that this configuration leads to a mass scaling $M_C \\propto t^2$. When diffusion mixes reactants and destroy these finger structures, the effective reaction rate slows down and we relate it to the longitudinal advective spreading providing $M_C \\propto \\sigma_x$. The transition time between these two regimes is characterized by the diffusion time over the transverse fingers cross section.
Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles
NASA Astrophysics Data System (ADS)
Bartling, Stephan; Pohl, Marga-Martina; Meiwes-Broer, Karl-Heinz; Barke, Ingo
2015-09-01
Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology.
Stoichiometry and kinetics of the reaction of nitrite with free chlorine in aqueous solutions
Diyamandoglu, V.; Marinas, B.J.; Selleck, R.E. )
1990-11-01
The reaction of nitrite with free chlorine in dilute aqueous solution (3.4 < pH < 11.5) was studied under continuous-flow mixing conditions. Chlorine, chloride, nitrite, and nitrate were all measured analytically. Stoichiometric balances demonstrated that nitrate was oxidized to nitrate, and chlorine was reduced to chloride, without the significant production of any other chemical species. The kinetic studies demonstrated that the reaction is very fast at neutral or acidic pH with the rate decreasing with increasing pH. The reaction was strictly bimolecular in the pH range of 9.5-11.6, whereas it was sufficiently slow to be followed with time. The reaction appears to proceed between nitrous and hypochlorous acid molecules, or HNO{sub 2} + HOCl {yields} 2H{sup +} + NO{sub 3}{sup {minus}} + Cl{sup {minus}}.
Kinetics of solid-state reactions in Ni-Zr thin films
Schwarz, R.B.; Rubin, J.B.
1991-01-01
We have studied the kinetic of the solid-state amorphizing reaction in thin film multilayers of Ni and Zr. Crystalline Ni and Zr films were deposited in ultra-high vacuum onto platinum resistance thermometer embedded in alumina. An electronic feedback circuit controls the temperature of the substrata by adjusting the power dissipated by the platinum resistors. We find that structural relaxation in the as-deposited Ni and Zr films affects the initial stages of the reaction. For long reaction times there is a discontinuous change in the reaction rate. The time to reach this transition increases with film thickness and depends exponentially on 1/T, with an apparent activation energy of 3 eV atom{sup {minus}1}. 25 refs., 9 figs.
Modeling of reaction kinetics for reactor selection in the case of L-erythrulose synthesis.
Vasic-Racki, D; Bongs, J; Schörken, U; Sprenger, G A; Liese, A
2003-03-01
To choose the most effective process design in enzyme process development it is important to find the most effective reactor mode of operation. This goal is achieved by modeling of the reaction kinetics as a tool of enzyme reaction engineering. With the example of the transketolase catalyzed L-erythrulose synthesis we demonstrate how the most effective reactor mode can be determined by kinetic simulations. This is of major importance if the biocatalyst deactivation is caused by one of the substrates as in this case by glycolaldehyde. The cascade of two membrane reactors in series with soluble enzyme is proposed as a solution for the enzyme deactivation by one of the substrates. PMID:14505172
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.
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.
A temperature dependent kinetic study of the reaction of the hydroxyl radical with CH2Br
NASA Technical Reports Server (NTRS)
Zhang, Zhengyu; Saini, Rameshwar D.; Kurylo, Michael; Huie, Robert E.
1992-01-01
Rate constants have been measured for the gas phase reaction of the hydroxyl radical (OH) with CH3Br over the temperature range 250 to 400 K. The Arrhenius expression k = (5.79 x 10 exp -12) exp(-1560/T) cu cm/molecule per sec was derived from the kinetic data. From the rate constant at 277 K, the tropospheric lifetime of CH3Br with respect to reaction with OH is estimated to be 2.2 years and the overall atmospheric lifetime to be 2.1 years.
Investigation of reaction kinetics and interfacial phase formation in Ti3Al + Nb composites
NASA Technical Reports Server (NTRS)
Wawner, F. E.; Gundel, D. B.
1992-01-01
Titanium aluminide metal matrix composites are prominent materials systems being considered for high temperature aerospace applications. One of the major problems with this material is the reactivity between existing reinforcements and the matrix after prolonged thermal exposure. This paper presents results from an investigation of reaction kinetics between Ti-14Al-21Nb (wt pct) and SCS-6 fibers and SiC fibers with surface coatings of TiB2, TiC, TiN, W, and Si. Microstructural evaluation of the reaction layers as well as matrix regions around the fibers is presented.
Kinetics of the reactions of alkyl radicals with HBr and DBr
NASA Technical Reports Server (NTRS)
Nicovich, J. M.; Van Dijk, C. A.; Kreutter, K. D.; Wine, P. H.
1991-01-01
The kinetics of the reactions CH3 + HBr, CD3 + HBr, CH3 + DBr, C2H5 + HBr, C2H5 + DBr, t-C4H9 + HBr, and t-C4H9 + DBr is studied as a function of temperature (257-430 K) and pressure (10-300 Torr of N2). Time-resolved resonance fluorescence detection of Br atom appearance following laser flash photolysis of RI was used in the experiments. Results show that the rates of all reactions increased as the temperature decreased.
Study of the Reaction Stages and Kinetics of the Europium Oxide Carbochlorination
NASA Astrophysics Data System (ADS)
Pomiro, Federico J.; Fouga, Gastón G.; Gaviría, Juan P.; Bohé, Ana E.
2015-02-01
The europium oxide (Eu2O3(s)) chlorination reaction with sucrose carbon was studied by thermogravimetry between room temperature and 1223 K (950 °C). The nonisothermal thermogravimetry showed that the reaction consists of three stages, and their stoichiometries were studied. The product of the first stage was europium oxychloride, and it showed independence of the reaction kinetics with the carbon content. Subsequently, in the second stage, the EuOCl(s) was carbochlorinated with formation of EuCl3(l) and its evaporation is observed in the third stage. The analysis by Fourier transform infrared spectroscopy of gaseous species showed that the reaction at second stage occurs with the formation of CO2(g) and CO(g). Both reactants and products were analyzed by X-ray diffraction, scanning electron microscopy and wavelength-dispersive X-ray fluorescence spectroscopy. The influence of carbon content, total flow rate, sample initial mass, chlorine partial pressure, and temperature were evaluated. The second stage kinetics was analyzed, which showed an anomalous behavior caused by generation of chlorine radicals during interaction of Cl2(g) and carbon. It was found that the reaction rate at 933 K (660 °C) was proportional to a potential function of the chlorine partial pressure whose exponent is 0.56. The conversion curves were analyzed with the Avrami-Erofeev model and it was obtained an activation energy of 154 ± 5 kJ mol-1.
Xie, Hong-Bin; Li, Chao; He, Ning; Wang, Cheng; Zhang, Shaowen; Chen, Jingwen
2014-01-01
Monoethanolamine (MEA) is a benchmark and widely utilized solvent in amine-based postcombustion CO2 capture (PCCC), a leading technology for reducing CO2 emission from fossil fuel power plants. The large-scale implementation of PCCC would lead to inevitable discharges of amines to the atmosphere. Therefore, understanding the kinetics and mechanisms of the transformation of representative amine MEA in the atmosphere is of great significance for risk assessment of the amine-based PCCC. In this study, the H-abstraction reaction of MEA with ·OH, and ensuing reactions of produced MEA-radicals, including isomerization, dissociation, and bimolecular reaction MEA-radicals+O2, were investigated by quantum chemical calculation [M06-2X/aug-cc-pVTZ//M06-2X/6-311++G(d,p)] and kinetic modeling. The calculated overall rate constant [(7.27 × 10(-11)) cm(3) molecule(-1) s(-1)] for H-abstraction is in excellent agreement with the experimental value [(7.02 ± 0.46) × 10(-11) cm(3) molecule(-1) s(-1)]. The results show that the product branching ratio of NH2CH2 · CHOH (MEA-?) (43%) is higher than that of NH2 · CHCH2OH (MEA-?) (39%), clarifying that MEA-? is not an exclusive product. On the basis of the unveiled reaction mechanisms of MEA-radicals + O2, the proton transfer reaction mass spectrometry signal (m/z 60.044), not recognized in the experiment, was identified. PMID:24438015
Gorban, Alexander N.
1980-01-01
React. Kinet. Catal. Lett., Vol. 15, No. 2,245-250 (1980) DYNAMICS OF CHEMICAL REACTIONS behavior of chemical reactions,in particular,the reasonsfor slow relaxa- tions. IIoKa3aHo, qTO 14[HdpKcaum~. Prolonged transientregimes were found experimentally in chemical reactions in greatlydifferenthomogeneous
Gunner, Marilyn
Modeling Binding Kinetics at the QA Site in Bacterial Reaction Centers Jennifer Madeo and M. R reaction centers (RCs) catalyze a series of electron-transfer reactions reducing a neutral quinone for these quinones range from 0.08 to 90 µM. For the eight neutral quinones, including duroquinone (DQ) and 2
ERIC Educational Resources Information Center
Sattsangi, Prem D.
2011-01-01
A microscale laboratory for teaching chemical kinetics utilizing the iodine clock reaction is described. Plastic pipets, 3 mL volume, are used to store and deliver precise drops of reagents and the reaction is run in a 24 well plastic tray using a total 60 drops of reagents. With this procedure, students determine the rate of reaction and the…
ERIC Educational Resources Information Center
Lombardo, Anthony
1982-01-01
Described is an advanced undergraduate kinetics experiment using buffer dilutions to determine spontaneous rate, catalyzed rate, and reaction order. The reaction utilized is hydrolysis of p-nitro-phenyl acetate in presence of imidazole, which has been shown to enhance rate of the reaction. (Author/JN)
Kinetics of lime/bentonite pozzolanic reactions at 20 and 50 °C: Batch tests and modeling
De Windt, Laurent; Deneele, Dimitri; Maubec, Nicolas
2014-05-01
The effects of duration (1–100 days) and temperature (20 and 50 °C) were assessed from batch tests for Ca-bentonite mixed with 10 wt.% lime. The pozzolanic processes were monitored over time by {sup 29}Si NMR (Cement Concr. Res. 42, 2012), TGA-DTA, XRD and chemical analysis. Modeling considered kinetics and thermodynamics of mineralogical transformations and cation exchange. Kinetic laws were dependent on pH and temperature (Arrhenius energy). Lime hydration occurs within hours, modifying the bentonite exchangeable population and increasing the pH. These alkaline conditions initiate the pozzolanic reactions in a second stage. The rate-limiting step is the dissolution kinetics of the bentonite minerals, i.e. a relatively fast and total consumption of cristobalite in parallel to a long-term slower dissolution of montmorillonite. First C–S–H and then C–A–S–H are formed consequently. Temperature speeds up the pozzolanic reaction kinetics by a factor 5 from 20 to 50 °C, corresponding to an apparent activation energy of 40–50 kJ/mol.
Sankaran, R.; Grout, R.
2012-01-01
Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high-performance code targeted for GPU accelerators.
Grout, Ray W
2012-01-01
Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high- performance code targeted for GPU accelerators.
Berry, Hugues
2002-01-01
Conventional equations for enzyme kinetics are based on mass-action laws, that may fail in low-dimensional and disordered media such as biological membranes. We present Monte Carlo simulations of an isolated Michaelis-Menten enzyme reaction on two-dimensional lattices with varying obstacle densities, as models of biological membranes. The model predicts that, as a result of anomalous diffusion on these low-dimensional media, the kinetics are of the fractal type. Consequently, the conventional equations for enzyme kinetics fail to describe the reaction. In particular, we show that the quasi-stationary-state assumption can hardly be retained in these conditions. Moreover, the fractal characteristics of the kinetics are increasingly pronounced as obstacle density and initial substrate concentration increase. The simulations indicate that these two influences are mainly additive. Finally, the simulations show pronounced S-P segregation over the lattice at obstacle densities compatible with in vivo conditions. This phenomenon could be a source of spatial self organization in biological membranes. PMID:12324410
Chemical Kinetic Reaction Mechanisms for Combustion of Hydrocarbon and Other Types of Chemical Fuels
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.
Non-meanfield deterministic limits in chemical reaction kinetics far from equilibrium
R. E. Lee DeVille; Cyrill B. Muratov; Eric Vanden-Eijnden
2005-12-25
A general mechanism is proposed by which small intrinsic fluctuations in a system far from equilibrium can result in nearly deterministic dynamical behaviors which are markedly distinct from those realized in the meanfield limit. The mechanism is demonstrated for the kinetic Monte-Carlo version of the Schnakenberg reaction where we identified a scaling limit in which the global deterministic bifurcation picture is fundamentally altered by fluctuations. Numerical simulations of the model are found to be in quantitative agreement with theoretical predictions.
