ERIC Educational Resources Information Center
Silvestri, Michael G.; Dills, Charles E.
1989-01-01
Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)
NASA Astrophysics Data System (ADS)
Zhang, Lei; Chen, Lingen; Sun, Fengrui
2016-03-01
The finite-time thermodynamic method based on probability analysis can more accurately describe various performance parameters of thermodynamic systems. Based on the relation between optimal efficiency and power output of a generalized Carnot heat engine with a finite high-temperature heat reservoir (heat source) and an infinite low-temperature heat reservoir (heat sink) and with the only irreversibility of heat transfer, this paper studies the problem of power optimization of chemically driven heat engine based on first and second order reaction kinetic theory, puts forward a model of the coupling heat engine which can be run periodically and obtains the effects of the finite-time thermodynamic characteristics of the coupling relation between chemical reaction and heat engine on the power optimization. The results show that the first order reaction kinetics model can use fuel more effectively, and can provide heat engine with higher temperature heat source to increase the power output of the heat engine. Moreover, the power fluctuation bounds of the chemically driven heat engine are obtained by using the probability analysis method. The results may provide some guidelines for the character analysis and power optimization of the chemically driven heat engines.
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...
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)
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.
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…
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 heavilyâ€¦
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...
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 particleâ€™s momentum in agreement with observational evidence from many sources. The scattering itself was done by scattering of the particleâ€™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 AlfvÃ©n 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 AlfvÃ©n 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 AlfvÃ©n 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 AlfvÃ©n 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)
Radiation-Reaction Force on a Small Charged Body to Second Order
NASA Astrophysics Data System (ADS)
Moxon, Jordan; Flanagan, Eanna
2015-04-01
In classical electrodynamics, an accelerating charge emits radiation and experiences a corresponding radiation reaction force, or self force. We extend to greater precision (higher order in perturbation theory) a previous rigorous derivation of the electromagnetic self force in flat spacetime by Gralla, Harte, and Wald. The method introduced by Gralla, Harte, and Wald computes the self-force from the Maxwell field equations and conservation of stress-energy, and does not require regularization of a singular point charge, as has been necessary in prior computations. For our higher order compuation, it becomes necessary to adopt an adjusted definition of the mass of the body to avoid including self-energy from the electromagnetic field sourced during the history of the body. We derive the evolution equations for the mass, spin, and center of mass position of an extended body through second order using our adjusted formalism. The final equations give an acceleration dependent evolution of the spin (self-torque), as well as a mixing between the extended body effects and the acceleration dependent effects on the overall body motion.
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.
Piponnier, Jean-Claude; Forget, Robert; Gagnon, Isabelle; McKerral, Michelle; Giguère, Jean-François; Faubert, Jocelyn
2016-01-15
Mild traumatic brain injury (mTBI) has subtle effects on several brain functions that can be difficult to assess and follow up. We investigated the impact of mTBI on the perception of sine-wave gratings defined by first- and second-order characteristics. Fifteen adults diagnosed with mTBI were assessed at 15 days, 3 months, and 12 months postinjury. Fifteen matched controls followed the same testing schedule. Reaction times (RTs) for flicker detection and motion direction discrimination were measured. Stimulus contrast of first- and second-order patterns was equated to control for visibility, and correct-response RT means, standard deviations (SDs), medians, and interquartile ranges (IQRs) were calculated. The level of symptoms was also evaluated to compare it to RT data. In general in mTBI, RTs were longer, and SDs as well as IQRs larger, than those of controls. In addition, mTBI participants' RTs to first-order stimuli were shorter than those to second-order stimuli, and SDs as well as IQRs larger for first- than for second-order stimuli in the motion condition. All these observations were made over the three sessions. The level of symptoms observed in mTBI was higher than that of control participants, and this difference did also persist up to 1 year after the brain injury, despite an improvement. The combination of RT measures with particular stimulus properties is a highly sensitive method for measuring mTBI-induced visuomotor anomalies and provides a fine probe of the underlying mechanisms when the brain is exposed to mild trauma. PMID:25950948
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.
NASA Astrophysics Data System (ADS)
Pesci, Adriana I.; Goldstein, Raymond E.; Uys, Hermann
2005-05-01
In previous work we have shown that the quantum potential can be derived from the classical kinetic equations both for particles with and without spin. Here, we extend these mappings to the relativistic case. The essence of the analysis consists of Fourier transforming the momentum coordinate of the distribution function. This procedure introduces a natural parameter ? with units of angular momentum. In the non-relativistic case the ansatz of either separability, or separability and additivity, imposed on the probability distribution function produces mappings onto the Schrödinger equation and the Pauli equation, respectively. The former corresponds to an irrotational flow, the latter to a fluid with non-zero vorticity. In this work we show that the relativistic mappings lead to the Klein-Gordon equation in the irrotational case and to the second-order Dirac equation in the rotational case. These mappings are irreversible; an approximate inverse is the Wigner function. Taken together, these results provide a statistical interpretation of quantum mechanics.
Hübner, U; Keller, S; Jekel, M
2013-11-01
The application of the R(CT)-concept for predicting the removal of trace organic compounds (TrOCs) in organic rich WWTP effluents is often problematic due to the fast ozone depletion with instantaneous ozone demand in the range of typically applied ozone dosages. In this study, the determination of OH-radical and ozone exposure from second order rate kinetics with two internal tracer substances was evaluated as alternative approach for these waters. Results from batch and semi-batch experiments showed a linear correlation of OH-radical exposure with ozone consumption, characterized by its slope indicating the formation efficiency of OH-radicals and a lag ozone consumption without significant formation of OH-radicals. Evaluation of data from the project PILOTOX on ozonation of secondary effluent confirmed reasonable prediction of ozone resistant compound removal from relative residual concentration of an internal tracer substance. In contrast, predicting the reduction of TrOCs by direct reactions with ozone from internal tracers was not feasible. Similar removal efficiencies for fast reacting compounds with different rate constants from k(O3) = 10(4) M(-1) s(-1) to k(O3) = 10(6) M(-1) s(-1) were observed indicating a limitation of the reaction by mass transfer. This effect was observed at low ozone dosages in semi-batch and pilot experiments as well as in batch experiments, where mass transfer from gas to liquid phase is not limiting. It is assumed that consumption of low ozone dosages is faster than sample homogenization in the batch reactors used. Thus, prediction of compound removal by direct reaction with ozone always needs to consider reactor design and geometry. PMID:24050684
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
Second order symmetry operators
NASA Astrophysics Data System (ADS)
Andersson, Lars; Bäckdahl, Thomas; Blue, Pieter
2014-07-01
Using systematic calculations in spinor language, we obtain simple descriptions of the second order symmetry operators for the conformal wave equation, the Dirac-Weyl equation and the Maxwell equation on a curved four-dimensional Lorentzian manifold. The conditions for existence of symmetry operators for the different equations are seen to be related. Computer algebra tools have been developed and used to systematically reduce the equations to a form which allows geometrical interpretation.
Cuzinatto, R.R. . E-mail: rodrigo@ift.unesp.br; Melo, C.A.M. de . E-mail: cassius.anderson@gmail.com; Pompeia, P.J. . E-mail: pompeia@ift.unesp.br
2007-05-15
A gauge theory of second order in the derivatives of the auxiliary field is constructed following Utiyama's program. A novel field strength G = {partial_derivative}F + fAF arises besides the one of the first order treatment, F = {partial_derivative}A - {partial_derivative}A + fAA. The associated conserved current is obtained. It has a new feature: topological terms are determined from local invariance requirements. Podolsky Generalized Eletrodynamics is derived as a particular case in which the Lagrangian of the gauge field is L {sub P} {proportional_to} G {sup 2}. In this application the photon mass is estimated. The SU (N) infrared regime is analysed by means of Alekseev-Arbuzov-Baikov's Lagrangian.
Kang, Chao; Wu, Hai-Long; Zhou, Chang; Xiang, Shou-Xia; Zhang, Xiao-Hua; Yu, Yong-Jie; Yu, Ru-Qin
2016-03-01
The metabolic coenzymes reduced nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) are the primary electron donor and acceptor respectively, participate in almost all biological metabolic pathways. This study develops a novel method for the quantitative kinetic analysis of the degradation reaction of NADH and the formation reaction of FAD in human plasma containing an uncalibrated interferent, by using three-way calibration based on multi-way fluorescence technique. In the three-way analysis, by using the calibration set in a static manner, we directly predicted the concentrations of both analytes in the mixture at any time after the start of their reactions, even in the presence of an uncalibrated spectral interferent and a varying background interferent. The satisfactory quantitative results indicate that the proposed method allows one to directly monitor the concentration of each analyte in the mixture as the function of time in real-time and nondestructively, instead of determining the concentration after the analytical separation. Thereafter, we fitted the first-order rate law to their concentration data throughout their reactions. Additionally, a four-way calibration procedure is developed as an alternative for highly collinear systems. The results of the four-way analysis confirmed the results of the three-way analysis and revealed that both the degradation reaction of NADH and the formation reaction of FAD in human plasma fit the first-order rate law. The proposed methods could be expected to provide promising tools for simultaneous kinetic analysis of multiple reactions in complex systems in real-time and nondestructively. PMID:26873466
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.
NASA Astrophysics Data System (ADS)
Watanabe, T.; Sakai, Y.; Nagata, K.; Ito, Y.; Hayase, T.
2014-10-01
The reactive scalar field near the turbulent/non-turbulent (T/NT) interface is analyzed using a direct numerical simulation (DNS) of a planar jet with an isothermal second-order chemical reaction A + B ? P. Reactants A and B are supplied from the jet and ambient flows, respectively. The DNS of the reactive jet is performed for Damköhler numbers Da = 0.1, 1, and 10. A visualization of the T/NT interface shows that most of the product P is contained in the turbulent region. The conditional mean concentrations of the reactive species change sharply near the T/NT interface. The width of the jump in the conditional mean concentration is almost independent of the chemical species and the Damköhler number. For the slow reaction (Da = 0.1), the conditional average of the chemical production rate gradually increases from the non-turbulent region toward the turbulent region. In contrast, the conditional average of the production rate for Da = 1 and 10 has a large peak value slightly inside the T/NT interface. The chemical reaction near the T/NT interface strongly depends on the interface orientation. The reactant A is deficient near the T/NT interface. The production rate is large near the interface toward which the deficient reactant A is frequently transported by the velocity fields. The transport due to the velocity relative to the interface movement strongly depends on the relationship between the interface geometry and the mean flow field. The dependence of the chemical reaction on the interface orientation becomes strong as Da increases. When the interface propagates toward the non-turbulent region, the reactant A and product P are contained in the turbulent region although the molecular diffusion and reaction contribute to the increase in the concentrations of A (non-reactive case) and P in the non-turbulent region. In contrast, the interface propagation toward the turbulent region leaves the fluids containing A and P in the non-turbulent region.
Local reaction kinetics by imaging
NASA Astrophysics Data System (ADS)
Suchorski, Yuri; Rupprechter, GÃ¼nther
2016-01-01
In the present contribution we present an overview of our recent studies using the "kinetics by imaging" approach for CO oxidation on heterogeneous model systems. The method is based on the correlation of the PEEM image intensity with catalytic activity: scaled down to the Î¼m-sized surface regions, such correlation allows simultaneous local kinetic measurements on differently oriented individual domains of a polycrystalline metal-foil, including the construction of local kinetic phase diagrams. This allows spatially- and component-resolved kinetic studies and, e.g., a direct comparison of inherent catalytic properties of Pt(hkl)- and Pd(hkl)-domains or supported Î¼m-sized Pd-powder agglomerates, studies of the local catalytic ignition and the role of defects and grain boundaries in the local reaction kinetics.
Local reaction kinetics by imagingâ˜†
Suchorski, Yuri; Rupprechter, GÃ¼nther
2016-01-01
In the present contribution we present an overview of our recent studies using the â€œkinetics by imagingâ€ approach for CO oxidation on heterogeneous model systems. The method is based on the correlation of the PEEM image intensity with catalytic activity: scaled down to the Î¼m-sized surface regions, such correlation allows simultaneous local kinetic measurements on differently oriented individual domains of a polycrystalline metal-foil, including the construction of local kinetic phase diagrams. This allows spatially- and component-resolved kinetic studies and, e.g., a direct comparison of inherent catalytic properties of Pt(hkl)- and Pd(hkl)-domains or supported Î¼m-sized Pd-powder agglomerates, studies of the local catalytic ignition and the role of defects and grain boundaries in the local reaction kinetics. PMID:26865736
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.
Kinetics of actinide complexation reactions
Nash, K.L.; Sullivan, J.C.
1997-09-01
Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions.
Second Order Corrected Hadamard Formulae
NASA Astrophysics Data System (ADS)
Epele, L. N.; Fanchiotti, H.; Garcia Canal, C. A.
The second order correction to the Hadamard formulae for the Green function, harmonic measures and period matrix of a two-dimensional domain is obtained iu the context of the domain variational theory.Translated AbstractDie Hadmard-Formel mit Korrekturen der zweiten OrdnungDie Korrekturen der zweiten Ordnung zur Hadamard Formel für die Greensche Funktion, harmonische Maße und die Perioden-Matrix eines zweidimensionalen Bereichs werden berechnet im Rahmen der Theorie der Variation des Definitionsbereichs.
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 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.
Virtual Instrument for Determining Rate Constant of Second-Order Reaction by pX Based on LabVIEW 8.0
Meng, Hu; Li, Jiang-Yuan; Tang, Yong-Huai
2009-01-01
The virtual instrument system based on LabVIEW 8.0 for ion analyzer which can measure and analyze ion concentrations in solution is developed and comprises homemade conditioning circuit, data acquiring board, and computer. It can calibrate slope, temperature, and positioning automatically. When applied to determine the reaction rate constant by pX, it achieved live acquiring, real-time displaying, automatical processing of testing data, generating the report of results; and other functions. This method simplifies the experimental operation greatly, avoids complicated procedures of manual processing data and personal error, and improves veracity and repeatability of the experiment results. PMID:19730752
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
Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji
2014-10-21
We report reaction paths starting from N({sup 2}D) + H{sub 2}O for doublet spin states, D{sub 0} and D{sub 1}. The potential energy surfaces are explored in an automated fashion using the global reaction route mapping strategy. The critical points and reaction paths have been fully optimized at the complete active space second order perturbation theory level taking all valence electrons in the active space. In addition to direct dissociation pathways that would be dominant, three roaming processes, two roaming dissociation, and one roaming isomerization: (1) H{sub 2}ON â†’ Hâ€“O(H)N â†’ Hâ€“HON â†’ NO({sup 2}Î ) + H{sub 2}, (2) cis-HNOH â†’ HNOâ€“H â†’ Hâ€“HNO â†’ NO + H{sub 2}, (3) H{sub 2}NO â†’ Hâ€“HNO â†’ HNOâ€“H â†’ trans-HNOH, are confirmed on the D{sub 0} surface.
Francés-Monerris, Antonio; Merchán, Manuela; Roca-Sanjuán, Daniel
2013-08-21
Addition of ?OH radicals to pyrimidine nucleobases is a common reaction in DNA/RNA damage by reactive oxygen species. Among several experimental techniques, transient absorption spectroscopy has been during the last decades used to characterize such compounds. Discrepancies have however appeared in the assignment of the adduct or adducts responsible for the reported transient absorption UV-Vis spectra. In order to get an accurate assignment of the transient spectra and a unified description of the absorption properties of the ?OH reaction products of pyrimidines, a systematic complete active space self-consistent field second-order perturbation (CASPT2//CASSCF) theory study has been carried out on the uracil, thymine, and cytosine ?OH addition adducts, as well as on the 5,6-dihydrouracil hydrogen abstraction products. With the obtained findings, the C5OH contributions to the lowest-energy band can be finally discarded. Instead, a bright (2)(?2) state of the C6OH adducts is determined to be the main responsible in all compounds for the absorption band in the Vis range. PMID:23968062
Factors Affecting Reaction Kinetics of Glucose Oxidase
NASA Astrophysics Data System (ADS)
Johnson, Kristin A.
2002-01-01
Basic principles of enzyme kinetics are demonstrated using the enzyme glucose oxidase. The glucose oxidase enzymatic reaction is coupled to horseradish peroxidase, which in turn catalyzes the oxidation of a dye to a bright blue-green color. The appearance of the blue-green dye is used to monitor the course of the reaction and is quite visible in a classroom setting. A series of reactions are arranged that vary the enzyme concentration, substrate concentration, temperature, and the substrate used in the reaction. By monitoring the rate of the color change in each beaker, the reaction kinetics of glucose oxidase in each series is observed.
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.
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
Kinetic Isotope Effects in Asymmetric Reactions
Giagou, Thomas; Meyer, Matthew P.
2010-01-01
Kinetic isotope effects are exquisitely sensitive probes of transition structure. As such, kinetic isotope effects offer a uniquely useful probe for the symmetry-breaking process that is inherent to stereoselective reactions. In this Concept article, we explore the role of steric and electronic effects in stereocontrol, and we relate these concepts to recent studies carried out in our laboratory. We also explore the way in which kinetic isotope effects serve as useful points of contact with computational models of transition structures. Finally, we discuss future opportunities for kinetic isotope effects to play a role in asymmetric catalyst development. PMID:20669194
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 aâ€¦
Radioactive iodine exchange reaction of HIPDM: kinetics and mechanism
Lui, B.; Chang, J.; Sun, J.S.; Billings, J.; Steves, A.; Ackerhalt, R.; Molnar, M.; Kung, H.F.
1987-03-01
In conjunction with single photon emission computed tomography (SPECT), iodine-123 (/sup 123/I)-labeled N,N,N'-trimethyl-(2-hydroxy-3-methyl-5-iodobenzyl)-1,3-propanediamine (HIPDM) has been used clinically as a regional cerebral perfusion imaging agent. The (/sup 123/I)HIPDM can be prepared by a simple aqueous exchange reaction in a kit form. We synthesized unlabeled HIPDM by condensation of 2-hydroxy-3-methyl-5-iodobezaldehyde and N,N,N'-trimethyl-1,3-propanediamine, followed by a sodium borohydride reduction reaction. The kinetics of the radioactive iodine exchange reaction for the preparation of (/sup 123/I)HIDM is controlled by the pH, the temperature, and the presence of reductant (sodium bisulfite), and oxidant (sodium iodate). The reaction is a second order iodine-iodine exchange with an activation energy of 30.6 kcal/mole. The mechanism of this reaction probably involves the formation of an active 1+ or iodine free radical, which is sensitive to the presence of a reductant, such as sodium bisulfite.
Radioactive iodine exchange reaction of HIPDM: kinetics and mechanism.
Lui, B; Chang, J; Sun, J S; Billings, J; Steves, A; Ackerhalt, R; Molnar, M; Kung, H F
1987-03-01
In conjunction with single photon emission computed tomography (SPECT), iodine-123 (123I)-labeled N,N,N'-trimethyl-[2-hydroxy-3-methyl-5-iodobenzyl]-1,3-propanediamine (HIPDM) has been used clinically as a regional cerebral perfusion imaging agent. The [123I]HIPDM can be prepared by a simple aqueous exchange reaction in a kit form. We synthesized unlabeled HIPDM by condensation of 2-hydroxy-3-methyl-5-iodobezaldehyde and N,N,N'-trimethyl-1,3-propanediamine, followed by a sodium borohydride reduction reaction. The kinetics of the radioactive iodine exchange reaction for the preparation of [123I]HIDM is controlled by the pH, the temperature, and the presence of reductant (sodium bisulfite), and oxidant (sodium iodate). The reaction is a second order iodine-iodine exchange with an activation energy of 30.6 kcal/mole. The mechanism of this reaction probably involves the formation of an active 1+ or iodine free radical, which is sensitive to the presence of a reductant, such as sodium bisulfite. PMID:3819852
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.
Kinetics of the reaction of hypobromous acid and organic matters in water treatment processes.
Echigo, S; Minear, R A
2006-01-01
The fate of bromine species from human activity is affected by the bromination reaction in water treatment processes. In this study, kinetic information of the reaction between hypobromous acid (HOBr) and seven different natural organic matters (NOM) was collected by sequential stopped-flow techniques. Multiple reaction phases were found in the reaction between HOBr and NOM. The number of reaction sites for the faster reaction phase ranged from 0.26 to 0.92 micromole (mg DOC)(-1), and was correlated to both SUVA and specific phenolic content at pH 7.0. The apparent second-order rate constants for the faster reaction phase at pH 7.0 ranged from 5.4 x 10(5) to 1.4 x 10(6) M(-1) x s(-1), indicating that vanillin-like structures are involved in this reaction phase. PMID:16862795
Second Order Symmetries of the Conformal Laplacian
NASA Astrophysics Data System (ADS)
Michel, Jean-Philippe; Radoux, Fabian; Šilhan, Josef
2014-02-01
Let (M,g) be an arbitrary pseudo-Riemannian manifold of dimension at least 3. We determine the form of all the conformal symmetries of the conformal (or Yamabe) Laplacian on (M,g), which are given by differential operators of second order. They are constructed from conformal Killing 2-tensors satisfying a natural and conformally invariant condition. As a consequence, we get also the classification of the second order symmetries of the conformal Laplacian. Our results generalize the ones of Eastwood and Carter, which hold on conformally flat and Einstein manifolds respectively. We illustrate our results on two families of examples in dimension three.