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)
SECOND{ORDER AND HIGHER{ORDER PERTURBATIONS OF TRAVEL TIME IN ISOTROPIC AND ANISOTROPIC MEDIA
Cerveny, Vlastislav
SECOND{ORDER AND HIGHER{ORDER PERTURBATIONS OF TRAVEL TIME IN ISOTROPIC AND ANISOTROPIC MEDIA Lud derivatives of travel time with respect to model parameters are re- ferred to as perturbations. Explicit equations for the second{order and higher{order perturbations of travel time in both isotropic
Grid travel{time tracing: second{order method for the rst arrivals in smooth media
Cerveny, Vlastislav
Grid travel{time tracing: second{order method for the #12;rst arrivals in smooth media Lud#20;ek{arrival travel times on a rectan- gular grid of points is proposed. The new proposed method is of second{order accuracy. This means that the error of the calculated travel time is proportional to the second power
Grid travel{time tracing: second{order method for the rst arrivals in smooth media *
Cerveny, Vlastislav
Grid travel{time tracing: second{order method for the #12;rst arrivals in smooth media * Lud#20;ek the #12;rst{arrival travel times on a rectangular grid of points is proposed. Whereas the former "#12;nite is of the second{order accu- racy. It means that the relative propagation{velocity error of calculated travel time
Minimum Time Control of A Second-Order System Zhaolong Shen and Sean B. Andersson
Minimum Time Control of A Second-Order System Zhaolong Shen and Sean B. Andersson Department algorithm for determining the switching time and final time for the minimum-time control of a second- order, then the switching time and final time are related through an affine mapping. This mapping is determined
Second-order accurate particle image velocimetry S. T. Wereley, C. D. Meinhart
Meinhart, Carl
Second-order accurate particle image velocimetry S. T. Wereley, C. D. Meinhart Abstract An adaptive, second-order accurate particle image velocimetry (PIV) technique is presented. The technique uses two of particle image velocimetry (PIV), researchers have realized that PIV algorithms do not generally make
Adaptation of Log Domain Second Order Filters Implemented by Floating Gate MOSFETs
Maryland at College Park, University of
Adaptation of Log Domain Second Order Filters Implemented by Floating Gate MOSFETs Yiming Zhai, MD 20742, USA ymzhai, pabshire@umd.edu Abstract--We describe an adaptive log domain second order transistors to realize on-line learning of quality factor and time constant. We use adaptive dynamical system
International Association for Cryptologic Research (IACR)
Gold functions Ruchi Gode and Sugata Gangopadhyay Department of Mathematics Indian Institute are concatenations of quadratic Gold functions. A lower bound of second-order nonlinearities of these functions Gold functions. A lower bound of second-order nonlinearities of these functions is obtained. This bound
Kinetics of trans-cis isomerization in azobenzene dimers at an air-water interface
Kumar, Bharat; Suresh, K. A.
2009-08-15
We have studied the kinetics of trans to cis isomerization under the illumination of ultraviolet light, in the Langmuir monolayer of mesogenic azobenzene dimer, bis-[5-(4{sup '}-n-dodecyloxy benzoyloxy)-2-(4{sup ''}-methylphenylazo)phenyl] adipate, at an air-water interface. We find that the trans to cis isomerization reaction of the molecules in the monolayer shows deviation from the first-order kinetics unlike those reported on Langmuir monolayers of azobenzene molecules. We attribute the deviation from first-order kinetics to the simultaneous photoisomerization of trans isomers to form cis isomers and the reverse thermal isomerization of cis isomers to form trans isomers. Our analysis of the rate of change of mole fraction of trans isomers to form cis isomers indicates a first-order kinetics for trans to cis photoisomerization reaction and a second-order kinetics for cis to trans thermal isomerization reaction. This second-order kinetics mechanism is similar to the Lindemann-Hinshelwood mechanism for the unimolecular reactions at low concentration of reactants. The formation of the activated cis isomer by collisions is a slow process as compared to the decay of the activated cis isomer to trans isomer in the liquid expanded phase. This results in the second-order kinetics for the thermal isomerization of cis isomers.
Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K.
1999-08-01
The authors are developing a new catalyst-free process of cellulose decomposition in supercritical water. In their initial study on the cellulose decomposition in supercritical water, the main products of cellulose decomposition were found to be oligomers of glucose (cellobiose, cellotriose, etc.) and glucose at short residence times (400 C, 25 MPa, 0.05 s). The kinetics of glucose at these conditions can be useful in understanding the reaction pathways of cellulose. Experiments were performed on the products of glucose decomposition at short residence times to elucidate the reaction pathways and evaluate kinetics of glucose and fructose decomposition in sub- and supercritical water. The conditions were a temperature of 300--400 C and pressure of 25--40 MPa for extremely short residence times between 0.02 and 2 s. The products of glucose decomposition were fructose, a product of isomerization, 1,6-anhydroglucose, a product of dehydration, and erythrose and glyceraldehyde, products of C-C bond cleavage. Fructose underwent reactions similar to glucose except that it did not form 1,6-anhydroglucose and isomerization to glucose is negligible. The mechanism for the products formed from C-C bond cleavage could be explained by reverse aldol condensation and the double-bond rule of the respective enediols formed during the Lobry de Bruyn Alberda van Ekenstein transformation. The differential equations resulting from the proposed pathways were fit to experimental results to obtain the kinetic rate constants.
Refolded scFv Antibody Fragment against Myoglobin Shows Rapid Reaction Kinetics
Song, Hyung-Nam; Jang, Jun-Hyuck; Kim, Young-Wan; Kim, Dong-Hyung; Park, Sung-Goo; Lee, Myung Kyu; Paek, Se-Hwan; Woo, Eui-Jeon
2014-01-01
Myoglobin is one of the early biomarkers for acute myocardial infarction. Recently, we have screened an antibody with unique rapid reaction kinetics toward human myoglobin antigen. Antibodies with rapid reaction kinetics are thought to be an early IgG form produced during early stage of in vivo immunization. We produced a recombinant scFv fragment for the premature antibody from Escherichia coli using refolding technology. The scFv gene was constructed by connection of the VH–VL sequence with a (Gly4Ser)3 linker. The scFv fragment without the pelB leader sequence was expressed at a high level, but the solubility was extremely low. A high concentration of 8 M urea was used for denaturation. The dilution refolding process in the presence of arginine and the redox reagents GSH and GSSH successfully produced a soluble scFv protein. The resultant refolded scFv protein showed association and dissociation values of 9.32 × 10?4 M?1·s?1 and 6.29 × 10?3 s?1, respectively, with an affinity value exceeding 107 M?1 (kon/koff), maintaining the original rapid reaction kinetics of the premature antibody. The refolded scFv could provide a platform for protein engineering for the clinical application for diagnosis of heart disease and the development of a continuous biosensor. PMID:25530617
The Role of Comprehensive Detailed Chemical Kinetic Reaction Mechanisms in Combustion Research
Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M
2008-07-16
Recent developments by the authors in the field of comprehensive detailed chemical kinetic reaction mechanisms for hydrocarbon fuels are reviewed. Examples are given of how these mechanisms provide fundamental chemical insights into a range of combustion applications. Practical combustion consists primarily of chemical heat release from reactions between a fuel and an oxidizer, and computer simulations of practical combustion systems have become an essential tool of combustion research (Westbrook et al., 2005). At the heart of most combustion simulations, the chemical kinetic submodel frequently is the most detailed, complex and computationally costly part of a system model. Historically, the chemical submodel equations are solved using time-implicit numerical algorithms, due to the extreme stiffness of the coupled rate equations, with a computational cost that varies roughly with the cube of the number of chemical species in the model. While early mechanisms (c. 1980) for apparently simple fuels such as methane (Warnatz, 1980) or methanol (Westbrook and Dryer, 1979) included perhaps 25 species, current detailed mechanisms for much larger, more complex fuels such as hexadecane (Fournet et al., 2001; Ristori et al., 2001; Westbrook et al., 2008) or methyl ester methyl decanoate (Herbinet et al., 2008) have as many as 2000 or even 3000 species. Rapid growth in capabilities of modern computers has been an essential feature in this rapid growth in the size and complexity of chemical kinetic reaction mechanisms.
Splitting of CO2 by vibrational excitation in non-equilibrium plasmas: a reaction kinetics model
NASA Astrophysics Data System (ADS)
Kozák, Tomáš; Bogaerts, Annemie
2014-08-01
We present a zero-dimensional kinetic model of CO2 splitting in non-equilibrium plasmas. The model includes a description of the CO2 vibrational kinetics (25 vibrational levels up to the dissociation limit of the molecule), taking into account state-specific VT and VV relaxation reactions and the effect of vibrational excitation on other chemical reactions. The model is applied to study the reaction kinetics of CO2 splitting in an atmospheric-pressure dielectric barrier discharge (DBD) and in a moderate-pressure microwave discharge. The model results are in qualitative agreement with published experimental works. We show that the CO2 conversion and its energy efficiency are very different in these two types of discharges, which reflects the important dissociation mechanisms involved. In the microwave discharge, excitation of the vibrational levels promotes efficient dissociation when the specific energy input is higher than a critical value (2.0 eV/molecule under the conditions examined). The calculated energy efficiency of the process has a maximum of 23%. In the DBD, vibrationally excited levels do not contribute significantly to the dissociation of CO2 and the calculated energy efficiency of the process is much lower (5%).
Becerra, Rosa; Cannady, J Pat; Pfrang, Christian; Walsh, Robin
2015-11-19
Time-resolved kinetics studies of silylene, SiH2, generated by laser flash photolysis of phenylsilane, were performed to obtain rate coefficients for its bimolecular reaction with 2,5-dihydrofuran (2,5-DHF). The reaction was studied in the gas phase over the pressure range of 1-100 Torr in SF6 bath gas, at five temperatures in the range of 296-598 K. The reaction showed pressure dependences characteristic of a third body assisted association. The second-order rate coefficients obtained by Rice-Ramsperger-Kassel-Marcus (RRKM)-assisted extrapolation to the high-pressure limit at each temperature fitted the following Arrhenius equation where the error limits are single standard deviations: log(k/cm(3) molecule(-1) s(-1)) = (-9.96 ± 0.08) + (3.38 ± 0.62 kJ mol(-1))/RT ln 10. End-product analysis revealed no GC-identifiable product. Quantum chemical (ab initio) calculations indicate that reaction of SiH2 with 2,5-DHF can occur at both the double bond (to form a silirane) and the O atom (to form a donor-acceptor, zwitterionic complex) via barrierless processes. Further possible reaction steps were explored, of which the only viable one appears to be decomposition of the O-complex to give 1,3-butadiene + silanone, although isomerization of the silirane cannot be completely ruled out. The potential energy surface for SiH2 + 2,5-DHF is consistent with that of SiH2 with Me2O, and with that of SiH2 with cis-but-2-ene, the simplest reference reactions. RRKM calculations incorporating reaction at both ?- and O atom sites, can be made to fit the experimental rate coefficient pressure dependence curves at 296-476 K, giving values for k(?)(?) and k(?)(O) that indicate the latter is larger in magnitude at all temperatures, in contrast to values from individual model reactions. This unexpected result suggests that, in 2,5-DHF with its two different reaction sites, the O atom exerts the more pronounced electrophilic attraction on the approaching silylene. Arrhenius parameters for the individual pathways were obtained. The lack of a fit at 598 K is consistent with decomposition of the O-complex to give 1,3-butadiene + silanone. PMID:26487151
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.
Effects of Second-Order Hydrodynamics on a Semisubmersible Floating Offshore Wind Turbine: Preprint
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.
The effects of second-order hydrodynamics on a semisubmersible floating offshore wind turbine
NASA Astrophysics Data System (ADS)
Bayati, I.; Jonkman, J.; Robertson, A.; Platt, A.
2014-06-01
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 a floating 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 Maritime Research Institute Netherlands (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 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 was applied to the Offshore Code Comparison Collaboration Continuation OC4-DeepCwind semisubmersible platform, supporting the National Renewable Energy Laboratory's 5-MW baseline wind turbine. In this paper, the loads and response of the system caused by the second-order hydrodynamics are analysed and compared to the 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.
Wang Haifeng Popov, Pavel P.; Pope, Stephen B.
2010-03-01
We study a class of methods for the numerical solution of the system of stochastic differential equations (SDEs) that arises in the modeling of turbulent combustion, specifically in the Monte Carlo particle method for the solution of the model equations for the composition probability density function (PDF) and the filtered density function (FDF). This system consists of an SDE for particle position and a random differential equation for particle composition. The numerical methods considered advance the solution in time with (weak) second-order accuracy with respect to the time step size. The four primary contributions of the paper are: (i) establishing that the coefficients in the particle equations can be frozen at the mid-time (while preserving second-order accuracy), (ii) examining the performance of three existing schemes for integrating the SDEs, (iii) developing and evaluating different splitting schemes (which treat particle motion, reaction and mixing on different sub-steps), and (iv) developing the method of manufactured solutions (MMS) to assess the convergence of Monte Carlo particle methods. Tests using MMS confirm the second-order accuracy of the schemes. In general, the use of frozen coefficients reduces the numerical errors. Otherwise no significant differences are observed in the performance of the different SDE schemes and splitting schemes.