The curvature perturbation at second order
NASA Astrophysics Data System (ADS)
Dias, Mafalda; Elliston, Joseph; Frazer, Jonathan; Mulryne, David; Seery, David
2015-02-01
We give an explicit relation, up to second-order terms, between scalar-field fluctuations defined on spatially-flat slices and the curvature perturbation on uniform-density slices. This expression is a necessary ingredient for calculating observable quantities at second-order and beyond in multiple-field inflation. We show that traditional cosmological perturbation theory and the `separate universe' approach yield equivalent expressions for superhorizon wavenumbers, and in particular that all nonlocal terms can be eliminated from the perturbation-theory expressions.
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…
Urban Principals' Second Order Change Leadership
ERIC Educational Resources Information Center
Taylor, Rosemarye T.; La Cava, Gonzalo S.
2011-01-01
Urban school leaders have challenges in continually improving student achievement and making change as quickly as needed. To address this problem 37 non-Title I principals completed an on-line survey, Principal's Actions Survey (PAS), based on the seven responsibilities for second order change identified by Marzano, Waters, and McNulty (2005).…
Second order density perturbations for dust cosmologies
NASA Astrophysics Data System (ADS)
Uggla, Claes; Wainwright, John
2014-08-01
We present simple expressions for the relativistic first and second order fractional density perturbations for Friedmann-Lemaître cosmologies with dust, in four different gauges: the Poisson, uniform curvature, total matter and synchronous-comoving gauges. We include a cosmological constant and arbitrary spatial curvature in the background. A distinctive feature of our approach is our description of the spatial dependence of the perturbations using a canonical set of quadratic differential expressions involving an arbitrary spatial function that arises as a conserved quantity. This enables us to unify, simplify and extend previous seemingly disparate results. We use the primordial matter and metric perturbations that emerge at the end of the inflationary epoch to determine the additional arbitrary spatial function that arises when integrating the second order perturbation equations. This introduces a non-Gaussianity parameter into the expressions for the second order density perturbation. In the special case of zero spatial curvature we show that the time evolution simplifies significantly, and requires the use of only two nonelementary functions, the so-called growth suppression factor at the linear level, and one new function at the second order level. We expect that the results will be useful in applications, for example, studying the effects of primordial non-Gaussianity on the large scale structure of the Universe.
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 conditioningâ€¦
Stopped-flow kinetic analysis of the bacterial luciferase reaction.
Abu-Soud, H; Mullins, L S; Baldwin, T O; Raushel, F M
1992-04-21
The kinetics of the reaction catalyzed by bacterial luciferase have been measured by stopped-flow spectrophotometry at pH 7 and 25 degrees C. Luciferase catalyzes the formation of visible light, FMN, and a carboxylic acid from FMNH2, O2, and the corresponding aldehyde. The time courses for the formation and decay of the various intermediates have been followed by monitoring the absorbance changes at 380 and 445 nm along with the emission of visible light using n-decanal as the alkyl aldehyde. The synthesis of the 4a-hydroperoxyflavin intermediate (FMNOOH) was monitored at 380 nm after various concentrations of luciferase, O2, and FMNH2 were mixed. The second-order rate constant for the formation of FMNOOH from the luciferase-FMNH2 complex was found to be 2.4 x 10(6) M-1 s-1. In the absence of n-decanal, this complex decays to FMN and H2O2 with a rate constant of 0.10 s-1. The enzyme-FMNH2 complex was found to isomerize prior to reaction with oxygen. The production of visible light reaches a maximum intensity within 1 s and then decays exponentially over the next 10 s. The formation of FMN from the intermediate pseudobase (FMNOH) was monitored at 445 nm. This step of the reaction mechanism was inhibited by high levels of n-decanal which indicated that a dead-end luciferase-FMNOH-decanal could form. The time courses for these optical changes have been incorporated into a comprehensive kinetic model. Estimates for 15 individual rate constants have been obtained for this model by numeric simulations of the various time courses. PMID:1567836
Transient Kinetics of Slag Metal Reactions
NASA Astrophysics Data System (ADS)
Brooks, G. A.; Rhamdhani, M. A.; Coley, K. S.; Subagyo; Pan, Y.
2009-06-01
The kinetics of slag metal reactions are complex and often transient, in the sense that interfacial area, the equilibrium driving force, temperature gradients, and fluid properties are changing with time. This highly transient behavior is challenging to model using simple ordinary differential equations, and new theoretical approaches must be developed to deal with the complexity associated with these systems. Three examples from recent studies are described to illustrate methods of analyzing transient behavior. The first is desulfurization of steel in ladle metallurgy where the equilibrium driving force is changing with time, and the second is the case of reacting droplets in oxygen steelmaking where “bloating” of the droplet has a dramatic effect on the kinetics. The third is in the case of reactions between an alloy droplet and slag that result in large changes in interfacial area due to surface tension driven flows.
Calculating Second-Order Effects in MOSFET's
NASA Technical Reports Server (NTRS)
Benumof, Reuben; Zoutendyk, John A.; Coss, James R.
1990-01-01
Collection of mathematical models includes second-order effects in n-channel, enhancement-mode, metal-oxide-semiconductor field-effect transistors (MOSFET's). When dimensions of circuit elements relatively large, effects neglected safely. However, as very-large-scale integration of microelectronic circuits leads to MOSFET's shorter or narrower than 2 micrometer, effects become significant in design and operation. Such computer programs as widely-used "Simulation Program With Integrated Circuit Emphasis, Version 2" (SPICE 2) include many of these effects. In second-order models of n-channel, enhancement-mode MOSFET, first-order gate-depletion region diminished by triangular-cross-section deletions on end and augmented by circular-wedge-cross-section bulges on sides.
Second-Order Invariants and Holography
NASA Astrophysics Data System (ADS)
Luongo, Orlando; Bonanno, Luca; Iannone, Gerardo
2012-12-01
Motivated by recent works on the role of the holographic principle in cosmology, we relate a class of second-order Ricci invariants to the IR cutoff characterizing the holographic dark energy density. The choice of second-order invariants provides an invariant way to account the problem of causality for the correct cosmological cutoff, since the presence of event horizons is not an a priori assumption. We find that these models work fairly well, by fitting the observational data, through a combined cosmological test with the use of SNeIa, BAO and CMB. This class of models is also able to overcome the fine-tuning and coincidence problems. Finally, to make a comparison with other recent models, we adopt the statistical tests AIC and BIC.
Pole Assignment for Second-Order Systems
NASA Astrophysics Data System (ADS)
CHU, E. K.
2002-01-01
This paper contains some results for pole assignment problems for the second-order system M ?(t)+D ?(t)+K x (t)=B u (t) . Specifically, Algorithm 0 constructs feedback matrices F1 and F2 such that the closed-loop quadratic pencil Pc( ?)= ?2M+ ? ( D+ BF2)+( K+ BF1) has a desired set of eigenvalues and the associated eigenvectors are well-conditioned. The method is a modification of the SVD-based method proposed by Juang and Maghami [1, 2] which is a second-order adaptation of the well-known robust eigenvalue assignment method by Kautsky et al. [3] for first-order systems. Robustness is achieved by minimising some not-so-well-known condition numbers of the eigenvalues of the closed-loop second-order pencil. We next consider the partial pole assignment problem. In 1997, Datta, Elhay and Ram proposed three biorthogonality relations for eigenvectors of symmetric definite quadratic pencils [4]. One of these relations was used to derive an explicit solution to the partial pole assignment problem by state feedback for the related single-input symmetric definite second-order control system. The solution shed new light on the stabilisation and control of large flexible space structures, for which only one small subset of the spectrum needs to be reassigned while retaining the complementary part of the spectrum. In this paper, the method has been generalised for multi-input and non-symmetric quadratic pencils. Finally, we discuss briefly the output feedback pole assignment problem.
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
NASA Astrophysics Data System (ADS)
Brink, Jeandrew
2010-01-01
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.
Spacetime encodings. III. Second order Killing tensors
Brink, Jeandrew
2010-01-15
This paper explores the Petrov type D, stationary axisymmetric vacuum (SAV) spacetimes that were found by Carter to have separable Hamilton-Jacobi equations, and thus admit a second-order Killing tensor. The derivation of the spacetimes presented in this paper borrows from ideas about dynamical systems, and illustrates concepts that can be generalized to higher-order Killing tensors. The relationship between the components of the Killing equations and metric functions are given explicitly. The origin of the four separable coordinate systems found by Carter is explained and classified in terms of the analytic structure associated with the Killing equations. A geometric picture of what the orbital invariants may represent is built. Requiring that a SAV spacetime admits a second-order Killing tensor is very restrictive, selecting very few candidates from the group of all possible SAV spacetimes. This restriction arises due to the fact that the consistency conditions associated with the Killing equations require that the field variables obey a second-order differential equation, as opposed to a fourth-order differential equation that imposes the weaker condition that the spacetime be SAV. This paper introduces ideas that could lead to the explicit computation of more general orbital invariants in the form of higher-order Killing tensors.
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.
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.
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.
Kinetics of rouleau formation. II. Reversible reactions.
Samsel, R W; Perelson, A S
1984-01-01
Red blood cells aggregate face-to-face to form long, cylindrical, straight chains and sometimes branched structures called rouleaux. Here we extend a kinetic model developed by R. W. Samsel and A. S. Perelson (1982, Biophys. J. 37:493-514) to include both the formation and dissociation of rouleaux. We examine thermodynamic constraints on the rate constants of the model imposed by the principle of detailed balance. Incorporation of reverse reactions allows us to compute mean sizes of rouleaux and straight chain segments within rouleaux, as functions of time and at equilibrium. Using the Flory - Stockmayer method from polymer chemistry, we obtain a closed-form solution for the size distribution of straight chain segments within rouleaux at any point in the evolution of the reaction. The predictions of our theory compare favorably with data collected by D. Kernick , A.W.L. Jay , S. Rowlands , and L. Skibo (1973, Can. J. Physiol. Pharmacol. 51:690-699) on the kinetics of rouleau formation. When rouleaux grow large, they may contain rings or loops and take on the appearance of a network. We demonstrate the importance of including the kinetics of ring closure in the development of realistic models of rouleaux formation. Images FIGURE 1 FIGURE 13 PMID:6426540
NASA Astrophysics Data System (ADS)
Medien, H. A. A.
1996-11-01
A new and sensitive spectrophotometric method is described for the determination of p-benzoquinone, p-chloranil and 1.4-naphthoquinone. The method is based on the reaction between quinones and barbituric acid, by which a color is developed with maximum absorption between 485 and 555 nm in 50% methyl alcohol-water mixture. The absorption of the product obeys Beer's law within the concentration range 0.025-05 mM of orginal quinone. The kinetics of the reaction between p-benzoquinone and barbituric acid was studied in a range of methyl alcohol-water mixtures. The reaction follows overall second order kinetics, first order in each of the reactants. The rate increases with increasing dielectric constant. The method was applied for determination of barbituric acid with p-benzoquinone in the concentration range of 0.025-0.345 mM. Other barbiturates do not interfere.