Kinetic study of the reaction of chlorine atoms with hydroxyacetone in gas-phase
NASA Astrophysics Data System (ADS)
Stoeffler, Clara; Joly, Lilian; Durry, Georges; Cousin, Julien; Dumelié, Nicolas; Bruyant, Aurélien; Roth, Estelle; Chakir, Abdelkhaleq
2013-12-01
In this letter the kinetics of the reaction of hydroxyacetone CH3C(O)CH2OH with Cl atoms is investigated using the relative rate technique. Experiments are carried out in a 65 L multipass photoreactor in the temperature range of 281-350 K. A mid-infrared spectrometer based on a quantum cascade laser in external cavity emitting at 9.5 ?m is used to analyze the reactants. The determined rate coefficient for the investigated reaction is (1.7 ± 0.3) × 10-11exp(381.5 ± 57.3/T). The results are presented and discussed in terms of precision and compared with those obtained previously. The impact of Cl atoms on the atmospheric life time of hydroxyacetone is also discussed. Developing analytical techniques to quantify this compound in the atmosphere. Several methods of measurement have been used including the technique of proton transfer mass spectrometry (PTR-MS) [2] and derivatization with a chemical agent such as dinitrophenylhydrazine (DNPH) [3,4] followed by GC/MS or HPLC analyses. The HA amount in the troposphere was found to be in the order of a few hundred parts per trillion by volume [4], Performing laboratory experiments in order to study the HA reactivity with atmospheric oxidants. The first study on the kinetic of the reaction between OH radicals and HA was made by Dagault et al. [5] whose work was performed at room temperature by flash photolysis-resonance fluorescence. The determined rate constant implies a lifetime of a few days for HA relative to oxidation by OH radicals. Orlando et al. performed mechanistic and kinetics studies of the reaction of HA with OH radicals and Cl atoms at room temperature using a relative method [6]. Products detection was performed using FTIR spectroscopy. Moreover, these authors studied the photolysis of HA to determine its quantum yield and UV absorption spectrum. These studies showed that HA is principally removed from the atmosphere by reaction with OH radicals. Kinetic studies of the reaction of OH radicals with HA as a function of temperature (233-298 K) were performed by Dillon et al. [7]. An experimental (laser photolysis/FIL) and theoretical approach (quantum calculation) were realized. This study showed that the oxidation of HA by OH-radicals has a negative temperature coefficient which is explained by an intermediate complex formation. Another study as a function of temperature was conducted by Butkovskaya et al. using the technique of a turbulent flow reactor coupled with a mass spectrometer chemical ionization [8]. This work was purely mechanistic and it shows that the mechanism of this reaction changes with temperature: a temperature increase favors the production yields of methanoic and ethanoic acids and reduces the formation yield of methylglyoxal [8]. Our work is motivated by the fact that the kinetic studies of the reaction of HA with chlorine radicals are rare in comparison with the kinetic studies of the reaction of HA with OH radicals. So far, only one such kinetic study is reported in the literature. It has been carried out by Orlando et al. at 294 K [6]. To the best of our knowledge, this reaction has not yet been studied as a function of temperature. Therefore, to enrich kinetic data concerning this compound, the study of HA with Cl atoms reaction as a function of temperature has been undertaken. Experiments are carried out using the relative technique in a simulation chamber coupled with an infrared Fourier transform (FTIR) spectrometer and a quantum cascade laser in external cavity (ECQCL) at 1 bar with the temperature ranging 277-350 K. Using both FTIR and ECQCL techniques allows comparing the measurements sensitivity and improving the kinetic precision determination. The FTIR spectroscopy is widely used to perform kinetic measurements whereas the ECQCL spectrometer is quite original in kinetic studies. Laser spectrometry indeed presents advantages such as high sensitivity, high resolution, and fast acquisition time compared to the FTIR spectrometer. The ECQCL principle is based on a quantum cascade laser coupled with an external cavity that includes a d
Nguyen, H.D.
1991-11-01
Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a glass like'' material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.
Nguyen, H.D.
1991-11-01
Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a ``glass like`` material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.
A First-Passage Kinetic Monte Carlo method for reaction–drift–diffusion processes
Mauro, Ava J.; Sigurdsson, Jon Karl; Shrake, Justin; Atzberger, Paul J.; Isaacson, Samuel A.
2014-02-15
Stochastic reaction–diffusion models are now a popular tool for studying physical systems in which both the explicit diffusion of molecules and noise in the chemical reaction process play important roles. The Smoluchowski diffusion-limited reaction model (SDLR) is one of several that have been used to study biological systems. Exact realizations of the underlying stochastic processes described by the SDLR model can be generated by the recently proposed First-Passage Kinetic Monte Carlo (FPKMC) method. This exactness relies on sampling analytical solutions to one and two-body diffusion equations in simplified protective domains. In this work we extend the FPKMC to allow for drift arising from fixed, background potentials. As the corresponding Fokker–Planck equations that describe the motion of each molecule can no longer be solved analytically, we develop a hybrid method that discretizes the protective domains. The discretization is chosen so that the drift–diffusion of each molecule within its protective domain is approximated by a continuous-time random walk on a lattice. New lattices are defined dynamically as the protective domains are updated, hence we will refer to our method as Dynamic Lattice FPKMC or DL-FPKMC. We focus primarily on the one-dimensional case in this manuscript, and demonstrate the numerical convergence and accuracy of our method in this case for both smooth and discontinuous potentials. We also present applications of our method, which illustrate the impact of drift on reaction kinetics.
Tensor factorizations of local second-order Møller-Plesset theory
NASA Astrophysics Data System (ADS)
Yang, Jun; Kurashige, Yuki; Manby, Frederick R.; Chan, Garnet K. L.
2011-01-01
Efficient electronic structure methods can be built around efficient tensor representations of the wavefunction. Here we first describe a general view of tensor factorization for the compact representation of electronic wavefunctions. Next, we use this language to construct a low-complexity representation of the doubles amplitudes in local second-order Møller-Plesset perturbation theory. We introduce two approximations—the direct orbital-specific virtual approximation and the full orbital-specific virtual approximation. In these approximations, each occupied orbital is associated with a small set of correlating virtual orbitals. Conceptually, the representation lies between the projected atomic orbital representation in Pulay-Saebø local correlation theories and pair natural orbital correlation theories. We have tested the orbital-specific virtual approximations on a variety of systems and properties including total energies, reaction energies, and potential energy curves. Compared to the Pulay-Saebø ansatz, we find that these approximations exhibit favorable accuracy and computational times while yielding smooth potential energy curves.
Tensor factorizations of local second-order Møller-Plesset theory.
Yang, Jun; Kurashige, Yuki; Manby, Frederick R; Chan, Garnet K L
2011-01-28
Efficient electronic structure methods can be built around efficient tensor representations of the wavefunction. Here we first describe a general view of tensor factorization for the compact representation of electronic wavefunctions. Next, we use this language to construct a low-complexity representation of the doubles amplitudes in local second-order Møller-Plesset perturbation theory. We introduce two approximations--the direct orbital-specific virtual approximation and the full orbital-specific virtual approximation. In these approximations, each occupied orbital is associated with a small set of correlating virtual orbitals. Conceptually, the representation lies between the projected atomic orbital representation in Pulay-Saebø local correlation theories and pair natural orbital correlation theories. We have tested the orbital-specific virtual approximations on a variety of systems and properties including total energies, reaction energies, and potential energy curves. Compared to the Pulay-Saebø ansatz, we find that these approximations exhibit favorable accuracy and computational times while yielding smooth potential energy curves. PMID:21280703
On the theory of the CO +OH reaction, including H and C kinetic isotope effects
NASA Astrophysics Data System (ADS)
Chen, Wei-Chen; Marcus, R. A.
2005-09-01
The effect of pressure, temperature, H /D isotopes, and C isotopes on the kinetics of the OH +CO reaction are investigated using Rice-Ramsperger-Kassel-Marcus theory. Pressure effects are treated with a step-ladder plus steady-state model and tunneling effects are included. New features include a treatment of the C isotope effect and a proposed nonstatistical effect in the reaction. The latter was prompted by existing kinetic results and molecular-beam data of Simons and co-workers [J. Phys. Chem. A 102, 9559 (1998); J. Chem. Phys. 112, 4557 (2000); 113, 3173 (2000)] on incomplete intramolecular energy transfer to the highest vibrational frequency mode in HOCO*. In treating the many kinetic properties two small customary vertical adjustments of the barriers of the two transition states were made. The resulting calculations show reasonable agreement with the experimental data on (1) the pressure and temperature dependence of the H /D effect, (2) the pressure-dependent C12/C13 isotope effect, (3) the strong non-Arrhenius behavior observed at low temperatures, (4) the high-temperature data, and (5) the pressure dependence of rate constants in various bath gases. The kinetic carbon isotopic effect is usually less than 10 per mil. A striking consequence of the nonstatistical assumption is the removal of a major discrepancy in a plot of the kOH +CO/kOD +CO ratio versus pressure. A prediction is made for the temperature dependence of the OD +CO reaction in the low-pressure limit at low temperatures.
La O', Gerardo Jose Cordova
Oxygen reduction reaction (ORR) kinetics was investigated on dense La?.?Sr?.?MnO? microelectrodes as a function of temperature and microelectrode thickness using electrochemical impedance spectroscopy. The surface oxygen ...
Reaction of anthracene with CH radicals: an experimental study of the kinetics between 58 and 470 K.
Goulay, Fabien; Rebrion-Rowe, Christiane; Biennier, Ludovic; Le Picard, Sébastien D; Canosa, André; Rowe, Bertrand R
2006-03-01
The rate coefficient of the reaction of the methylidine radical CH with anthracene has been studied over a wide temperature range (58-470 K) in a dedicated "Cinétique de Réaction en Ecoulement Supersonique Uniforme" (Reaction Kinetics in Uniform Supersonic Flow) apparatus. The reaction exhibits a slight positive temperature dependence, which can be fitted to the expression k(T) = (3.32 +/- 1.00) x 10(-10)(T/298)((0.46+/-0.14)) cm3 molecule(-1) s(-1). Even at the lowest temperature, the reaction remains very fast indicating that the kinetics are probably driven by a capture process. PMID:16509636
Surfkin: A program to solve transient and steady state heterogeneous reaction kinetics
COLTRIN,MICHAEL E.; WIXOM,RYAN R.; DANDY,DAVID S.
2000-05-01
Heterogeneous chemical reactions occurring at a gas/surface interface are fundamental in a variety of important applications, such as combustion, catalysis, chemical vapor deposition and plasma processing. Detailed simulation of these processes may involve complex, coupled fluid flow, heat transfer, gas-phase chemistry, in addition to heterogeneous reaction chemistry. This report documents the Surfkin program, which simulates the kinetics of heterogeneous chemical reactions. The program is designed for use with the Chemkin and Surface Chemkin (heterogeneous chemistry) programs. It calculates time-dependent or steady state surface site fractions and bulk-species production/destruction rates. The surface temperature may be specified as a function of time to simulate a temperature-programmed desorption experiment, for example. This report serves as a user's manual for the program, explaining the required input and format of the output. Two detailed example problems are included to further illustrate the use of this program.
Modelling the destruction of Escherichia coli on the base of reaction kinetics.
Reichart, O
1994-11-01
Assuming that the inactivation of microorganisms is due to a chemical reaction between a 'critical structure' of the cell and another reactant molecule, mathematical models of the reaction rates can be applied to the process. Considering the stoichiometric equation of the chemical reaction, the thermal death or disinfection of microbes can be described by an extension of the Eyring's model. The extended model is applicable not only to heat inactivation, but also to disinfection kinetics and to the effect of pH. Taking into account the effect of the water activity on heat destruction, the extended model has been modified empirically and fitted to experimental data on the heat destruction of Escherichia coli. PMID:7873343
Hammes-Schiffer, Sharon
, and Kinetic Isotope Effects He´le`ne Decornez and Sharon Hammes-Schiffer* Department of Chemistry, 152 Da isotope effects for proton-coupled electron transfer (PCET) reactions. These studies are based region. The kinetic isotope effects are predicted to increase as the probability of the EPT mechanism
NASA Astrophysics Data System (ADS)
Basilevsky, M. V.; Odinokov, A. V.; Titov, S. V.; Mitina, E. A.
2013-12-01
The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ?0 = ??0/kBT where ?0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (?0 < 1 - 3) and for low (?0 ? 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T ? 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.
Basilevsky, M. V.; Mitina, E. A.; Odinokov, A. V.; National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow ; Titov, S. V.
2013-12-21
The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ?{sub 0}=??{sub 0}/k{sub B}T where ?{sub 0} is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (?{sub 0} < 1 ? 3) and for low (?{sub 0}? 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T? 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.
Borrelli, Raffaele; Peluso, Andrea
2015-02-10
An analytical expression for the population dynamics of electronic radiationless transitions has been derived from the second order expansion of the quantum evolution operator in the Liouville space and the cumulant theory. The expression includes the effect of both normal mode displacements and Duschinsky rotations and allows to take into account both equilibrium and nonequilibrium initial conditions. The methodology has been applied to model the electron-transfer process between the accessory bacteriochlorophyll and the bacteriopheophytine in bacterial reactions centers, providing a rate in good agreement with experimental findings. PMID:26580904
Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction
NASA Technical Reports Server (NTRS)
Kreutter, K. D.; Nicovich, J. M.; Wine, P. H.
1997-01-01
A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.
On the kinetics of the Al13-+Cl2 reaction: Cluster degradation in consecutive steps
NASA Astrophysics Data System (ADS)
Olzmann, Matthias; Burgert, Ralf; Schnöckel, Hansgeorg
2009-11-01
The kinetics of the reaction system initiated by the Al13-+Cl2 reaction was experimentally studied in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The Al13- clusters were produced by laser desorption/ionization of LiAlH4, then transferred into the ICR cell, cooled by collisions with Ar, and exposed to an excess of Cl2 with a concentration of ˜108 cm-3. Relative concentration-time profiles of Aln- clusters with n =13, 11, 9, and 7 as well as profiles of Cl- ions have been recorded. Other ionic species, besides traces of Al12Cl-, were not found, which indicates a double-step degradation mechanism via the odd-numbered Aln- clusters. From a kinetic analysis of the experimental results, a rate coefficient of (5±2)×10-10 cm3 s-1 for the Al13-+Cl2 reaction was obtained. Furthermore, it is inferred from a simultaneous fit of all concentration-time profiles that the Aln-+Cl2 reactions for n =13, 11, 9, and 7 occur with rate coefficients near the Langevin limit in the range kbim˜(5±4)×10-10 cm3 s-1. The branching ratios between the Aln -2--producing and Cl--producing channels of a given cluster AlnCl2- indicate an increasing contribution of the Cl--producing channels with decreasing cluster size. Statistical rate theory calculations on the basis of molecular data from quantum chemical calculations show that the experimental Aln- profiles are compatible with a sequence of association-elimination reactions proceeding via the formation of highly excited AlnCl2- adducts followed by a sequential elimination of two AlCl molecules. Rate coefficients for these reactions were calculated, and the production of Cl- was shown probably not to proceed via these AlnCl2- intermediates.
Low-temperature Kinetic Studies of OH Radical Reactions Relevant to Planetary Atmospheres
NASA Astrophysics Data System (ADS)
Townsend, T. M.; Antiñolo, M.; Ballesteros, B.; Jimenez, E.; Canosa, A.
2011-05-01
In the solar system, the temperature (T) of the atmosphere of giant planets or their satellites is only several tens of Kelvin (K). The temperature of the tropopause of Titan (satellite of Saturn) and the surface of Mars is 70 K and 210 K, respectively. In the Earth's atmosphere, T decreases from 298 K (surface) to 210 K close to the T-inversion region (tropopause). The principal oxidants in the Earth's lower atmosphere are ozone, the hydroxyl (OH) radical and hydrogen peroxide. A number of critical atmospheric chemical problems depend on the Earth's oxidising capacity, which is essentially the global burden of these oxidants. In the interstellar clouds and circumstellar envelopes, OH radicals have also been detected. As the chemistry of atmospheres is highly influenced by temperature, the knowledge of the T-dependence of the rate coefficients for OH-reactions (k) is the key to understanding the underlying molecular mechanisms. In general, these reactions take place on a short temporal scale. Therefore, a detection technique with high temporal resolution is required. Measurements of k at low temperatures can be achieved by maintaining a thermalised environment using either cryogenic cooling (T>200 K) or supersonic gas expansion with a Laval nozzle (several tens of K). The pulsed laser photolysis technique coupled with laser induced fluorescence detection has been widely used in our laboratory to determine the rate coefficients of OH-reactions with different volatile organic compounds, such as alcohols (1), saturated and unsaturated aliphatic aldehydes (2), linear ketones (3), as a function of temperature (260 350 K). An experimental system based on the CRESU (Cinetique de Reaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique is currently under construction. This technique will allow the performance of kinetic studies of OH-reactions of astrophysical interest at temperatures lower than 200 K.
Experimental study of the reactions of limonene with OH and OD radicals: kinetics and products.
Braure, Tristan; Bedjanian, Yuri; Romanias, Manolis N; Morin, Julien; Riffault, Véronique; Tomas, Alexandre; Coddeville, Patrice
2014-10-01
The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 ? products (1), OD + C10H16 ? products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K. PMID:25211148
First and second order approximations to stage numbers in multicomponent enrichment cascades
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)
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.
[Population Dynamics of Cancer: a Model of Second Order Phase Transition].
Soukhovolsky, V G; Ivanova, Y D; Shulman, K; Mazharov, V F; Tarasova, I V; Tarasova, O V; Khlebopros, R G
2015-01-01
The paper deals with an approach to the description of the age and temporal dynamics of cancer, based on the model describing the dynamics of the age of cancer as a second order phase transition. This approach is widely used for studying physical systems. This model of cancer development as second order phase transitions is in a good agreement with medical statistics. The cancer incidence dynamics is described only with two free parameters, easily verified according to statistics and well interpreted. The applicability of the second order phase transition model for description of a non-physical system defines the universal nature of the processes occurring during phase transitions. PMID:26394478
First and Second Order Necessary Conditions for Stochastic Optimal Control Problems
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.
The Quantum-Kinetic Chemical Reaction Model for Navier-Stokes Codes
NASA Astrophysics Data System (ADS)
Gallis, Michael A.; Wagnild, Ross M.; Torczynski, John R.
2013-11-01
The Quantum-Kinetic chemical reaction model of Bird is formulated as a non-equilibrium chemical reaction model for Navier-Stokes codes. The model is based solely on thermophysical, molecular-level information and is capable of reproducing measured equilibrium reaction rates without using any experimentally measured reaction-rate information. The model recognizes the principal role of vibrational energy in overcoming the reaction energy threshold. The effect of rotational non-equilibrium is introduced as a perturbation to the effect of vibrational non-equilibrium. Since the model uses only molecular-level properties, it is inherently able to predict reaction rates for arbitrary non-equilibrium conditions. This ability is demonstrated in the context of both Navier-Stokes and DSMC codes. 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.
Zhang, Jun; Yang, Y Isaac; Yang, Lijiang; Gao, Yi Qin
2015-11-12
High potential energy barriers and engagement of solvent coordinates set challenges for in silico studies of chemical reactions, and one is quite commonly limited to study reactions along predefined reaction coordinate(s). A systematic protocol, QM/MM MD simulations using enhanced sampling of reactive trajectories (ESoRT), is established to quantitatively study chemical transitions in complex systems. A number of trajectories for Claisen rearrangement in water and toluene were collected and analyzed, respectively. Evidence was found that the bond making and breaking during this reaction are concerted processes in solutions, preferentially through a chairlike configuration. Water plays an important dynamic role that helps stabilize the transition sate, and the dipole-dipole interaction between water and the solute also lowers the transition barrier. The calculated rate coefficient is consistent with the experimental measurement. Compared with water, the reaction pathway in toluene is "narrower" and the reaction rate is slower by almost three orders of magnitude due to the absence of proper interactions to stabilize the transition state. This study suggests that the "in-water" nature of the Claisen rearrangement in aqueous solution influences its thermodynamics, kinetics, as well as dynamics. PMID:26485567
Precipitation kinetics option for the EQ6 geochemical reaction path code
Delany, J.M.; Puigdomenech, I.; Wolery, T.J.
1986-05-19
The EQ6 reaction path code has been modified to permit the modeling of mineral growth kinetics. This modeling option complements a pre-existing capability that allows mineral dissolution kinetics to be calculated. Before this option was added, mineral precipitation in EQ6 was required to follow instantaneous saturation equilibrium. A review of the rate laws pertaining to mineral precipitation and dissolution has led to several rate laws for precipitation, paralleling those for dissolution being programmed into EQ6. Included are rate laws for transition-state theory expressions and activity-term expressions. To use the modeling option, EQ6 users must choose an appropriate rate law and provide the necessary constants for each kinetically governed reaction in the input file. Additional rate laws can be added with little difficulty. We have exercised the new capability for some relatively simple cases and partially verified it against closed-forms solutions for cases of precipitation and recrystallization of pure silica phases. This capability facilitates the extrapolation and testing of rate laws in systems where precipitation is important, including the case of mineral transformations involving coupled dissolution and precipitation. It also permits more realistic simulation modeling of relatively short-term rock/water interaction experiments and of long-term interactions that are inaccessible by experiment.
Ticianelli, E.A.; Mukerjee, S.; McBreen, J.; Adzic, G.D.; Johnson, J.R.; Reilly, J.J.
1998-12-31
This was a study of electrode degradation mechanisms and the reaction kinetics of LaNi{sub 4.7}Sn{sub 0.3}, La{sub (1{minus}x)} Y{sub x}Ni{sub 4.7}Sn{sub 0.3} (x = 0.1, 0.2, and 0.3) and La{sub 0.7}Y{sub 0.3}Ni{sub 4.6}Sn{sub 0.3}Co{sub 0.1} metal hydride electrodes. Alloy characterization included x-ray diffraction (XRD), x-ray absorption (XAS), hydrogen absorption in a Sieverts apparatus, and electrochemical cycling of alloy electrodes. The atomic volume of H was determined for two of the alloys. Electrochemical kinetic measurements were made using steady state galvanostatic measurements, galvanodynamic sweep, and electrochemical impedance techniques. XAS was used to examine the degree of corrosion of the alloys with cycling. Alloying with Y decreased the corrosion rate. The results are consistent with corrosion inhibition by a Y containing passive film. The increase in the kinetics of the hydrogen oxidation reaction (HOR) with increasing depth of discharge was much greater on the Y containing alloys. This may be due to the dehydriding of the catalytic species on the surface of the metal hydride particles.
NASA Technical Reports Server (NTRS)
Hynes, A. J.; Wine, P. H.
1997-01-01
The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.
Numerical modeling of surface reaction kinetics in electrokinetically actuated microfluidic devices.
Sadeghi, Arman; Amini, Younes; Saidi, Mohammad Hassan; Chakraborty, Suman
2014-08-01
We outline a comprehensive numerical procedure for modeling of species transport and surface reaction kinetics in electrokinetically actuated microfluidic devices of rectangular cross section. Our results confirm the findings of previous simplified approaches that a concentration wave is created for sufficiently long microreactors. An analytical solution, developed for the wave propagation speed, shows that, when normalizing with the fluid mean velocity, it becomes a function of three parameters comprising the channel aspect ratio, the relative adsorption capacity, and the kinetic equilibrium constant. Our studies also reveal that the reactor geometry idealized as a slit, instead of a rectangular shape, gives rise to the underestimation of the saturation time. The extent of this underestimation increases by increasing the Damkohler number or decreasing the dimensionless Debye-Hückel parameter. Moreover, increasing the values of the Damkohler number, the dimensionless Debye-Hückel parameter, the relative adsorption capacity, and the velocity scale ratio results in lower saturation times. PMID:25064245
HTP kinetics studies on isolated elementary combustion reactions over wide temperature ranges
Fontijn, A.; Adusei, G.Y.; Hranisavlevic, J.; Bajaj, P.N.
1993-12-01
The goals of this project are to provide accurate data on the temperature dependence of the kinetics of elementary combustion reactions, (i) for use by combustion modelers, and (ii) to gain a better fundamental understanding of, and hence predictive ability for, the chemistry involved. Experimental measurements are made mainly by using the pseudo-static HTP (high-temperature photochemistry) technique. While continuing rate coefficient measurements, further aspects of kinetics research are being explored. Thus, starting from the data obtained, a method for predicting the temperature dependence of rate coefficients of oxygen-atom olefin experiment and confirms the underlying mechanistic assumptions. Mechanistic information of another sort, i.e. by product analysis, has recently become accessible with the inauguration of our heated flow tube mass spectrometer facility; early results are reported here. HTP experiments designed to lead to measurements of product channels by resonance fluorescence have started.
Kinetic studies of overlapping pyrolysis reactions in industrial waste activated sludge.
Yang, Xiaoyi; Jiang, Zhenpeng
2009-07-01
A sludge pyrolytic kinetics model was established in this study. Two types of sewage sludge from different industrial wastewater treatment plant produced different DTG (Derivative Thermogravimetry) shapes with an overlapping pattern. The multi-heating rate method was conducted to evaluate the kinetics for obtaining reasonable pyrolysis mechanisms and DTG curves were divided into several peaks using the Lorentz fitting method based on the composition of the sludge and the desire for precision. The peaks formed corresponded to the pyrolysis reactions of volatile matter, microbe cells, proteins, inorganic substances and char respectively, which can be reasonably explained based on the results from the flue gas analyzer and the chemical analysis. Two types of sewage sludge were found to have similar pyrolysis mechanisms. Reasonable reasons were also given to explain the distortion and lag observed in the DTG curves and pyrolysis mechanism. PMID:19342231
Xin, Jie; Zhang, Guanghui; Deng, Yi; Zhang, Heng; Lei, Aiwen
2015-11-18
The difference between Pd and Ni has been investigated based on the Negishi-type oxidative coupling reactions in which reductive elimination was proved to be the rate determining step. Although DFT calculations illustrate that the Pd catalyzed reaction should be faster than the Ni catalyzed reaction under these conditions, kinetic experiments indicate that the reaction rate of Pd and Ni is dependent on the concentration of the catalyst precursor. The Pd catalyzed reaction is faster than the Ni catalyzed reaction only when the precursor concentration is as low as 1 × 10(-7) M. PMID:26536236
Kinetic, structural, and reaction engineering studies of inorganic-organic sol-gel copolymers
NASA Astrophysics Data System (ADS)
Rankin, Stephen Edward
This work describes quantitative modeling of the kinetics of structure development during polymerization of alkoxysilanes. The modeling includes both deterministic chemical kinetics and stochastic simulation. Polycondensation is experimentally monitored mainly by 29Si nuclear magnetic resonance (NMR). For hydrolysis and polycondensation of (poly)methyl (poly)ethoxysilanes in homogeneous solution, three necessary modeling features are identified: (1) hydrolysis reversibility and rapidness leading to pseudoequilibrium, (2) condensation reactivity decreasing strongly as connectivity increases, and (3) extensive cyclization. Failure to model cyclization can lead to erroneous conclusions. The effects of organic substituents and solvent on polycondensation kinetics are examined by fitting a model with these features to 29Si NMR data. While organic substitution and the extents of hydrolysis and condensation of a silicon site affect the hydrolysis rate, these substituents do not affect hydrolysis equilibrium. Substitution at the reacting site also affects the magnitude but not the existence of a negative condensation substitution effect. Cyclization depends strongly on organic substitution. The deterministic kinetic model fit to NMR data provides direct information only about local structure development, not about the polymer size and shape distribution. To understand the structural implications of the kinetic trends found, this thesis presents kinetic Monte Carlo simulations of alkoxysilane polymerization. The simulations show that extensive cyclization plays a major role in predicting structural features such as the gelation point. Cyclization also causes the polymer structure to depend on monomer concentration---a feature absent from previous models. These simulations allow better agreement with experiment and will be useful in process design. For instance in coating operations, the simulations indicate that structure gradients appear and may cause excess shrinkage and stress at the free surface---problems which may be addressed with design calculations. Finally, this thesis extends quantitative kinetic modeling to copolymerization of pairs of alkoxysilanes. More kinetic parameters must be determined for these systems. To do so, the extent of copolymerization is determined indirectly by the dependence on composition of reaction rates in a semibatch reactor. These copolymerization models allow optimization of copolymer homogeneity and molecular structure by reactor design.