Understanding arsenate reaction kinetics with ferric hydroxides.
Farrell, James; Chaudhary, Binod K
2013-08-01
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
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
Second order Kerr-Newman time delay
NASA Astrophysics Data System (ADS)
He, G.; Lin, W.
2016-01-01
The explicit form for the post-Newtonian gravitational time delay of light signals propagating on the equatorial plane of a Kerr-Newman black hole is derived. Based on the null geodesic in Kerr-Newman spacetime, we adopt the iterative method to calculate the time delay. Our result reduces to the previous formulation for the Kerr black hole if we drop the contribution from the electrical charge. Our time-delay formula for the Reissner-Nordström geometry is different from the previous publication [Phys. Rev. D 69, 023002 (2004)], in which the largest second order contribution to the time delay is missing.
Robust stability of second-order systems
NASA Technical Reports Server (NTRS)
Chuang, C. H.
1993-01-01
This report presents a robust control design using strictly positive realness for second-order dynamic systems. The robust strictly positive real controller allows the system to be stabilized with only acceleration measurements. An important property of this design is that stabilization of the system is independent of the system parameters. The control design connects a virtual system to the given plant. The combined system is positive real regardless of system parameter uncertainty. Then any strictly positive real controllers can be used to achieve robust stability. A spring-mass system example and its computer simulations are presented to demonstrate this controller design.
Second-order conditioning in Drosophila
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 (SOC) protocol that further demonstrates the flexibility of fly behavior. In SOC, a previously conditioned stimulus (CS1) is used as reinforcement for a second conditioned stimulus (CS2) in associative learning. This higher-order context presents an opportunity for reassessing the roles of known learning and memory genes and neuronal networks in a new behavioral paradigm. PMID:21441302
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.
Iterative second-order optical eigenmode imaging
NASA Astrophysics Data System (ADS)
Zhang, Suzhen; Wang, Wei; Yu, Rong; Yang, Xiaoxue
2016-01-01
Optical eigenmode imaging (OEI) reconstructs a complex object by using the orthogonality of optical eigenmodes. The image quality of OEI is limited by the missing of high-order eigenmodes. Here, we propose a universal method to improve the image quality of OEI by applying the iterative operation on the image collected by the second-order OEI (SOEI). The numerical simulations show that both the detrimental side bands and the position dependence of the point spread function by using OEI are largely mitigated.
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.
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
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.
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.
Reaction rates for mesoscopic reaction-diffusion kinetics
NASA Astrophysics Data System (ADS)
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.
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.
Preparation of a copolymer for second-order nonlinear optics
NASA Astrophysics Data System (ADS)
Albu, Ana M.; Marculescu, Bogdan; Manaila-Maximean, Doina; Trouillet, Alain
2000-02-01
During the last decade the interest in polymeric material for second-order nonlinear optical properties has been constantly growing. They combine structural electronic properties, with good thermal and mechanical stability, a relatively low cost and easy processability. The second order nonlinear optical (NLO) properties of such materials have electronic origin, with an ultra-fast response time. In the present paper, we report the preparation and characterization of a new material with a higher concentration of a NLO chromophore. We have synthesized a new dye monomer by the phase transfer catalyzed reaction. We have prepared the copolymer with styrene, by bulk copolymerization; the initiator was di-t-butyl peroxide at 120 degrees C. We have characterized the monomer and the copolymer by IR; UV-Vis; H-NMR spectroscopy. The glass transition temperature and the melting point have been obtained using the differential scanning calorimetry. For studying the NLO properties, the samples have been poled by the Corona poling method, in an electric field of approximately 100V/micrometers . We have appreciated the second- order nonlinear coefficient by comparing the light signal passing through the sample, with the signal passing through a standard quartz plate.
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.
Development of a second order closure model for computation of turbulent diffusion flames
NASA Technical Reports Server (NTRS)
Varma, A. K.; Donaldson, C. D.
1974-01-01
A typical eddy box model for the second-order closure of turbulent, multispecies, reacting flows developed. The model structure was quite general and was valid for an arbitrary number of species. For the case of a reaction involving three species, the nine model parameters were determined from equations for nine independent first- and second-order correlations. The model enabled calculation of any higher-order correlation involving mass fractions, temperatures, and reaction rates in terms of first- and second-order correlations. Model predictions for the reaction rate were in very good agreement with exact solutions of the reaction rate equations for a number of assumed flow distributions.
Kinetic analysis of free-radical reactions in the low-temperature autoxidation of triglycerides
Zhu, Jingmin; Sevilla, M.D. )
1990-02-22
The kinetics of the low-temperature autoxidation of triglycerides has been investigated by electron spin resonance spectroscopy. After initial radical production, four reaction stages are found in the overall autoxidation of unsaturated lipids: (1) formation of peroxyl radicals by addition of molecular oxygen to the initial carbon radicals, (2) consumption of oxygen in the autoxidation cycle, (3) decay of the lipid peroxyl radical into allylic and pentadienyl radicals, and (4) recombination of the carbon-centered radicals. Peroxyl radical decay in saturated lipids follows second-order kinetics with an apparent activation energy of ca. 50 kJ/mol. The authors find that, for polyunsaturated lipids, even at quite low temperatures (120 K), the autoxidation process occurs readily and must be considered in the storage of biological samples.
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…
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 toâ€¦
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)
Second-Order Nonlinear Optical Imaging of Chiral Crystals
Kissick, David J.; Wanapun, Debbie; Simpson, Garth J.
2012-01-01
Second-order nonlinear optical imaging of chiral crystals (SONICC) is an emerging technique for crystal imaging and characterization. We provide a brief overview of the origin of second harmonic generation signals in SONICC and discuss recent studies using SONICC for biological applications. Given that they provide near-complete suppression of any background, SONICC images can be used to determine the presence or absence of protein crystals through both manual inspection and automated analysis. Because SONICC creates high-resolution images, nucleation and growth kinetics can also be observed. SONICC can detect metastable, homochiral crystalline forms of amino acids crystallizing from racemic solutions, which confirms Ostwaldâ€™s rule of stages for crystal growth. SONICCâ€™s selectivity, based on order, and sensitivity, based on background suppression, make it a promising technique for numerous fields concerned with chiral crystal formation. PMID:21469954
Sreedhara, S.; Huh, Kang Y.
2005-12-01
The performance of second-order conditional moment closure (CMC) depends on models to evaluate conditional variances and covariances of temperature and species mass fractions. In this paper the closure schemes based on the steady laminar flamelet model (SLFM) are validated against direct numerical simulation (DNS) involving extinction and ignition. Scaling is performed to reproduce proper absolute magnitudes, irrespective of the origin of mismatch between local flamelet structures and scalar dissipation rates. DNS based on the pseudospectral method is carried out to study hydrogen-air combustion with a detailed kinetic mechanism, in homogeneous, isotropic, and decaying turbulent media. Lewis numbers are set equal to unity to avoid complication of differential diffusion. The SLFM-based closures for correlations among fluctuations of reaction rate, scalar dissipation rate, and species mass fractions show good comparison with DNS. The variance parameter in lognormal PDF and the constants in the dissipation term have been estimated from DNS results. Comparison is made for the resulting conditional profiles from DNS, first-order CMC, and second-order CMC with correction to the most critical reaction step according to sensitivity analysis. Overall good agreement ensures validity of the SLFM-based closures for modeling conditional variances and covariances in second-order CMC.
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 theâ€¦
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…
Kinetic Profiling of Catalytic Organic Reactions as a Mechanistic Tool.
Blackmond, Donna G
2015-09-01
The use of modern kinetic tools to obtain virtually continuous reaction progress data over the course of a catalytic reaction opens up a vista that provides mechanistic insights into both simple and complex catalytic networks. Reaction profiles offer a rate/concentration scan that tells the story of a batch reaction time course in a qualitative "fingerprinting" manner as well as in quantitative detail. Reaction progress experiments may be mathematically designed to elucidate catalytic rate laws from only a fraction of the number of experiments required in classical kinetic measurements. The information gained from kinetic profiles provides clues to direct further mechanistic analysis by other approaches. Examples from a variety of catalytic reactions spanning two decades of the author's work help to delineate nuances on a central mechanistic theme. PMID:26285166
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)
Simulations of the reaction kinetics on nanometer supported catalyst particles
NASA Astrophysics Data System (ADS)
Zhdanov, V. P.; Kasemo, B.
2000-07-01
Real catalysts frequently consist of nm-sized (1-100 nm) metal particles deposited on the internal surface of a more or less inactive porous support. The complexity of such systems in combination with relatively high (atmospheric) reactant pressures, typical for practical catalysis, hinders the application of surface science methods to their full potential and makes it difficult to interpret the measured reaction kinetics on the basis of kinetic data for single-crystal samples. To bridge these pressure and structure gaps and to form a conceptual basis for the understanding of reactions occurring on supported catalyst, we have performed simulations scrutinizing qualitatively new effects in the reaction kinetics on the nm scale. The attention is focused on the particle size range, where the catalyst particles have reached sufficient size to essentially have the electronic properties of bulk crystals, but where they are still small enough that the kinetic effects connected with the particle size are important. We treat in detail such factors inherent for nm chemistry as reactant supply via the support, interplay of the reaction kinetics on different facets of supported particles due to interfacet diffusion, adsorbate-induced reshaping of catalyst particles, and oscillation and chaos on the nm scale. All these factors are demonstrated to be especially important in the case of rapid catalytic reactions occurring far from the adsorption-desorption equilibrium. The kinetics of chemically induced Ostwald ripening of nm catalyst particles and also the gas-phase diffusion limitations in reactions on model supported nm catalysts, prepared by employing electron beam lithography, are discussed as well. As a general conclusion, we find that kinetic effects alone (i.e., no special kinetic effects or "active sites") can cause large differences in reaction kinetics on nm particles and single crystals. Practical consequences and experimental opportunities to measure these effects are briefly discussed.
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, fourâ€¦
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…
Second-Order Model to Predict Microbial Degradation of Organic Compounds in Natural Waters
Paris, Doris F.; Steen, William C.; Baughman, George L.; Barnett, John T.
1981-01-01
The reliability of second-order rate constants for assessing microbial degradation kinetics in natural waters was examined by using three compounds that undergo hydrolytic degradation. The butoxyethyl ester of 2,4-dichlorophenoxyacetic acid was studied in water samples from 31 sites, malathion was examined in water from 14 sites, and chlorpropham was studied in samples from 11 sites. The coefficient of variation for rate constants for each compound was less than 65% over all sites. Additional studies indicated that the rate conformed to second-order kinetics; that is, the rate was proportional to both bacterial and xenobiotic concentrations. PMID:16345729
Karlesa, Anggita; De Vera, Glen Andrew D; Dodd, Michael C; Park, Jihye; Espino, Maria Pythias B; Lee, Yunho
2014-09-01
Oxidation of ?-lactam antibiotics by aqueous ferrate(VI) was investigated to determine reaction kinetics, reaction sites, antibacterial activity changes, and transformation products. Apparent second-order rate constants (kapp) were determined in the pH range 6.0-9.5 for the reaction of ferrate(VI) with penicillins (amoxicillin, ampicillin, cloxacillin, and penicillin G), a cephalosporin (cephalexin), and several model compounds. Ferrate(VI) shows an appreciable reactivity toward the selected ?-lactams (kapp for pH 7 = 110-770 M(-1) s(-1)). The pH-dependent kapp could be well explained by considering species-specific reactions between ferrate(VI) and the ?-lactams (with reactions occurring at thioether, amine, and/or phenol groups). On the basis of the kinetic results, the thioether is the main reaction site for cloxacillin and penicillin G. In addition to the thioether, the amine is a reaction site for ampicillin and cephalexin, and amine and phenol are reaction sites for amoxicillin. HPLC/MS analysis showed that the thioether of ?-lactams was transformed to stereoisomeric (R)- and (S)-sulfoxides and then to a sulfone. Quantitative microbiological assay of ferrate(VI)-treated ?-lactam solutions indicated that transformation products resulting from the oxidation of cephalexin exhibited diminished, but non-negligible residual activity (i.e., ?24% as potent as the parent compound). For the other ?-lactams, the transformation products showed much lower (<5%) antibacterial potencies compared to the parent compounds. Overall, ferrate(VI) oxidation appears to be effective as a means of lowering the antibacterial activities of ?-lactams, although alternative approaches may be necessary to achieve complete elimination of cephalosporin activities. PMID:25073066
Kinetics of the Fischer-Tropsch reaction.
Markvoort, Albert J; van Santen, Rutger A; Hilbers, Peter A J; Hensen, Emiel J M
2012-09-01
Long carbon chains: Self-assembly of monomeric carbon intermediates into long-chain hydrocarbons on catalytically reactive surface was studied when full reversibility of the chain growth is included in the kinetic model. Using BrÃ¸nsted-Evans-Polanyi relations, the maximum chain growth as a function of the surface reactivity is predicted. PMID:22829559
Second-order electro-optic effect in diamond.
NASA Technical Reports Server (NTRS)
Anastassakis, E.; Burstein, E.
1971-01-01
Observation of a second-order electrooptic effect in diamond, leading to the determination of an order of magnitude for the appropriate second-order electrooptic coefficient of diamond. A linear effect, forbidden by symmetry, is also observed and attributed to random residual strains, an average estimate of which is obtained as .00001 for the particular sample used in this experiment. Birefringence due to second-order dispersion effects is also discussed.
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.
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
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.
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.
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.
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…
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.
Reaction kinetics between fiber and matrix
NASA Technical Reports Server (NTRS)
Kopp, M. W.; Tien, J. K.; Petrasek, D. W.
1988-01-01
Interdiffusion and interdiffusion controlled intermediate phase formation in metal matrix composites can be of interest for the prolonged application of these systems at high temperatures. Methods are discussed that address the kinetics of interdiffusion in systems that exhibit solid solution intermixing or the formation of a third intermediate phase at the fiber/matrix interface, or both. The tungsten fiber reinforced niobium and tungsten fiber reinforced superalloy systems are employed as model systems for experimentation and discussion. In an effort to impede interdiffusion, the concept of ion implanted diffusion barriers have been examined. Preliminary results on the feasibility and effectiveness of ion implanted diffusion barriers are presented.
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.
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.
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
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
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.
NASA Astrophysics Data System (ADS)
Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief
2015-12-01
Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60Â°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60Â°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.
Oxidation of diclofenac by potassium ferrate (VI): reaction kinetics and toxicity evaluation.
Wang, Yingling; Liu, Haijin; Liu, Guoguang; Xie, Youhai; Gao, Shuyan
2015-02-15
The reaction kinetics and toxicity of diclofenac (DCF) oxidation by ferrate (VI) under simulated water disinfection conditions were investigated. Experimental results indicated that the reaction between DCF and Fe(VI) followed first-order kinetics with respect to each reactant. Furthermore, the effects of pH and temperature on DCF oxidation by Fe(VI) were elucidated using a systematic examination. The apparent second-order rate constants (kapp) increased significantly from 2.54 to 11.6M(-1)s(-1), as the pH of the solution decreased from 11.0 to 7.0, and the acid-base equilibriums of Fe(VI) and DCF were proposed to explain the pH dependence of kapp. The acute toxicity of DCF solution during Fe(VI) oxidation was evaluated using a Microtox bioassay. Overall, the DCF degradation process resulted in a rapid increase of the inhibition rate of luminescent bacteria. These toxicity tests suggest that the formation of enhanced toxic intermediates during the Fe(VI) disinfection process may pose potential health risk to consumers. PMID:25460958
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.
Study of second order upwind differencing in a recirculating flow
NASA Technical Reports Server (NTRS)
Vanka, S. P.
1985-01-01
The accuracy and stability of the second order upwind differencing scheme was investigated. The solution algorithm employed is based on a coupled solution of the nonlinear finite difference equations by the multigrid technique. Calculations have been made of the driven cavity flow for several Reynolds numbers and finite difference grids. In comparison with the hybrid differencing, the second order upwind differencing is somewhat more accurate but it is not monotonically accurate with mesh refinement. Also, the convergence of the solution algorithm deteriorates with the use of the second order upwind differencing.
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.
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
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.
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.
Fast second-order consensus via predictive mechanisms
NASA Astrophysics Data System (ADS)
Wu, Jie; Zhang, Li-Yi; Bai, Yu
2015-01-01
In this paper, we discuss second-order consensus problems for multi-agent systems with dynamic agents and fixed topologies. A new second-order consensus protocol incorporating the predictive mechanism is proposed and a convergence analysis related to the real and imaginary parts of the eigenvalues of the Laplacian matrix of the corresponding network is provided. We establish a direct connection between the eigenvalues of the Laplacian matrix and parameters of the proposed second-order consensus model, and we compute a lower bound for the sum of parameters. It is proved under general conditions related to the second-order consensus protocol and the network topology that the asymptotic consensus is achieved and the convergence speed is increased via designing a state predictor. Finally, simulation results are provided to verify the effectiveness of the proposed protocol and the analytical claims.
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.
A Numerical Method for Differential Equations of Second Order
NASA Astrophysics Data System (ADS)
Cui, Douxing; Huang, Tian-Yi
1993-04-01
A new algorithm of order five is presented for the solution of the initial value problem where the system of ordinary differential equations is of second order and does not contain the first derivative.
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.
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.
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.
Second-order-accurate radiative hydrodynamics and multidimensional protostellar collapse
NASA Astrophysics Data System (ADS)
Boss, Alan P.; Myhill, Elizabeth A.
1995-08-01
A second-order-accurate numerical scheme for computing the radiative hydrodynamics of three-dimensional, collapsing protostellar clouds has been developed and implemented in both spherical and cartesian coordinates. The scheme employs spatially second-order-accurate advective fluxes based on van Leer monotonic interpolation and consistent advection. The advective fluxes also contain the terms necessary to make the scheme temporally second-order-accurate in the presence of spatially and temporally varying velocity fields. A predictor-corrector treatment of the source terms completes the requirements for second-order accuracy in time. The Poisson equation for the gravitational potential is solved by either a spherical harmonic expansion or a Green's function method. Radiative transfer in the Eddington approximation is handled through the solution of a mean intensity equation. The numerical scheme has been shown to be second-order-accurate through convergence testing and has been shown to improve the performance on a shock propagation problem compared to schemes that do not contain the spatially and temporally second-order-accurate terms.
Second-order gauge-invariant perturbations during inflation
Finelli, F.; Marozzi, G.; Vacca, G. P.; Venturi, G.
2006-10-15
The evolution of gauge invariant second-order scalar perturbations in a general single field inflationary scenario are presented. Different second-order gauge-invariant expressions for the curvature are considered. We evaluate perturbatively one of these second order curvature fluctuations and a second-order gauge-invariant scalar field fluctuation during the slow-roll stage of a massive chaotic inflationary scenario, taking into account the deviation from a pure de Sitter evolution and considering only the contribution of super-Hubble perturbations in mode-mode coupling. The spectra resulting from their contribution to the second order quantum correlation function are nearly scale-invariant, with additional logarithmic corrections with respect to the first order spectrum. For all scales of interest the amplitude of these spectra depends on the total number of e-folds. We find, on comparing first and second order perturbation results, an upper limit to the total number of e-folds beyond which the two orders are comparable.
Kinetic study of the indomethacin synthesis and thermal decomposition reactions.
Rusu, M; Olea, M; Rusu, D
2000-12-01
The kinetics of indomethacin synthesis (achieved through a new method) was studied at 80 degrees C. The reaction proceeds in four steps. In the first step, by the condensation of levulinic acid with p-chlorobenzoyl-p-methoxy-phenyl-hydrazine in homogeneous acidic catalysis an intermediate is formed. In the second step, by the isomerisation of this intermediate a hydrazo compound is formed. In the third step, the isomerisation is followed by the o-benzydinic transposition of the reaction product mentioned above. In the fourth step, indomethacin is formed through a cyclization reaction. The rate constant of the indomethacin synthesis reaction was determined assuming that the cyclization reaction constitutes the rate-determining step. Spectrophotometric methods were used both in order to investigate the kinetics of the synthesis reaction and to verify the proposed mechanism. Then, a thermogravimetric study was performed on the purpose of finding out the temperature range in which indomethacin is stable. From the thermogravimetric curve kinetic parameters have been derived, using different calculation techniques. PMID:11108535
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...
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...
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)
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.
Palm fatty acid biodiesel: process optimization and study of reaction kinetics.
Yadav, Praveen K S; Singh, Onkar; Singh, R P
2010-01-01
The relatively high cost of refined oils render the resulting fuels unable to compete with petroleum derived fuel. In this study, biodiesel is prepared from palm fatty acid (PFA) which is a by-product of palm oil refinery. The process conditions were optimized for production of palm fatty acid methyl esters. A maximum conversion of 94.4% was obtained using two step trans-esterification with 1:10 molar ratio of oil to methanol at 65Â°C. Sulfuric acid and Sodium hydroxide were used as acid and base catalyst respectively. The composition of fatty acid methyl esters (FAME) obtained was similar to that of palm oil. The biodiesel produced met the established specifications of biodiesel of American Society for Testing and Materials (ASTM). The kinetics of the trans-esterification reaction was also studied and the data reveals that the reaction is of first order in fatty acid and methanol (MeOH) and over all the reaction is of second order. PMID:20972357
Reaction kinetics of CO2 absorption in to phosphonium based anion-functionalized ionic liquids.