Comparison of second-order orbital-dependent DFT correlation functionals
NASA Astrophysics Data System (ADS)
Grabowski, Ireneusz
The choice of the orbital-dependent second-order correlation functional plays the prime role in the description of the correlation effects in orbital-dependent DFT calculations. Using second-order perturbation theory we were able to derive the simplest orbital-dependent correlation functional, but even at this lowest correlation level, we had several possibilities to define it. Applications of different second-order correlation functionals for the atomic as well as molecular systems are presented. The ab initio DFT-type OEP2 functionals based on Møller-Plesset or semicanonical partitioning (OEP2-sc) are compared with those based on Epstein-Nesbet type partitioning, showing that the latter ones can fail in more difficult molecular problems, e.g., the Be dimer potential curve. We show that currently the best performing orbital-dependent second-order correlation functional is the OEP2-sc one.
First-Order System Least Squares for Second-Order Partial ...
Dec 6, 2003 ... have obtained prior permission, you may not download an entire issue of a journal or multiple copies of articles, and you may .... the second-order elliptic problem into a system of ?rst order. ...... computational fluid dynamics.
B polarization of cosmic background radiation from second-order scattering sources
Beneke, M.; Fidler, C.; Klingmüller, K.
2011-04-01
B-mode polarization of the cosmic background radiation is induced from purely scalar primordial sources at second order in perturbations of the homogeneous, isotropic universe. We calculate the B-mode angular power spectrum C{sub l}{sup BB} sourced by the second-order scattering term in the full second-order Boltzmann equations for the polarized radiation phase-space density, which have recently become available. We find that at l ? 200 the second-order effect is comparable to the first-order effect for a tensor-to-scalar ratio of r = 10{sup ?6}, and to about 2·10{sup ?4} at l ? 1000. It is always negligible relative to the weak-lensing induced contribution.
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.
Mueller, Amy V.
In this paper a second-order method for blind source separation of noisy instantaneous linear mixtures is presented for the case where the signal order k is unknown. Its performance advantages are illustrated by simulations ...
Comparison of Second-Order Loads on a Tension-Leg Platform for Wind Turbines: Preprint
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.
Mesh independent convergence of modified inexact Newton methods for second order nonlinear problems
Kim, Taejong
2006-08-16
In this dissertation, we consider modified inexact Newton methods applied to second order nonlinear problems. In the implementation of Newton's method applied to problems with a large number of degrees of freedom, it is often necessary to solve...
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.
Yang, Daoqi
Improved Error Estimation of Dynamic Finite Element Methods for Second Order Parabolic Equations problems. Standard, characteristic, and mixed finite element methods with dynamic function spaces the finite element method requires capabilities for efficient, dynamic, and selfadaptive local grid
PointDistributed Algorithms for Second Order Elliptic Equations in Mixed Form
Ewing, Richard E.
PointDistributed Algorithms for Second Order Elliptic Equations in Mixed Form Richard E. Ewing, 1 by Douglas, Ewing, Russell, Wheeler, and colleagues in [1012, 17, 18]. Other applications to elasticity
Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics
NASA Technical Reports Server (NTRS)
Kawa, S. Randolph; Stolarski, 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 aspect of out 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 to simulate these process in numerical models of chemistry and transport. These models depend on laboratory-measured kinetic reaction rates and photlysis cross section to simulate molecular interactions. 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 evaluation are applied in random combinations. We determine the key reaction 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.
Reaction kinetics, P-T-t paths and rates of tectonic processes
Bohlen, S.R.; Hankins, W.B.; Eckert, J.O. Jr.; Kirby, S.H.; Liu, J. ); Hacker, B.R.; Mosenfelder, J.L. . Dept. of Geology)
1992-01-01
The interpretation of portions of P-T-time (t) paths in metamorphic rocks assumes that continuous and discontinuous reactions record local equilibrium as P-T conditions change, implying that the kinetics of many reactions are rapid relative to dT/dt and dP/dt. Occurrence of eclogite veins in granulites from Bergen, Norway as well as occurrences of coesite and diamond in crustal rocks imply that, under certain conditions, this assumption is wrong. Knowledge of the kinetics of important reactions under appropriate conditions would provide limits on the duration of relatively narrowly defined P-T conditions, allow inference of the rates of exhumation of rocks containing high-pressure phases, and allow the calculation of the time required for the conversion of gabbro to eclogite in the lower crust as a function of P-T-t. The authors are currently assessing the rates of key phase transformations: calcite to aragonite, albite to jadeite + quartz, coesite to quartz, opx[sub Fs[sup 80
Accurate label-free reaction kinetics determination using initial rate heat measurements
Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Jacobs, Denise; Hagen, Wilfred R.
2015-01-01
Accurate label-free methods or assays to obtain the initial reaction rates have significant importance in fundamental studies of enzymes and in application-oriented high throughput screening of enzyme activity. Here we introduce a label-free approach for obtaining initial rates of enzyme activity from heat measurements, which we name initial rate calorimetry (IrCal). This approach is based on our new finding that the data recorded by isothermal titration calorimetry for the early stages of a reaction, which have been widely ignored, are correlated to the initial rates. Application of the IrCal approach to various enzymes led to accurate enzyme kinetics parameters as compared to spectroscopic methods and enabled enzyme kinetic studies with natural substrate, e.g. proteases with protein substrates. Because heat is a label-free property of almost all reactions, the IrCal approach holds promise in fundamental studies of various enzymes and in use of calorimetry for high throughput screening of enzyme activity. PMID:26574737
Reaction Kinetics of CO2 Carbonation with Mg-Rich Minerals
Kwon, Dr. Soonchul; Fan, Maohong; DaCosta, Dr. Herbert F.M.; Russell, Dr. Armistead; Tsouris, Costas
2011-01-01
Due to their low price, wide availability, and stability of the resulting carbonates, Mg-rich minerals are promising materials for carbonating CO{sub 2}. Direct carbonation of CO{sub 2} with Mg-rich minerals reported in this research for the first time could be considerably superior to conventional liquid extraction processes from an energy consumption perspective due to its avoidance of the use of a large amount of water with high specific heat capacity and latent heat of vaporization. Kinetic models of the reactions of the direct CO{sub 2} carbonation with Mg-rich minerals and within simulated flue gas environments are important to the scale-up of reactor designs. Unfortunately, such models have not been made available thus far. This research was initiated to fill that gap. Magnesium silicate (Mg{sub 2}SiO{sub 4}), a representative compound in Mg-rich minerals, was used to study CO{sub 2} carbonation reaction kinetics under given simulated flue gas conditions. It was found that the chosen sorbent deactivation model fits well the experimental data collected under given conditions. A reaction order of 1 with respect to CO{sub 2} is obtained from experimental data. The Arrhenius form of CO{sub 2} carbonation with Mg{sub 2}SiO{sub 4} is established based on changes in the rate constants of the chosen deactivation model as a function of temperature.
Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald; Alba-Rubio, Ana C.; Dumesic, James A.; Mavrikakis, Manos
2014-04-01
A combined theoretical and experimental approach is presented that uses a comprehensive mean-field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self-consistent, generalized gradient approximation (GGA-PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO21H2) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is 4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts.
Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics
Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.
2009-12-23
Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).
El-Morshedy, Hassan A
2010-01-01
New global attractivity criteria are obtained for the second order difference equation \\[ x_{n+1}=cx_{n}+f(x_{n}-x_{n-1}),\\quad n=1, 2, ... \\] via a Lyapunov-like method. Some of these results are sharp and support recent related conjectures. Also, a necessary and sufficient condition for the oscillation of this equation is obtained using comparison with a second order linear difference equation with positive coefficients.
Applications of the second-order achromat concept to the design of particle accelerators
Brown, K.L.; Servranckx, R.V.
1985-05-01
A property of the second-order achromat, whereby dipole and sextupole families may be inserted into a lattice for chromatic corrections without introducing second-order geometrical (on momentum) optical distortions, has been incorporated in several new particle accelerator designs. These include the SLC at SLAC, LEP at CERN, the EROS pulse stretcher ring at Saskatoon, the CEBAF ring at SURA, and the MIT ring.
Asymptotic approximations for second-order linear difference equations in Banach algebras, II
NASA Astrophysics Data System (ADS)
Soldà, Tania; Spigler, Renato; Vianello, Marco
2008-04-01
A Liouville-Green (WKB) asymptotic approximation theory is developed for some classes of linear second-order difference equations in Banach algebras. The special case of linear matrix difference equations (or, equivalently, of second-order systems) is emphasized. Rigorous and explicitly computable bounds for the error terms are obtained, and this when both, the sequence index and some parameter that may enter the coefficients, go to infinity. A simple application is made to orthogonal matrix polynomials in the Nevai class.
Laser flash photolysis studies of radical-radical reaction kinetics: The HO{sub 2} + IO reaction
Cronkhite, J.M.; Stickel, R.E.; Nicovich, J.M.; Wine, P.H.
1999-04-29
Reactive iodine as a potential tropospheric O{sub 3} sink has received considerable attention recently. Laser flash photolysis of Cl{sub 2}/CH{sub 3}OH/O{sub 2}/I{sub 2}/NO{sub 2}/SF{sub 6}N{sub 2} mixtures at 308 nm has been coupled with simultaneous time-resolved detection of HO{sub 2} (by infrared tunable diode laser absorption spectroscopy) and IO (by visible absorption spectroscopy) to investigate the kinetics of the atmospherically important reaction HO{sub 2} + IO {r_arrow} products over the temperature range 274--373 K in N{sub 2} buffer gas at pressures of 12 and 25 Torr. All experiments were performed under near pseudo-first-order conditions with HO{sub 2} in excess over IO. At 298 K, the rate coefficient was determined to be (9.7 {+-} 2.9) {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}, with the primary source of uncertainty being knowledge of the infrared line strength(s) required to convert measured HO{sub 2} absorbances to absolute concentrations. The temperature dependence of the HO{sub 2} + IO rate coefficient was found to be adequately described by the Arrhenius expression k = 9.3 {times} 10{sup {minus}12} exp(680/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The results reported in this study are compared with other recent studies of HO{sub 2} + IO kinetics, and the potential roles of this reaction in atmospheric chemistry are discussed.
Photochemistry and kinetics of gas phase reactions involving HO and Cl radicals
Nelson, H.H.
1980-11-01
The kinetics of the reaction of the HO radical with HNO/sub 3/ and H/sub 2/O/sub 2/, the kinetics of Cl atom reactions with ClNO and ClNO/sub 2/, and the photochemistry of ClNO/sub 2/ and ClONO/sub 2/ were examined. The ultraviolet absorption cross sections of HNO/sub 3/ and ClNO/sub 2/ were also determined as part of the kinetics work. The rate constant for the reaction of HO with HNO/sub 3/ at room temperature was measured to be (8.2 +- 1.8) x 10/sup -14/ cm/sup 3/ molecule/sup -1/ s/sup -1/, where the uncertainty reported here and in all cases reflects twice the experimental standard deviation plus an estimate of systematic errors. The rate constant for the reaction HO + H/sub 2/O/sub 2/ was measured as (1.57 +- 0.23) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This agrees well with the two latest determinations and serves as a calibration of the experimental apparatus used. The Cl + ClNO reaction rate constant was determined to be (1.65 +- 0.32) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The rate constant for the reaction of Cl + ClNO/sub 2/ was found to be (5.05 +- 0.75) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This is the first direct measurement of this rate constant. The photodissociation of ClNO/sub 2/ was studied in great detail. The absorption cross sections were measured in the ultraviolet and found to be substantially lower than the literature values in the Cl/sub 2/ absorption region (300 to 360 nm). Two product channels were investigated; products representative of the two channels were Cl and O atoms. Absolute calibration for the product detection systems was provided by Cl/sub 2/ and NO/sub 2/ photolysis respectively. The quantum uields measured for photolysis at 350 nm, calcualted using the absorption spectrum measured in this work, are: 0.93 +- 0.1 for Cl and less than or equal to 0.025 for O. An upper limit of 0.1 was measured for the O atom channel in ClOHO/sub 2/ photolysis.
Kinetic resolution of acids in acylation reactions in the presence of chiral tertiary amines
Potapov, V.M.; Dem'yanovich, V.M.; Khlebnikov, V.A.
1988-07-10
Asymmetric synthesis has now become an important method for the production of optically active compounds, and its most attractive form is asymmetric catalysis. This work was devoted to an investigation into asymmetric catalysis with chiral tertiary amines in acylation reactions. During the acylation of alcohols and amines by the action of racemic 2-phenylpropionic and 2-methyl-3-phenylpropionic acids in the presence of S-nicotine the initial acids are resolved kinetically. The (R)-2-phenylpropionic acid obtained in this way had an optical purity of 0.5-1.5%.
The kinetics of dolomite reaction rim growth under isostatic and non-isostatic pressure conditions
NASA Astrophysics Data System (ADS)
Helpa, V.; Rybacki, E.; Morales, L. G.; Abart, R.; Dresen, G. H.
2013-12-01
During burial and exhumation, rocks are simultaneously exposed to metamorphic reactions and tectonic stresses. Therefore, the reaction rate of newly formed minerals may depend on chemical and mechanical driving forces. Here, we investigate the reaction kinetics of dolomite (CaMg[CO3]2) rim growth by solid-state reactions experiments on oriented calcite (CaCO3) and magnesite (MgCO3) single crystals under isostatic and non-isostatic pressure conditions. Cylindrical samples of 3-5 mm length and 7 mm diameter were drilled and polished perpendicular to the rhombohedral cleavage planes of natural clear crystals. The tests were performed using a Paterson-type deformation apparatus at P = 400 MPa confining pressure, temperatures, T, between 750 and 850°C, and reaction durations, t, of 2 - 146 h to calculate the kinetic parameters of dolomite rim growth under isostatic stress conditions. For non-isostatic reaction experiments we applied in addition differential stresses, ?, up to 40 MPa perpendicular to the contact interface at T = 750°C for 4 - 171 h duration, initiating minor inelastic deformation of calcite. The thickness of the resulting dolomite reaction rims increases linearly with the square root of time, indicating a diffusion-controlled reaction. The rims consist of two different textural domains. Granular dolomite grains (? 2 -5 ?m grain size) form next to calcite and elongated palisade-shaped grains (1-6 ?m diameter) grow perpendicular to the magnesite interface. Texture measurements with the electron backscatter diffraction technique indicate that the orientations of dolomite grains are mainly influenced by the orientation of the calcite educt crystal, in particular in the granular rim. To some extent, the texture of dolomite palisades is also influenced by the orientation of magnesite. The thickness of the two individual layers increases with temperature. At 400 MPa isostatic pressure, T = 750°C and t = 29 hours, a 5 ?m thick granular dolomite layer and a 7 ?m thick palisade-shaped layer evolve. At similar conditions and a differential stress of 30 MPa, the rim thickness remains similar; consequently the effect of non-isostatic stress on dolomite rim growth is negligible. Platinum markers show that the initial calcite-magnesite interface is located between granular and palisade-forming dolomite, indicating that rim growth occurs by counter diffusion of MgO and CaO. Diffusion of MgO across the dolomite reaction rim into calcite forms additionally magnesio-calcite grains with diameters of ? 13 - 46 ?m, depending on the experimental conditions and increasing with increasing distance to the dolomite boundary. At T = 750°C, t = 29 hours, the thickness of the magnesio-calcite layer is 32 ?m (isostatic) - 35 ?m (? = 30 MPa). The experiments indicate that solid-state reaction rim growth of dolomite between calcite and magnesite is primarily controlled by diffusion of MgO and CaO, forming layers with different microstructures during growth into the educt phases. The kinetics of the reaction in the carbonate system are not significantly changed by differential stresses up to 40 MPa. We suggest that volume diffusion is the dominant transport mechanism, which is presumably less affected by non-isostatic stresses than grain boundary diffusion.
Kinetics and Reaction Pathways for Propane Dehydrogenation and Aromatization on Co/H-ZSM5 and H-ZSM5
Iglesia, Enrique
Kinetics and Reaction Pathways for Propane Dehydrogenation and Aromatization on Co/H-ZSM5 and H Co/H-ZSM5 catalyzes propane dehydrogenation and aromatization reactions. Initial product selectivities, product site-yields, and the 13C content and distribution in the products of 2-13C-propane show
A system consisting of a photochemical reaction was used to evaluate the kinetic parameters, such as reaction order and rate constant for the elemental mercury uptake by TiO2 in the presence of uv irradiation. TiO2 particles generated by an aerosol route were used in a fixed bed...
The DNA Binding Activity of p53 Displays Reaction-Diffusion Kinetics Peter Hinow,* Carl E. Rogers,y
Hinow, Peter
The DNA Binding Activity of p53 Displays Reaction-Diffusion Kinetics Peter Hinow,* Carl E. Rogers that bind temporarily to a spatially homogeneous immobile structure with binding and release rates k1 and k2 slower than that of GFP alone, DGFP ¼ 41.6 mm2 sÿ1 . The reaction rates of the binding and unbinding of p
NASA Astrophysics Data System (ADS)
Gao, Shuqin; Liao, Lifu; Xiao, Xilin; Zhao, Zhiyuan; Du, Nan; Du, Jiangfeng
2010-05-01
A new spectrophotometric method for the determination of nicotine in mixtures without pre-separation has been proposed. Nicotine could react with 2,4-dinitrophenol through a charge-transfer reaction to form a colored complex. The second-order data from the visible absorption spectra of the complex in a series of ethanol-water binary solvents with various water volume fractions could be expressed as the combination of two bilinear data matrices. With the bilinear model, the second-order spectra data of mixtures containing nicotine and other interferents could be analysed by using second-order calibration algorithms, and the determination of nicotine in the mixtures could be achieved. The algorithm used here was parallel factor analysis. The method has been successfully used to determine nicotine in tobacco samples with satisfactory results.
On the Upscaling of Reaction-Transport Processes in Porous Media with Fast Kinetics
Kechagi, P.; Tsimpanogiannis, I.; Yortsos, Y.C.; Lichtner, P.
2001-01-09
This report is organized as follows: Provide a brief review of the upscaling constraints of the type (2) for a typical diffusion-reaction system. In this an analogy with two-phase flow in porous media was drawn. Then, using the methodology of QW a problem at the unit cell for the computation of the effective mass transfer coefficient, in processes where local thermodynamic equilibrium applies was derived. This problem is found to be different than in QW, as it depends on the gradients of the macroscale variable, and can be cast in terms of an eigenvalue problem. Two simple, examples, one involving advection-dissolution and another involving drying in a pore network, was presented to illustrate the coupling between scales and to show the quantitative effect in case this coupling was neglected. Finally, similar ideas and an illustrative example was applied to reaction-diffusion systems with fast kinetics, where an equilibrium state is approached.
NASA Astrophysics Data System (ADS)
Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi
2014-08-01
Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.
Origin of fatty acid synthesis - Thermodynamics and kinetics of reaction pathways
NASA Technical Reports Server (NTRS)
Weber, Arthur L.
1991-01-01
The primitiveness of contemporary fatty acid biosynthesis was evaluated by using the thermodynamics and kinetics of its component reactions to estimate the extent of its dependence on powerful and selective catalysis by enzymes. Since this analysis indicated that the modern pathway is not primitive because it requires sophisticated enzymatic catalysis, an alternative pathway of primitive fatty acid synthesis is proposed that uses glycolaldehyde as a substrate. In contrast to the modern pathway, this primitive pathway is not dependent on an exogenous source of phosphoanhydride energy. Furthermore, the chemical spontaneity of its reactions suggests that it could have been readily catalyzed by the rudimentary biocatalysts available at an early stage in the origin of life.
NASA Astrophysics Data System (ADS)
Kovalenko, Sergii; Soloviev, Veniamin
2014-12-01
In the framework of the quantum-mechanical theory of elementary act of non-adiabatic electrochemical reactions, it is carried out the calculation of the discharge current of ions at the semiconductor-electrolyte solution interface using the model of isotropic spherically symmetric band. It is shown that our results generalize the well-known formulae for the current density obtained by Dogonadze, Kuznetsov, and Chizmadzhev [R. R. Dogonadze, A. M. Kuznetsov, and Yu. A. Chizmadzhev, The kinetics of some heterogeneous reactions at semiconductor-electrolyte interface, Zhur. Fiz. Khim. 38, 1195 (1964)]. The average densities of states in the valence band and the conduction band of the semiconductor electrode in the heterogeneous charge transfer are found.
Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction
NASA Technical Reports Server (NTRS)
Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.
1997-01-01
Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.
Deuterium kinetic isotope effects and the mechanism of the bacterial luciferase reaction.
Francisco, W A; Abu-Soud, H M; DelMonte, A J; Singleton, D A; Baldwin, T O; Raushel, F M
1998-02-24
A combined experimental and theoretical investigation of the deuterium isotope effects on the bacterial luciferase reaction is described. The experimental studies focus on determining if the unusual aldehydic deuterium isotope effect of approximately 1.5 observed in these reactions is an intrinsic isotope effect resulting from a single rate-limiting step or is a composite of multiple rate-limiting steps. The isotope effect observed is not significantly affected by variation in the aldehyde chain length, changes in the pH over a range of 6-9, use of alphaC106A and alphaC106S site-directed mutants, or chloride substitution at the 8-position of the reduced flavin, though the isotope effect is decreased when the 8-methoxy-substituted flavin is used as a substrate. From these observations it is concluded that the aldehydic isotope effect arises from the change in rate of a single kinetic step. A stopped-flow kinetic analysis of the microscopic rate constants for the reactions of 1-[1H]decanal and 1-[2H]decanal in the bacterial luciferase reaction was carried out, and aldehyde hydration isotope effects were determined. From the results it is estimated that the aldehydic deuterium isotope effect is approximately 1.9 after formation of an intermediate flavin C4a-hydroperoxy hemiacetal. Ab initio calculations were used to examine the transformation of the aldehyde into a carboxylic acid and to predict isotope effects for possible mechanisms. These calculations indicate that the mechanism involving rate-limiting electron transfer from the flavin C4a-hydroxide to an intermediate dioxirane is consistent with the enigmatic aldehydic isotope effect and that the intermediacy of a dioxirane is energetically plausible. PMID:9485410
The Role of Defects in the Local Reaction Kinetics of CO Oxidation on Low-Index Pd Surfaces
2013-01-01
The role of artificially created defects and steps in the local reaction kinetics of CO oxidation on the individual domains of a polycrystalline Pd foil was studied by photoemission electron microscopy (PEEM), mass spectroscopy (MS), and scanning tunneling microscopy (STM). The defects and steps were created by STM-controlled Ar+ sputtering and the novel PEEM-based approach allowed the simultaneous determination of local kinetic phase transitions on differently oriented ?m-sized grains of a polycrystalline sample. The independent (single-crystal-like) reaction behavior of the individual Pd(hkl) domains in the 10–5 mbar pressure range changes upon Ar+ sputtering to a correlated reaction behavior, and the reaction fronts propagate unhindered across the grain boundaries. The defect-rich surface shows also a significantly higher CO tolerance as reflected by the shift of both the global (MS-measured) and the local (PEEM-measured) kinetic diagrams toward higher CO pressure. PMID:23785524
McAuliffe, J.J. ); Perry, S.B. ); Brooks, E.E. ); Ingwall, J.S. Harvard Medical School, Boston, MA )
1991-03-12
Here the authors define the kinetics of the creatine kinase (CK) reaction in an intact mammalian heart containing the full rnage of CK isoenzymes. Previously derived kinetic constants were refit for the reaction occurring at 37C. Steady-state metabolite concentrations from {sup 31}P NMR and standard biochemical techniques were determined. {sup 31}P magnetization transfer data were obtained to determine unidirectional creatine kinase fluxes in hearts with differing total creatine contents and differing mitochondrial CK activities during KCl arrest and isovolumic work for both the forward reaction (MgATP synthesis) and reverse reaction (phosphocreatine synthesis). The NMR kinetic data and substrate concentrations data were used in conjunction with a kinetic model based on MM-CK in solution to determine the applicability of the solution-based kinetic models to the CK kinetics of the intact heart. The results indicated that no single set of rate equation constants could describe both the KCl-arrested and working hearts. Analysis of the results indicated that the CK reaction is rate limited in the direction of ATP synthesis, the size of the guanidino substrate pool drives the measured CK flux in the intact heart, and during isovolumic work, the CK reaction operates under saturating conditions; that is, the substrate concentrations are at least 2-fold greater than the K{sub m} or K{sub im} for each substrate. However, during KCl arrest the reaction does not operate under saturating conditions and the CK reaction velocity is strongly influenced by the guanidino substrate pool size.
Reaction kinetics of coarse-grained equilibrium polymers: a Brownian Dynamics study
C-C Huang; H. Xu; F. Crevel; J. Wittmer; J. -P. Ryckaert
2006-04-11
Self-assembled linear structures like giant cylindrical micelles or discotic molecules in solution stacked in flexible columns are systems reminiscent of polydisperse polymer solutions.These supramolecular polymers have an equilibrium length distribution, the result of a competition between the random breakage of chains and the fusion of chains to generate longer ones. In the present work, we review the basic theoretical concepts of these ``equilibrium polymers" and some of the important results obtained by simulation approaches. We propose a new version of a mesoscopic model in continuous space based on the bead and FENE spring polymer model which is treated by Brownian Dynamics and Monte-Carlo binding/unbinding reversible changes for adjacent monomers in space, characterized by an attempt frequency parameter. For a dilute and a moderately semi-dilute state-points which both correspond to dynamically unentangled regimes, the dynamic properties are found to depend upon $\\omega$ through the effective life time $\\tau_b$ of the average size chain which, in turn, yields the kinetic reaction coefficients of the mean-field kinetic model proposed by Cates. Simple kinetic theories seem to work for times $ t \\geq \\tau_b$ while at shorter time, strong dynamical correlation effects are observed.
Weese, R K; Burnham, A K
2005-09-28
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 and isothermal heating, 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. Differential scanning calorimetry, DSC, was used to monitor CP decomposition at linear heating rates of 1-7 C min{sup -1} in perforated pans and of 0.1-1.0 C min{sup -1} in sealed pans. The kinetic triplet was calculated using the LLNL code Kinetics05, and predictions for 210 and 240 C are compared to isothermal thermogravimetric analysis (TGA) experiments. Values are also reported for spark, friction, and impact sensitivity.