Gurkan, Burcu E; Gohndrone, Thomas R; McCready, Mark J; Brennecke, Joan F
2013-05-28
The reaction kinetics between CO2 and trihexyl(tetradecyl)phosphonium ([P66614])-based ionic liquids (ILs) with prolinate ([Pro]), 2-cyanopyrrolide ([2-CNpyr]), and 3-(trifluoromethyl)pyrazolide ([3-CF3pyra]) anions are studied at temperatures from 22-60 Â°C. The absorption of CO2 is carried out in a stirred reactor under pseudo first order conditions. ILs are diluted to concentrations of 0.05, 0.1 and 0.15 M with tetraglyme--a nonreactive, low volatility solvent with much lower viscosity than the ILs. Physical solubility of CO2 in the mixtures is calculated using correlations developed from CO2 solubility measurements in tetraglyme and the N2O-analogy for ILs and dilute IL solutions. The diffusivity of CO2 is estimated from viscosity-dependent correlations chosen after a thorough literature review. The results indicate partial first order reaction kinetics with respect to IL with values ranging from 19,500 L mol(-1) s(-1) ([P66614][Pro]) to 3200 L mol(-1) s(-1) ([P66614][3-CF3pyra]) at 22 Â°C. The second order reaction rate constants follow Arrhenius behavior with the highest activation energy of 43 kJ mol(-1) measured for [P66614][Pro]. ILs with aprotic heterocylic anions (AHA), on the other hand, show small activation energies of 18 and 11 kJ mol(-1) for [P66614][3-CF3pyra] and [P66614][2-CNpyr], respectively. The ILs studied in this work exhibit reactivity comparable to or higher than common aqueous amines. High reaction rates and tunable capacity make ILs, and AHA ILs in particular, attractive solvents for CO2 separations. PMID:23598368
Spatial variances of wind fields and their relation to second-order structure functions and spectra
NASA Astrophysics Data System (ADS)
Vogelzang, Jur; King, Gregory P.; Stoffelen, Ad
2015-02-01
Kinetic energy variance as a function of spatial scale for wind fields is commonly estimated either using second-order structure functions (in the spatial domain) or by spectral analysis (in the frequency domain). Both techniques give an order-of-magnitude estimate. More accurate estimates are given by a statistic called spatial variance. Spatial variances have a clear interpretation and are tolerant for missing data. They can be related to second-order structure functions, both for discrete and continuous data. Spatial variances can also be Fourier transformed to yield a relation with spectra. The flexibility of spatial variances is used to study various sampling strategies, and to compare them with second-order structure functions and spectral variances. It is shown that the spectral sampling strategy is not seriously biased to calm conditions for scatterometer ocean surface vector winds. When the second-order structure function behaves like rp, its ratio with the spatial variance equals >(p+1>)>(p+2>). Ocean surface winds in the tropics have p between 2/3 and 1, so one-sixth to one-fifth of the second-order structure function value is a good proxy for the cumulative variance.
Spatial Variances of Wind Fields and Their Relation to Second-Order Structure Functions and Spectra
NASA Astrophysics Data System (ADS)
King, G. P.; Vogelzang, J.; Stoffelen, A.; Portabella, M.
2014-12-01
Kinetic energy variance as a function of spatial scale for wind fields is commonly estimated either using second-order structure functions (in the spatial domain) or by spectral analysis (in the frequency domain). It will be demonstrated that neither spectra nor second-order structure functions offer a good representation of the variance as a function of scale. These difficulties can be circumvented by using a statistical quantity called spatial variance. It combines the advantages of spectral analysis and spatial statistics. In particular, when applied to observations, spatial variances have a clear interpretation and are tolerant for missing data. They can be related to second-order structure functions, both for discrete and continuous data. For data sets without missing points the relation is statistically exact. Spatial variances can also be Fourier transformed to yield a relation with spectra. The flexibility of spatial variances is used to study various sampling strategies, and to compare them with second-order structure functions and spectral variances. It is shown that the spectral sampling strategy is not seriously biased to calm conditions for scatterometer ocean surface vector winds, and that one-fifth of the second-order structure function value is a good proxy for the cumulative variance.
Pulsed ion beam investigation of the kinetics of surface reactions
NASA Technical Reports Server (NTRS)
Horton, C. C.; Eck, T. G.; Hoffman, R. W.
1989-01-01
Pulsed ion beam measurements of the kinetics of surface reactions are discussed for the case where the width of the ion pulse is comparable to the measured reaction time, but short compared to the time between successive pulses. Theoretical expressions are derived for the time dependence of the ion-induced signals for linear surface reactions. Results are presented for CO emission from surface carbon and CF emission from Teflon induced by oxygen ion bombardment. The strengths and limitations of this technique are described.
Radical scavenging reaction kinetics with multiwalled carbon nanotubes
Tsuruoka, Shuji; Matsumoto, Hidetoshi; Koyama, Kenichi; Akiba, Eiji; Yanagisawa, Takashi; Cassee, Flemming R.; Saito, Naoto; Usui, Yuki; Kobayashi, Shinsuke; Porter, Dale W.; Castranova, Vincent; Endo, Morinobu
2016-01-01
Progress in the development of carbon nanotubes (CNTs) has stimulated great interest among industries providing new applications. Meanwhile, toxicological evaluations on nanomaterials are advancing leading to a predictive exposure limit for CNTs, which implies the possibility of designing safer CNTs. To pursue safety by design, the redox potential in reactions with CNTs has been contemplated recently. However, the chemical reactivity of CNTs has not been explored kinetically, so that there is no scheme to express a redox reaction with CNTs, though it has been investigated and reported. In addition, the reactivity of CNTs is discussed with regard to impurities that consist of transition metals in CNTs, which obfuscates the contribution of CNTs to the reaction. The present work aimed at modeling CNT scavenging in aqueous solution using a kinetic approach and a simple first-order reaction scheme. The results show that CNTs follow the redox reaction assumption in a simple chemical system. As a result, the reaction with multiwalled CNTs is semi-quantitatively denoted as redox potential, which suggests that their biological reactions may also be evaluated using a redox potential scheme.
Kinetic modeling of electro-Fenton reaction in aqueous solution.
Liu, H; Li, X Z; Leng, Y J; Wang, C
2007-03-01
To well describe the electro-Fenton (E-Fenton) reaction in aqueous solution, a new kinetic model was established according to the generally accepted mechanism of E-Fenton reaction. The model has special consideration on the rates of hydrogen peroxide (H(2)O(2)) generation and consumption in the reaction solution. The model also embraces three key operating factors affecting the organic degradation in the E-Fenton reaction, including current density, dissolved oxygen concentration and initial ferrous ion concentration. This analytical model was then validated by the experiments of phenol degradation in aqueous solution. The experiments demonstrated that the H(2)O(2) gradually built up with time and eventually approached its maximum value in the reaction solution. The experiments also showed that phenol was degraded at a slow rate at the early stage of the reaction, a faster rate during the middle stage, and a slow rate again at the final stage. It was confirmed in all experiments that the curves of phenol degradation (concentration vs. time) appeared to be an inverted "S" shape. The experimental data were fitted using both the normal first-order model and our new model, respectively. The goodness of fittings demonstrated that the new model could better fit the experimental data than the first-order model appreciably, which indicates that this analytical model can better describe the kinetics of the E-Fenton reaction mathematically and also chemically. PMID:17258788
Second-order quasinormal mode of the Schwarzschild black hole
Nakano, Hiroyuki; Ioka, Kunihito
2007-10-15
We formulate and calculate the second-order quasinormal modes (QNMs) of a Schwarzschild black hole (BH). Gravitational waves (GW) from a distorted BH, the so-called ringdowns, are well understood as QNMs in general relativity. Since QNMs from binary BH mergers will be detected with a high signal-to-noise ratio by GW detectors, it is also possible to detect the second perturbative order of QNMs, generated by nonlinear gravitational interaction near the BH. In the BH perturbation approach, we derive the master Zerilli equation for the metric perturbation to second order and explicitly regularize it at the horizon and spatial infinity. We numerically solve the second-order Zerilli equation by implementing the modified Leaver continued fraction method. The second-order QNM frequencies are found to be twice the first-order ones, and the GW amplitude is up to {approx}10% that of the first order for the binary BH mergers. Since the second-order QNMs always exist, we can use their detections (i) to test the nonlinearity of general relativity, in particular, the no-hair theorem, (ii) to remove fake events in the data analysis of QNM GWs, and (iii) to measure the distance to the BH.
Children's understanding of second-order mental states.
Miller, Scott A
2009-09-01
The most popular topic in theory-of-mind research has been first-order false belief: the realization that it is possible to hold false beliefs about events in the world. A more advanced development is second-order false belief: the realization that it is possible to hold a false belief about someone else's belief. This article reviews research directed to second-order false belief and other forms of higher order, recursive mentalistic reasoning. Three general issues are considered. Research directed to developmental changes indicates that preschoolers typically fail second-order tasks and that success emerges at about age 5 or 6, although results vary some with method of assessment. Research directed to the consequences of second-order competence has revealed positive relations with a number of other aspects of children's development. Finally, measures of both language and executive function relate positively to performance on second-order tasks; the causal bases for the correlations, however, remain to be established. This article concludes with suggestions for future research. PMID:19702381
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
Reaction kinetics of some important site-specific endonucleases.
Hinsch, B; Kula, M R
1981-01-01
Reaction kinetics of the site-specific endonucleases BamHI, BgIII, C1aI, EcoRI, HpaII, PstI, SaII, SmaI, and XorII were investigated employing some frequently used substrates. Six of these enzymes could be analyzed under steady-state conditions. Kinetic data were obtained from progress curves applying an integrated Michaelis-Menten equation. KM ranged from 4 x 10(-9) M to 4 x 10(-11) M. Activities also spanned two orders of magnitude. In the case of C1aI the analysis of the pre-steady-state kinetics ("burst reaction") allowed the assessment of several rate constants. The rate-limiting step is the very slow dissociation of the enzyme-product complex (0.22 min(-1)). This complex is formed from the enzyme-bound nicked intermediate at a rate of 1.7 min(-1). The introduction of the first cut is again faster by a factor of about 6. SmaI and XorII resembled C1aI in their kinetics. The burst reaction can be used for the easy and unambiguous determination of molar concentrations of site-specific endonucleases in any preparation, which is free of non-specific DNases. PMID:6269074
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.
A unifying kinetic framework for modeling oxidoreductase-catalyzed reactions
Chang, Ivan; Baldi, Pierre
2013-01-01
Motivation: Oxidoreductases are a fundamental class of enzymes responsible for the catalysis of oxidationâ€“reduction reactions, crucial in most bioenergetic metabolic pathways. From their common root in the ancient prebiotic environment, oxidoreductases have evolved into diverse and elaborate protein structures with specific kinetic properties and mechanisms adapted to their individual functional roles and environmental conditions. While accurate kinetic modeling of oxidoreductases is thus important, current models suffer from limitations to the steady-state domain, lack empirical validation or are too specialized to a single system or set of conditions. Results: To address these limitations, we introduce a novel unifying modeling framework for kinetic descriptions of oxidoreductases. The framework is based on a set of seven elementary reactions that (i) form the basis for 69 pairs of enzyme state transitions for encoding various specific microscopic intra-enzyme reaction networks (micro-models), and (ii) lead to various specific macroscopic steady-state kinetic equations (macro-models) via thermodynamic assumptions. Thus, a synergistic bridge between the micro and macro kinetics can be achieved, enabling us to extract unitary rate constants, simulate reaction variance and validate the micro-models using steady-state empirical data. To help facilitate the application of this framework, we make available RedoxMech: a Mathematicaâ„¢ software package that automates the generation and customization of micro-models. Availability: The Mathematicaâ„¢ source code for RedoxMech, the documentation and the experimental datasets are all available from: http://www.igb.uci.edu/tools/sb/metabolic-modeling. Contact: pfbaldi@ics.uci.edu Supplementary information: Supplementary data are available at Bioinformatics online. PMID:23613486
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
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.
Weak value amplification via second-order correlated technique
NASA Astrophysics Data System (ADS)
Ting, Cui; Jing-Zheng, Huang; Xiang, Liu; Gui-Hua, Zeng
2016-02-01
We propose a new framework combining weak measurement and second-order correlated technique. The theoretical analysis shows that weak value amplification (WVA) experiment can also be implemented by a second-order correlated system. We then build two-dimensional second-order correlated function patterns for achieving higher amplification factor and discuss the signal-to-noise ratio influence. Several advantages can be obtained by our proposal. For instance, detectors with high resolution are not necessary. Moreover, detectors with low saturation intensity are available in WVA setup. Finally, type-one technical noise can be effectively suppressed. Project supported by the Union Research Centre of Advanced Spaceflight Technology (Grant No. USCAST2013-05), the National Natural Science Foundation of China (Grant Nos. 61170228, 61332019, and 61471239), and the High-Tech Research and Development Program of China (Grant No. 2013AA122901).
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.
Second order perturbations during inflation beyond slow-roll
Huston, Ian; Malik, Karim A. E-mail: k.malik@qmul.ac.uk
2011-10-01
We numerically calculate the evolution of second order cosmological perturbations for an inflationary scalar field without resorting to the slow-roll approximation or assuming large scales. In contrast to previous approaches we therefore use the full non-slow-roll source term for the second order Klein-Gordon equation which is valid on all scales. The numerical results are consistent with the ones obtained previously where slow-roll is a good approximation. We investigate the effect of localised features in the scalar field potential which break slow-roll for some portion of the evolution. The numerical package solving the second order Klein-Gordon equation has been released under an open source license and is available for download.
The second order Raman spectroscopy in carbon crystallinity
NASA Astrophysics Data System (ADS)
Lee, Young-Jae
2004-02-01
Cellulose was heated in the absence/presence of B to determine crystallinity changes due to heat treatment and B doping with the objectives of evaluating the characteristics of the second order Raman spectroscopy in comparison with X-ray diffraction (XRD) and the first order Raman spectroscopy. The crystallinity determined by XRD was similar to those of the first order Raman spectroscopy; crystallinity increases as heat treatment temperature (HTT) increases until 2300 °C. This increase in crystallinity was overturned at 2600 °C in B-doped carbon due to loss of B. But both techniques were not comparative on the determination of crystallite height ( La) and did not evidently present the crystallinity changes. The second order Raman spectroscopy was used as an alternative technique to clearly quantify the difference in crystallinity. It was confirmed that this new evaluation methodology from the second order Raman spectroscopy is effective for the determination of carbon crystallinity.
Second-order nonlinear optical activity vs. chromophore content in simple organic glass/PMMA system
NASA Astrophysics Data System (ADS)
Lee, Seung Mook; Jahng, Woong Sang; Lee, Jin Hyun; Rhee, Bum Ku; Park, Ki Hong
2005-08-01
A simple organic glass with a connection of two nonlinear optical (NLO) moieties was synthesized by condensation reaction of alkyl-substituted dibenzaldehyde with barbituric acid. This organic glass with Tg of 81 °C was formed to be optically transparent films without any phase separation even at the highest chromophore content (100 wt% loading without host matrix). The second-order NLO properties with various organic glass/PMMA composition systems were systematically studied by Maker fringe method at a wavelength of 1064 nm. We demonstrate that second-order optical nonlinearity of this organic glass/PMMA system can be progressively enlarged with increasing chromophore loading from 0 to 100 wt%.
Second order limit language in variants of splicing system
NASA Astrophysics Data System (ADS)
Ahmad, Muhammad Azrin; Sarmin, Nor Haniza; Heng, Fong Wan; Yusof, Yuhani
2014-07-01
The cutting and pasting processes that occur in DNA molecules have led to the formulation of splicing system. Since then, there are few models used to model the splicing system. The splicing language, which is the product of splicing system, can be categorized into two, namely the adult and limit language. In this research, limit language is extended to the second order limit language. Few problems are approached which lead to the formation of second order limit language which is then analyzed using various types of splicing system.
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.
Kubo Formulas for Second-Order Hydrodynamic Coefficients
Moore, Guy D.; Sohrabi, Kiyoumars A.
2011-03-25
At second order in gradients, conformal relativistic hydrodynamics depends on the viscosity {eta} and on five additional ''second-order'' hydrodynamical coefficients {tau}{sub {Pi}}, {kappa}, {lambda}{sub 1}, {lambda}{sub 2}, and {lambda}{sub 3}. We derive Kubo relations for these coefficients, relating them to equilibrium, fully retarded three-point correlation functions of the stress tensor. We show that the coefficient {lambda}{sub 3} can be evaluated directly by Euclidean means and does not in general vanish.
Elasto-plastic model with second order defect density tensor
NASA Astrophysics Data System (ADS)
Cleja-Å¢igoiu, Sanda
2011-05-01
The paper deals with a second order finite elasto-plastic model, which involves the defect density tensor, as a measure of the extra material defects existing in the damaged microstructure. The material behaviour is described with respect to an anholonomic configuration, which is introduced through the second order plastic deformation, consisting in plastic distortion and plastic connection. The defect density tensor enters the expression of the plastic connection through its gradient and represents a measure of non-metricity. The constitutive and evolution equations are derived to be compatible with the free energy imbalance. The evolution equation for the defect density tensor is non-local and coupled with the plastic distortion.
Human cooperation: second-order free-riding problem solved?
Fowler, James H
2005-09-22
Panchanathan and Boyd describe a model of indirect reciprocity in which mutual aid among cooperators can promote large-scale human cooperation without succumbing to a second-order free-riding problem (whereby individuals receive but do not give aid). However, the model does not include second-order free riders as one of the possible behavioural types. Here I present a simplified version of their model to demonstrate how cooperation unravels if second-round defectors enter the population, and this shows that the free-riding problem remains unsolved. PMID:16177738
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
Determination of thermodynamics and kinetics of RNA reactions by force
Tinoco, Ignacio; Li, Pan T. X.; Bustamante, Carlos
2008-01-01
Single-molecule methods have made it possible to apply force to an individual RNA molecule. Two beads are attached to the RNA; one is on a micropipette, the other is in a laser trap. The force on the RNA and the distance between the beads are measured. Force can change the equilibrium and the rate of any reaction in which the product has a different extension from the reactant. This review describes use of laser tweezers to measure thermodynamics and kinetics of unfolding/refolding RNA. For a reversible reaction the work directly provides the free energy; for irreversible reactions the free energy is obtained from the distribution of work values. The rate constants for the folding and unfolding reactions can be measured by several methods. The effect of pulling rate on the distribution of force-unfolding values leads to rate constants for unfolding. Hopping of the RNA between folded and unfolded states at constant force provides both unfolding and folding rates. Force-jumps and force-drops, similar to the temperature jump method, provide direct measurement of reaction rates over a wide range of forces. The advantages of applying force and using single-molecule methods are discussed. These methods, for example, allow reactions to be studied in non-denaturing solvents at physiological temperatures; they also simplify analysis of kinetic mechanisms because only one intermediate at a time is present. Unfolding of RNA in biological cells by helicases, or ribosomes, has similarities to unfolding by force. PMID:17040613
Reaction Kinetics of Alanine Solutions at Elevated Temperatures
NASA Astrophysics Data System (ADS)
Cox, J. S.; Seward, T. M.
2002-12-01
The reaction kinetics of ?-alanine under non-enzymatic, aqueous hydrothermal conditions has been the subject of few experimental studies. Varying conclusions on the alanine system have been reached, with some observing breakdown by pathways such as decarboxylation, and others observing polymerization and cyclization reactions (e.g. Abelson et al.(1957), Berhardt et al.(1984), Kawamura et al.(2001), Li et al.(2002), Vallentyne et al.(1964)). We have been able to observe the reaction kinetics of alanine in situ at temperature and pressure with a special gold-lined spectrophotometric cell which is also itself the reaction vessel. The identities of the reaction products were further confirmed using ion chromatography (Dionex AminoPAC). A postulated reaction scheme involving reversible polymerization and irreversible breakdown pathways will be presented and its dependence on temperature and other factors will be discussed, with an aim to reconciling conflicting data in the literature. Rate constants for this scheme, derived mathematically from the experimental data using a factor analysis-based method, will be presented up to 185 °C and 20 bar.
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
Reactions of allylic radicals that impact molecular weight growth kinetics.
Wang, Kun; Villano, Stephanie M; Dean, Anthony M
2015-03-01
The reactions of allylic radicals have the potential to play a critical role in molecular weight growth (MWG) kinetics during hydrocarbon oxidation and/or pyrolysis. Due to their stability (when compared to alkyl radicals), they can accumulate to relatively high concentrations. Thus, even though the rate coefficients for their various reactions are small, the rates of these reactions may be significant. In this work, we use electronic structure calculations to examine the recombination, addition, and abstraction reactions of allylic radicals. For the recombination reaction of allyl radicals, we assign a high pressure rate rule that is based on experimental data. Once formed, the recombination product can potentially undergo an H-atom abstraction reaction followed by unimolecular cyclization and ?-scission reactions. Depending upon the conditions (e.g., higher pressures) these pathways can lead to the formation of stable MWG species. The addition of allylic radicals to olefins can also lead to MWG species formation. Once again, cyclization of the adduct followed by ?-scission is an important energy accessible route. Since the recombination and addition reactions produce chemically-activated adducts, we have explored the pressure- and temperature-dependence of the overall rate constants as well as that for the multiple product channels. We describe a strategy for estimating these pressure-dependencies for systems where detailed electronic structure information is not available. We also derive generic rate rules for hydrogen abstraction reactions from olefins and diolefins by methyl and allyl radicals. PMID:25648200
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.