Ion-Molecule Reactions and Ion Kinetics in DC Townsend Discharges in Dielectric Gases
NASA Technical Reports Server (NTRS)
Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)
1998-01-01
In gas discharges the identify, transport, relative intensities, and kinetic energy distributions (KEDs) of ions may be dominated by ion-molecule reactions. In order to understand these discharges, there is a need for cross section data for various ion-molecule reactions, including symmetric and asymmetric charge-transfer, collisional detachment, and ion conversion reactions, especially for low to intermediate ion-impact energies. In view of the importance of dielectric gases, we have recently measured the KEDs of various positive and negative ions produced in DC Townsend discharges in SF6, CF4, CHF3, O2, and CO2. The relative abundance and mean energies of ions are obtained from the measured KEDs. The effective cross sections (Qeff) describing the KEDs of various ions can be derived by using the mean ion energies and the electric field-to-gas density ratios (E/N). In the case of SF6 and O2 discharges, the determined cross sections (Qeff) for the negative-ion molecule reactions are consistent with previously measured cross section data obtained by crossed-beam experiment. The availability of these cross section values enabled us to understand the ion data reasonably well. However, the lack of adequate cross section data for positive ions in all of the above gases is a major obstacle in understanding ion transport in these gas discharges.
Reaction Kinetics in Reactive Polymer Blends: End vs. Mid-functional Reactive Compatibilizer
NASA Astrophysics Data System (ADS)
Jeon, Hyun K.; Macosko, Christopher W.; Moon, Bongjin; Hoye, Thomas R.
2001-03-01
We have studied the reaction kinetics in reactive polymer blends of PMMA/PS using end-functional polymer and mid-functional polymer as reactive compatibilizers to see the effect of structure on a reactive compatibilization. We synthesized PMMA-mPA with an phthalic anhydride group in the middle of the chain and PMMA-ePA with the same functional group at the chain end by ATRP. For PS, we have used aliphatic (or aromatic amine) end functional PS-NH2 (or PS-ArNH_2). We have found little difference in the reaction rate between PS-NH2 with PMMA-ePA and PMMA-mPA and that the reaction conversion reached 90 min. Pure block or graft copolymers were formed as verified by SEC and TEM observation. We decreased the reactivity by employing PS-ArNH_2. We have also measured the reaction rate for the bilayer samples to remove the convection effect and to minimize the interfacial area generation by flow.
Kinetics of the Reactions of IO Radicals with NO and NO2
NASA Technical Reports Server (NTRS)
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 reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.
Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms
NASA Astrophysics Data System (ADS)
Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso
2012-01-01
Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10 13 s -1, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G ?? level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.
Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle
NASA Technical Reports Server (NTRS)
Fegley, Bruce, Jr.
1988-01-01
The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.
Two-scale large deviations for chemical reaction kinetics through second quantization path integral
Tiejun Li; Feng Lin
2015-08-26
Motivated by the study of the rare event for a typical genetic switching model in systems biology, we aim to establish the general two-scale large deviations for chemical reaction kinetic systems in this paper. We build a formal approach to explicitly obtain the large deviation rate functionals of the considered two-scale processes based upon the second-quantization path integral technique. This approach is shown to be superior than the well-known WKB asymptotics in giving the correct large deviation rate functionals rather than a non-unique Hamilton-Jacobi equation for the quasi-potential. We get three important types of large deviation results when the underlying two times scales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by path integral. We find that the three regimes correspond to the same mean-field deterministic limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit in chemical reaction kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes.
Yamada, Y.; Kawase, Y. . E-mail: bckawase@mail.eng.toyo.ac.jp
2006-07-01
In order to examine the optimal design and operating parameters, kinetics for microbiological reaction and oxygen consumption in composting of waste activated sludge were quantitatively examined. A series of experiments was conducted to discuss the optimal operating parameters for aerobic composting of waste activated sludge obtained from Kawagoe City Wastewater Treatment Plant (Saitama, Japan) using 4 and 20 L laboratory scale bioreactors. Aeration rate, compositions of compost mixture and height of compost pile were investigated as main design and operating parameters. The optimal aerobic composting of waste activated sludge was found at the aeration rate of 2.0 L/min/kg (initial composting mixture dry weight). A compost pile up to 0.5 m could be operated effectively. A simple model for composting of waste activated sludge in a composting reactor was developed by assuming that a solid phase of compost mixture is well mixed and the kinetics for microbiological reaction is represented by a Monod-type equation. The model predictions could fit the experimental data for decomposition of waste activated sludge with an average deviation of 2.14%. Oxygen consumption during composting was also examined using a simplified model in which the oxygen consumption was represented by a Monod-type equation and the axial distribution of oxygen concentration in the composting pile was described by a plug-flow model. The predictions could satisfactorily simulate the experiment results for the average maximum oxygen consumption rate during aerobic composting with an average deviation of 7.4%.
Hughes, Arwel V.; Rees, Paul; Heathcote, Peter; Jones, Michael R.
2006-01-01
The temperature-induced denaturation of the photosynthetic reaction center from Rhodobacter sphaeroides has been studied through the changes that occur in the absorption spectrum of the bound chromophores on heating. At elevated temperatures, the characteristic absorbance bands of the bacteriochlorins bound to the polypeptides within the reaction center are lost, and are replaced by features typical of unbound bacteriochlorophyll and bacteriopheophytin. The kinetics of the spectral changes cannot be explained by a direct conversion from the functional to the denatured form of the protein, and require the presence of at least one intermediate. Possible mechanisms for the transformation via an intermediate are examined using a global analysis of the kinetic data, and the most likely mechanism is shown to involve a reversible transformation between the native state and an off-pathway intermediate, coupled to an irreversible transformation to the denatured state. The activation energies for the transformations between the three components are calculated from the effect of temperature on the individual rate constants, and the likely structural changes of the protein during the temperature-induced transformation are discussed. PMID:16533858
NASA Technical Reports Server (NTRS)
Sugg, E.; Mason, J. G.
1983-01-01
Work has revealed that diamine derivatives of diphenylmethane (IV), diphenyl ether (V), benzophenone (IV), fluorene (VII), and fluorenone (VIII) polymerizations with pyromellitic dianhydride in DMA were dependent on the basicity of the amine compound. The correlation between the basicity of the amine and its reactivity with phthalic anhydride was determined. Basicity measurements were made by potentiometric titration of each amine in an acetonitrile-water solvent system, from which the pKa of the amine could be determined. Reactivity was defined in terms of the second order rate constant derived form spectrophotometric examination of the reaction between each amine and phthalic anhydride in DMA. This reaction was expected to proceed in either one (for a monoamine) or two (for a diamine) stages.
Hu, Baichuan; Baird, James K
2010-01-14
The rate of iodination of acetone has been measured as a function of temperature in the binary solvent isobutyric acid (IBA) + water near the upper consolute point. The reaction mixture was prepared by the addition of acetone, iodine, and potassium iodide to IBA + water at its critical composition of 38.8 mass % IBA. The value of the critical temperature determined immediately after mixing was 25.43 degrees C. Aliquots were extracted from the mixture at regular intervals in order to follow the time course of the reaction. After dilution of the aliquot with water to quench the reaction, the concentration of triiodide ion was determined by the measurement of the optical density at a wavelength of 565 nm. These measurements showed that the kinetics were zeroth order. When at the end of 24 h the reaction had come to equilibrium, the critical temperature was determined again and found to be 24.83 degrees C. An Arrhenius plot of the temperature dependence of the observed rate constant, k(obs), was linear over the temperature range 27.00-38.00 degrees C, but between 25.43 and 27.00 degrees C, the values of k(obs) fell below the extrapolation of the Arrhenius line. This behavior is evidence in support of critical slowing down. Our experimental method and results are significant in three ways: (1) In contrast to in situ measurements of optical density, the determination of the optical density of diluted aliquots avoided any interference from critical opalescence. (2) The measured reaction rate exhibited critical slowing down. (3) The rate law was pseudo zeroth order both inside and outside the critical region, indicating that the reaction mechanism was unaffected by the presence of the critical point. PMID:19928887
Borja Reina; Raül Vera
2015-08-08
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 $m_0$ (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 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.
Hilbe, Christian; Traulsen, Arne; Röhl, Torsten; Milinski, Manfred
2014-01-14
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
Stochastic Response Analysis of FRP using the Second-Order Perturbation-Based Homogenization Method
NASA Astrophysics Data System (ADS)
Sakata, Sei-Ichiro; Ashida, Fumihiro; Zako, Masaru
This paper discusses a stochastic response analysis using the perturbation-based homogenization method for a homogenization problem of a fiber reinforced composite material considering microscopic uncertainty. Since an estimated result of the stochastic characteristics such as the expectation and variance using the first order perturbation-based homogenization method includes a large error in some cases, applicability and effectiveness of the second or higher order perturbation method should be investigated. In this paper, at first, the second order perturbation-based homogenization method is formulated. A second order perturbation-based procedure for estimating the stochastic characteristics of equivalent elastic constants of an orthotropic material is also introduced. Next, the second-order perturbation-based stochastic homogenization method is applied to the stochastic analysis of a homogenized elastic property caused by uncertainty in material property of a microstructure. As a numerical example, the stochastic characteristics of the homogenized elastic properties of a unidirectional fiber reinforced plastic caused by the microscopic material uncertainty are estimated using the Monte-Calro simulation, the first and second order perturbation method. Also, a detailed stochastic analysis for a homogeneous isotropic material is performed. From the numerical results, effectiveness and a problem of the second-order perturbation method are illustrated.
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
Kinetics of the reaction of aqueous iron(vi) (FeVIO42-) with ethylenediaminetetraacetic acid.
Noorhasan, Nadine N; Sharma, Virender K
2008-04-14
The reaction of aqueous iron(vi) (FeVIO42-, Fe(vi)) with ethylenediaminetetraacetic acid (EDTA) was studied kinetically as a function of pH (1.98-12.40) and temperature (15-45 degrees C) using a stopped flow kinetic technique. The rate law for the reaction of Fe(vi) with EDTA was found to be first-order with respect to each reactant over the entire studied pH range. The observed rate constants, k, decrease with an increase in pH, varying from 4.19 x 10(4) to 8.60 x 10(-2) M(-1) s(-1) over the pH range. The speciation of Fevi (H3FeO4+, H2FeO4, HFeO4-, and FeO42-) and EDTA (H4Y, H3Y-, H2Y2-, HY3-, and Y4-, Y = EDTA) species was used to explain the pH dependence of the k values. From the temperature effect on k at pH 5.4, 7.1, and 9.2, activation parameters, DeltaS(double dagger) and DeltaH(double dagger), were obtained for the reactions of Fe(VI) with EDTA. The values of DeltaS(double dagger) for the reactions were found to be negative, implying a highly ordered transition state in the reaction. The DeltaH(double dagger) for the reaction at pH 7.1 and 9.2 showed similar values within experimental error. Using the observed enthalpy parameters and the enthalpy of deprotonation of HFeO4- and EDTA species (HEDTA3- and H2EDTA2-), the enthalpy of deprotonation of H2FeO4 (DeltaH0H2FeO4) was determined as 5.7 +/- 3.0 kJ mol(-1). The reactivity of Fe(VI) with aminopolycarboxylates (APCs) was also studied in alkaline medium. The order of reactivity was determined as primary > secondary > tertiary, which suggests that FeVIO42- attacks at the nitrogen atom sites of APCs. PMID:18369495
NASA Astrophysics Data System (ADS)
Bergeat, Astrid; Caubert, Philippe; Costes, Michel; Daugey, Nicolas; Loison, Jean-Christophe
CH radical reactions with hydrocarbons could play a role in the atmospheres of Titan, Pluto or Triton as well as in interstellar clouds (ISCs), where the hydrocarbon compounds were detected and the temperatures are very low, i.e. ~ 95 K down to ~ 38 K at the surface of these satellites and planet and from 50 K down to 10 K in ISCs. In fact, in modelling the processes occurring in these low-temperature environments, researchers generally still have to extrapolate the high-temperature kinetic data mainly obtained in the temperature range above 300 K. However, for many neutral-neutral reactions studied, the rate constants exhibit essentially non-Arrhenius behaviour at low temperatures. The temperature dependences of the methylidyne radical reactions with methane, allene, methylacetylene and propene were studied in our new supersonic flow reactor coupled with pulsed laser photolysis (PLP) and laser induced fluorescence (LIF) techniques. Three Laval nozzles were designed to provide uniform supersonic expansions down to 77 K. The rate constants for the CH + CH4 reaction are in good agreement with the temperature dependence proposed by A. Canosa et al., i.e. 3.96 × 10-8 ×(T/K)-1.04 exp(-36.1K/T) in the range 23-298 K. The rate constants of the CH + C3H4 (allene), CH + C3H4 (methylacetylene) and CH + C3H6 (propene) reactions exhibit a small temperature dependence between 77 and 170 K, are close to the gas kinetic limit and could thus contribute to the chemistry in the dense molecular clouds or outer planets atmospheres (Titan, Pluto and Triton for example) rich in hydrocarbons. The reactions of CH radical with several saturated and unsaturated hydrocarbons were studied, at room temperature, in a low-pressure fast-flow reactor. The absolute atomic hydrogen productions were determined at 300 K by V.U.V. resonance fluorescence, the reference used being the H production from the CH + CH4 and H2S reactions. Ab initio studies of the different stationary points relevant to some of those reactions and RRKM calculations have been performed for extrapolations at low temperatures. For the CH + saturated hydrocarbons reactions (C2H6, n-C3H8, n-C4H10, n, iso and neo-C5H12 and n-C6H14), the H production is rarely the main channel, which means that these reactions lead to a large variety of unsaturated hydrocarbons and radicals. On the other hand, CH radical is a good candidate in the synthesis of large organic molecules, by producing mainly H atoms and larger carbon skeleton when CH radical reacts with the unsaturated hydrocarbons C2H2, C3H4, C2H4, C3H6 and C4H8, compared to the carbon atom reactions that we have studied previously.
The strange kinetics of the C{sub 2}H{sub 6} + CN reaction explained.
Georgievskii, Y.; Klippenstein, S. J.; Chemistry; SNL
2007-05-17
In this paper, we employ state of the art quantum chemical and transition state theory methods in making a priori kinetic predictions for the abstraction reaction of CN with ethane. This reaction, which has been studied experimentally over an exceptionally broad range of temperature (25-1140 K), exhibits an unusually strong minimum in the rate constant near 200 K. The present theoretical predictions, which are based on a careful consideration of the two distinct transition state regimes, quantitatively reproduce the measured rate constant over the full range of temperature, with no adjustable parameters. At low temperatures, the rate-determining step for such radical-molecule reactions involves the formation of a weakly bound van der Waals complex. At higher temperatures, the passage over a sub-threshold saddle point on the potential energy surface, related to the formation and dissolution of chemical bonds, becomes the rate-determining step. The calculations illustrate the changing importance of the two transition states with increasing temperature and also clearly demonstrate the need for including accurate treatments of both transition states. The present two transition state model is an extension of that employed in our previous work on the C2H4 + OH. It incorporates direct ab initio evaluations of the potential in classical phase space integral based calculations of the fully coupled anharmonic transition state partition functions for both transition states. Comparisons with more standard rigid-rotor harmonic oscillator representations for the 'inner' transition state illustrate the importance of variational, anharmonic, and nonrigid effects. The effects of tunneling through the 'inner' saddle point and of dynamical correlations between the two transition states are also discussed. A study of the kinetic isotope effect provides a further test for the present two transition state model.
Exact calculation of three-body contact interaction to second order
N. Kaiser
2012-03-28
For a system of fermions with a three-body contact interaction the second-order contributions to the energy per particle $\\bar E(k_f)$ are calculated exactly. The three-particle scattering amplitude in the medium is derived in closed analytical form from the corresponding two-loop rescattering diagram. We compare the (genuine) second-order three-body contribution to $\\bar E(k_f)\\sim k_f^{10}$ with the second-order term due to the density-dependent effective two-body interaction, and find that the latter term dominates. The results of the present study are of interest for nuclear many-body calculations where chiral three-nucleon forces are treated beyond leading order via a density-dependent effective two-body interaction.
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.
Second order asymptotics of mixed quantum source coding via universal codes
Felix Leditzky; Nilanjana Datta
2015-08-13
The simplest example of a quantum information source with memory is a mixed source which emits signals entirely from either one of two memoryless quantum sources with given a priori probabilities. For such a source, we derive the second order asymptotic rates for fixed-length (visible) source coding. This provides the first example of second order asymptotics for a quantum information-processing task employing a resource with memory. For the case of a classical mixed source (using a finite alphabet), our results reduce to those obtained by Nomura and Han [IEEE Trans. on Inf. Th. 59.1 (2013), pp. 1-16]. To prove the achievability part of our main result, we introduce universal quantum source codes achieving second order asymptotic rates. These are obtained by an extension of Hayashi's construction [IEEE Trans. on Inf. Th. 54.10 (2008), pp. 4619-4637] of their classical counterparts.
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.
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, {{? }(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.
NASA Astrophysics Data System (ADS)
Kedziora, David J.; Ankiewicz, Adrian; Akhmediev, Nail
2012-06-01
We present an explicit analytic form for the two-breather solution of the nonlinear Schrödinger equation with imaginary eigenvalues. It describes various nonlinear combinations of Akhmediev breathers and Kuznetsov-Ma solitons. The degenerate case, when the two eigenvalues coincide, is quite involved. The standard inverse scattering technique does not generally provide an answer to this scenario. We show here that the solution can still be found as a special limit of the general second-order expression and appears as a mixture of polynomials with trigonometric and hyperbolic functions. A further restriction of this particular case, where the two eigenvalues are equal to i, produces the second-order rogue wave with two free parameters considered as differential shifts. The illustrations reveal a precarious dependence of wave profile on the degenerate eigenvalues and differential shifts. Thus we establish a hierarchy of second-order solutions, revealing the interrelated nature of the general case, the rogue wave, and the degenerate breathers.
Beneke, M.; Fidler, C.
2010-09-15
Non-Gaussianity and B-mode polarization are particularly interesting features of the cosmic microwave background, as--at least in the standard model of cosmology--their only sources to first order in cosmological perturbation theory are primordial, possibly generated during inflation. If the primordial sources are small, the question arises how large is the non-Gaussianity and B-mode background induced in second order from the initially Gaussian and scalar perturbations. In this paper we derive the Boltzmann hierarchy for the microwave background photon phase-space distributions at second order in cosmological perturbation theory including the complete polarization information, providing the basis for further numerical studies. As an aside we note that the second-order collision term contains new sources of B-mode polarization and that no polarization persists in the tight-coupling limit.
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.
Quantum control landscape for a $?$-atom in the vicinity of second order traps
Alexander Pechen; David J. Tannor
2015-08-17
We show that the second order traps in the control landscape for a three-level $\\Lambda$-system found in our previous work {\\it Phys. Rev. Lett.} {\\bf 106}, 120402 (2011) are not local maxima: there exist directions in the space of controls in which the objective grows. The growth of the objective is slow --- at best 4th order for weak variations of the control. This implies that simple gradient methods would be problematic in the vicinity of second order traps, where more sophisticated algorithms that exploit the higher order derivative information are necessary to climb up the control landscape efficiently. The theory is supported by a numerical investigation of the landscape in the vicinity of the $\\varepsilon(t)=0$ second order trap, performed using the GRAPE and BFGS algorithms.
Second-order all-fiber comb filter based on polarization-diversity loop configuration.
Lee, Yong Wook; Kim, Hyun-Tak; Lee, Yong Wan
2008-03-17
By concatenating three birefringence loops in series, a second-order all-fiber comb filter based on a polarization-diversity loop configuration is newly proposed. The proposed filter consists of one polarization beam splitter, polarization-maintaining fibers, and two halfwave plates. The effect of a second-order structure of polarization-maintaining fiber loops on a bandwidth of the filter passband was theoretically analyzed and experimentally demonstrated. Transmission output of the second-order filter (flat-top and narrow-band transmission spectra) could be obtained by adjusting two half-wave plates. 1 and 3 dB bandwidths of the proposed filter in flat-top and narrow-band operations were greater by approximately 102.9 and 44.3 % and smaller by approximately 47.9 and 47.1 % than those of a conventional Sagnac birefringence filter, respectively. PMID:18542484
First- or second-order transition in the melting of repeat sequence DNA.
Chen, Y Z; Prohofsky, E W
1994-01-01
Both theoretical analysis and observation of the continuity of the melted fraction of base pairs indicate that the melting transition in DNA is second order. Analysis of the salt dependence of the transition by polyelectrolyte limiting laws, however, has first-order dynamics imbedded in the analysis. This paper proposes that the observation taken to be a latent heat of melting in the limiting law analysis could instead be a specific heat anomaly associated with a second-order transition. The limiting laws can be reconstructed based on a second-order transition with a specific heat anomaly. The T2M dependence of this excess heat is also consistent with its being a specific heat anomaly of a system displaying classical critical behavior. Classical critical behavior indicates that theoretical mean field approaches such as MSPA should be particularly appropriate to helix melting studies. PMID:8130338
Kowalsky, Michael B.; Moridis, George J.
2006-05-12
In this study we compare the use of kinetic and equilibrium reaction models in the simulation of gas (methane) hydrates in porous media. Our objective is to evaluate through numerical simulation the importance of employing kinetic versus equilibrium reaction models for predicting the response of hydrate-bearing systems to external stimuli, such as changes in pressure and temperature. Specifically, we (1) analyze and compare the responses simulated using both reaction models for production in various geological settings and for the case of depressurization in a core during extraction; and (2) examine the sensitivity to factors such as initial hydrate saturation, hydrate reaction surface area, and numerical discretization. We find that for systems undergoing thermal stimulation and depressurization, the calculated responses for both reaction models are remarkably similar, though some differences are observed at early times. Given these observations, and since the computational demands for the kinetic reaction model far exceed those for the equilibrium reaction model, the use of the equilibrium reaction model often appears to be justified and preferred for simulating the behavior of gas hydrates.
Kinetics of the monomer-dimer reaction of yeast hexokinase PI.
Hoggett, J G; Kellett, G L
1992-01-01
Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kass.) and dissociation (kdiss.) were determined as a function of glucose concentration using values of the equilibrium association constant of the monomer-dimer reaction derived from sedimentation ultracentrifugation studies under similar conditions, and also from the dependence of tau-2 on enzyme concentration. kass. was almost independent of glucose concentration and its value (2 x 10(5) M-1.s-1) was close to that expected for a diffusion-controlled process. The influence of glucose on the monomer-dimer reaction is entirely due to effects on kdiss., which increases from 0.21 s-1 in the absence of glucose to 25 s-1 at saturating concentrations. The monomer and dimer forms of hexokinase have different affinities and Km values for glucose, and the results reported here imply that there may be a significant lag in the response of the monomer-dimer reaction to changes in glucose concentrations in vivo with consequent hysteretic effects on the hexokinase activity. Images Fig. 1. PMID:1445216
Kinetics of the monomer-dimer reaction of yeast hexokinase PI.
Hoggett, J G; Kellett, G L
1992-10-15
Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kass.) and dissociation (kdiss.) were determined as a function of glucose concentration using values of the equilibrium association constant of the monomer-dimer reaction derived from sedimentation ultracentrifugation studies under similar conditions, and also from the dependence of tau-2 on enzyme concentration. kass. was almost independent of glucose concentration and its value (2 x 10(5) M-1.s-1) was close to that expected for a diffusion-controlled process. The influence of glucose on the monomer-dimer reaction is entirely due to effects on kdiss., which increases from 0.21 s-1 in the absence of glucose to 25 s-1 at saturating concentrations. The monomer and dimer forms of hexokinase have different affinities and Km values for glucose, and the results reported here imply that there may be a significant lag in the response of the monomer-dimer reaction to changes in glucose concentrations in vivo with consequent hysteretic effects on the hexokinase activity. PMID:1445216
Imaging in scattering media via the second-order correlation of light field
Wenlin Gong; Pengli Zhang; Xia Shen; Shensheng Han
2009-08-03
Imaging with the second-order correlation of two light fields is a method to image an object by two-photon interference involving a joint detection of two photons at distant space-time points. We demonstrate for the first time that an image with high quality can still be obtained in the scattering media by applying the second-order correlation of illuminating light field. The scattering effect on the visibility of images is analyzed both theoretically and experimentally. Potential applications and the methods to further improve the visibility of the images in scattering media are also discussed.
Observed galaxy number counts on the lightcone up to second order: I. Main result
Bertacca, Daniele; Maartens, Roy; Clarkson, Chris E-mail: roy.maartens@gmail.com
2014-09-01
We present the galaxy number overdensity up to second order in redshift space on cosmological scales for a concordance model. The result contains all general relativistic effects up to second order that arise from observing on the past light cone, including all redshift effects, lensing distortions from convergence and shear, and contributions from velocities, Sachs-Wolfe, integrated SW and time-delay terms. This result will be important for accurate calculation of the bias on estimates of non-Gaussianity and on precision parameter estimates, introduced by nonlinear projection effects.
Observed galaxy number counts on the light cone up to second order: III. Magnification bias
NASA Astrophysics Data System (ADS)
Bertacca, Daniele
2015-10-01
We study up to second order the galaxy number over-density that depends on magnification in redshift space on cosmological scales for a concordance model. The result contains all general relativistic effects up to second order which arise from observations of the past light cone, including all redshift and lensing distortions, contributions from velocities, Sachs-Wolfe, integrated SW, and time-delay terms. We find several new terms and contributions that could be potentially important for an accurate calculation of the bias on estimates of non-Gaussianity and on precision parameter estimates.
Quadratic curvature gravity with second order trace and massive gravity models in three dimensions
NASA Astrophysics Data System (ADS)
Baykal, Ahmet
2012-08-01
The quadratic curvature lagrangians having metric field equations with second order trace are constructed relative to an orthonormal coframe. In n > 4 dimensions, pure quadratic curvature lagrangian having second order trace constructed contains three free parameters in the most general case. The fourth order field equations of some of these models, in arbitrary dimensions, are cast in a particular form using the Schouten tensor. As a consequence, the field equations for the New massive gravity theory are related to those of the Topologically massive gravity. In particular, the conditions under which the latter is "square root" of the former are presented.
NASA Astrophysics Data System (ADS)
Wang, Zhengzi
2015-08-01
The influence of ambient temperature is a big challenge to robust infrared face recognition. This paper proposes a new ambient temperature normalization algorithm to improve the performance of infrared face recognition under variable ambient temperatures. Based on statistical regression theory, a second order polynomial model is learned to describe the ambient temperature's impact on infrared face image. Then, infrared image was normalized to reference ambient temperature by the second order polynomial model. Finally, this normalization method is applied to infrared face recognition to verify its efficiency. The experiments demonstrate that the proposed temperature normalization method is feasible and can significantly improve the robustness of infrared face recognition.
Second-order infinitesimal bendings of surfaces of revolution with flattening at the poles
Sabitov, I Kh
2014-12-31
We study infinitesimal bendings of surfaces of revolution with flattening at the poles. We begin by considering the minimal possible smoothness class C{sup 1} both for surfaces and for deformation fields. Conditions are formulated for a given harmonic of a first-order infinitesimal bending to be extendable into a second order infinitesimal bending. We finish by stating a criterion for nonrigidity of second order for closed surfaces of revolution in the analytic class. We also give the first concrete example of such a nonrigid surface. Bibliography: 15 entries.