Yang, Bin; Ying, Guang-Guo; Zhao, Jian-Liang; Zhang, Li-Juan; Fang, Yi-Xiang; Nghiem, Long Duc
2011-02-15
The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0-10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC-MS and RRLC-MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k(app), being 754.7 M(-1) s(-1) at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7(±1.9)×10(2) M(-1) s(-1), while that measured for anionic triclosan was 7.6(±0.6)×10(3) M(-1) s(-1). The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth. PMID:21093982
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 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-orderâ€¦
A stable second order method for training back propagation networks
NASA Technical Reports Server (NTRS)
Nachtsheim, Philip R.
1993-01-01
A simple method for improving the learning rate of the back-propagation algorithm is described. The basis of the method is that approximate second order corrections can be incorporated in the output units. The extended method leads to significant improvements in the convergence rate.
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 Conditioning of Human Causal Learning
ERIC Educational Resources Information Center
Jara, Elvia; Vila, Javier; Maldonado, Antonio
2006-01-01
This article provides the first demonstration of a reliable second-order conditioning (SOC) effect in human causal learning tasks. It demonstrates the human ability to infer relationships between a cause and an effect that were never paired together during training. Experiments 1a and 1b showed a clear and reliable SOC effect, while Experiments 2aâ€¦
Second-Order Conditioning of Human Causal Learning
ERIC Educational Resources Information Center
Jara, Elvia; Vila, Javier; Maldonado, Antonio
2006-01-01
This article provides the first demonstration of a reliable second-order conditioning (SOC) effect in human causal learning tasks. It demonstrates the human ability to infer relationships between a cause and an effect that were never paired together during training. Experiments 1a and 1b showed a clear and reliable SOC effect, while Experiments 2a…
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…
Children's Understanding of Second-Order Mental States
ERIC Educational Resources Information Center
Miller, Scott A.
2009-01-01
The most popular topic in theory-of-mind research has been first-order false belief: the realization that it is possible to hold false beliefs about events in the world. A more advanced development is second-order false belief: the realization that it is possible to hold a false belief about someone else's belief. This article reviews researchâ€¦
Second-order phase transition in causal dynamical triangulations.
AmbjÃ¸rn, Jan; Jordan, S; Jurkiewicz, J; Loll, R
2011-11-18
Causal dynamical triangulations are a concrete attempt to define a nonperturbative path integral for quantum gravity. We present strong evidence that the lattice theory has a second-order phase transition line, which can potentially be used to define a continuum limit in the conventional sense of nongravitational lattice theories. PMID:22181870
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.
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…
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...
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.
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.
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 wereâ€¦
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 powerâ€¦
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 factorisationâ€¦
Second-order variational equations for N-body simulations
NASA Astrophysics Data System (ADS)
Rein, Hanno; Tamayo, Daniel
2016-03-01
First-order variational equations are widely used in N-body simulations to study how nearby trajectories diverge from one another. These allow for efficient and reliable determinations of chaos indicators such as the Maximal Lyapunov characteristic Exponent (MLE) and the Mean Exponential Growth factor of Nearby Orbits (MEGNO). In this paper we lay out the theoretical framework to extend the idea of variational equations to higher order. We explicitly derive the differential equations that govern the evolution of second-order variations in the N-body problem. Going to second order opens the door to new applications, including optimization algorithms that require the first and second derivatives of the solution, like the classical Newton's method. Typically, these methods have faster convergence rates than derivative-free methods. Derivatives are also required for Riemann manifold Langevin and Hamiltonian Monte Carlo methods which provide significantly shorter correlation times than standard methods. Such improved optimization methods can be applied to anything from radial-velocity/transit-timing-variation fitting to spacecraft trajectory optimization to asteroid deflection. We provide an implementation of first and second-order variational equations for the publicly available REBOUND integrator package. Our implementation allows the simultaneous integration of any number of first and second-order variational equations with the high-accuracy IAS15 integrator. We also provide routines to generate consistent and accurate initial conditions without the need for finite differencing.
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.
High temperature heterogeneous reaction kinetics and mechanisms of tungsten oxidation
NASA Astrophysics Data System (ADS)
Sabourin, Justin L.
Tungsten, which is a material used in many high temperature applications, is limited by its susceptibility to oxidation at elevated temperatures. Although tungsten has the highest melting temperature of any metal, at much lower temperatures volatile oxides are formed during oxidation with oxygen containing species. This differs from many heterogeneous oxidation reactions involving metals since most reactions form very stable oxides that have higher melting or boiling points than the pure metal (e.g., aluminum, iron). Understanding heterogeneous oxidation and vaporization processes may allow for the expansion and improvement of high temperature tungsten applications. In order to increase understanding of the oxidation processes of tungsten, there is a need to develop reaction mechanisms and kinetics for oxidation processes involving oxidizers and environmental conditions of interest. Tungsten oxidation was thoroughly studied in the past, and today there is a good phenomenological understanding of these processes. However, as the design of large scale systems increasingly relies on computer modeling there becomes a need for improved descriptions of chemical reactions. With the increase in computing power over the last several decades, and the development of quantum chemistry and physics theories, heterogeneous systems can be modeled in detail at the molecular level. Thermochemical parameters that may not be measured experimentally may now be determined theoretically, a tool that was previously unavailable to scientists and engineers. Additionally, chemical kinetic modeling software is now available for both homogeneous and heterogeneous reactions. This study takes advantage of these new theoretical tools, as well as a thermogravimetric (TG) flow reactor developed as part of this study to learn about mechanisms and kinetics of tungsten oxidation. Oxidizers of interest are oxygen (O2), carbon dioxide (CO 2), water (H2O), and other oxidizers present in combustion and energy systems. The primary application for this research topic is the migration of erosion processes in solid rocket motor nozzles. Since oxidation is the primary erosion mechanism of tungsten based nozzles, mitigation of this process through improved comprehension of the chemical mechanisms will increase performance of future rocket systems. In this dissertation, results of the high temperature reaction rates of bulk tungsten are studied using TG analysis in oxidizing atmospheres of O2, CO2, and H2O using helium (He) as an inert carrier gas. Isothermal reaction rates were determined at temperatures up to 1970 K, and oxidizing species partial pressures up to 64.6 torr. Kinetic parameters such as activation energies, frequency factors, and pressure exponents were determined for each reactive system. An important contribution of this work was quantifying the effects of carbon monoxide (CO) on the CO2 reaction, and hydrogen (H2) on the H2O reaction. In both cases the non-oxidizing species significantly reduced oxidation rates. Results have led to new interpretations and thought processes for limiting nozzle erosion in rocket motors. Combined with the TG analysis, as well as recent theoretical interpretations of reaction thermodynamics and kinetics, a new mechanism for tungsten and O2 oxidation has been developed using a one-dimensional numerical model of the TG flow reactor. Important chemical processes and species are also identified for reaction systems involving H2O and CO2. In the future, additional studies are needed to improve our understanding of these chemical species and processes so that more advanced kinetic mechanisms may be developed. In addition to a detailed analysis of high temperature tungsten corrosion processes, synthetic graphite corrosion processes are studied in detail as well. Details of these studies are presented in an attached appendix of this dissertation. These studies considered not only oxidation processes, but decomposition of synthetic graphite in the presence of reducing and inert gas environments.
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 1.57Â±0.02 M(-1) s(-1) at pH 7 and 20 Â°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
Second order optical nonlinearity in silicon by symmetry breaking
NASA Astrophysics Data System (ADS)
Cazzanelli, Massimo; Schilling, Joerg
2016-03-01
Although silicon does not possess a dipolar bulk second order nonlinear susceptibility due to its centro-symmetric crystal structure, in recent years several attempts were undertaken to create such a property in silicon. This review presents the different sources of a second order susceptibility (Ï‡(2)) in silicon and the connected second order nonlinear effects which were investigated up to now. After an introduction, a theoretical overview discusses the second order nonlinearity in general and distinguishes between the dipolar contributionâ€”which is usually dominating in non-centrosymmetric structuresâ€”and the quadrupolar contribution, which even exists in centro-symmetric materials. Afterwards, the classic work on second harmonic generation from silicon surfaces in reflection measurements is reviewed. Due to the abrupt symmetry breaking at surfaces and interfaces locally a dipolar second order susceptibility appears, resulting in, e.g., second harmonic generation. Since the bulk contribution is usually small, the study of this second harmonic signal allows a sensitive observation of the surface/interface conditions. The impact of covering films, strain, electric fields, and defect states at the interfaces was already investigated in this way. With the advent of silicon photonics and the search for ever faster electrooptic modulators, the interest turned to the creation of a dipolar bulk Ï‡(2) in silicon. These efforts have been focussing on several experiments applying an inhomogeneous strain to the silicon lattice to break its centro-symmetry. Recent results suggesting the impact of electric fields which are exerted from fixed charges in adjacent covering layers are also included. After a subsequent summary on "competing" concepts using not Si but Si-related materials, the paper will end with some final conclusions, suggesting possible future research direction in this dynamically developing field.
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
Second-order viscous corrections to the harmonic spectrum in heavy-ion collisions
NASA Astrophysics Data System (ADS)
Teaney, D.; Yan, L.
2014-01-01
We calculate the second-order viscous correction to the kinetic distribution, ?f(2), and use this result in a hydrodynamic simulation of heavy-ion collisions to determine the complete second-order correction to the harmonic spectrum, vn. At leading order in a conformal fluid, the first viscous correction is determined by one scalar function, ?0p. One moment of this scalar function is constrained by the shear viscosity. At second order in a conformal fluid, we find that ?f (p) can be characterized by two scalar functions of momentum, ?1p and ?2p. The momentum dependence of these functions is largely determined by the kinematics of the streaming operator. Again, one moment of these functions is constrained by the parameters of second-order hydrodynamics, ?? and ?1. The effect of ?f(2) on the integrated flow is small (up to v4) but is quite important for the higher harmonics at modestly large pT. Generally, ?f(2) increases the value of vn at a given pT and is most important in small systems.
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)
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 ÂµMâˆ’1sâˆ’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 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 â€œforeignâ€ 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, Âµ-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.
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.
Reaction kinetics of the CN radical with methyl bromide
NASA Astrophysics Data System (ADS)
Hodny, Michael; Hershberger, John F.
2016-02-01
The kinetics of the CN + CH3Br reaction were studied using transient infrared laser absorption spectroscopy to detect CN reactants and HCN products. This reaction has a rate constant of k = (2.20 ± 0.6) × 10-12 exp (453 ± 98/T) cm3 molecule-1 s-1 over the range 298-523 K. Hydrogen abstraction to produce HCN + CH2Br is only a minor reaction product, with a branching fraction of 0.12 ± 0.02. Other product channels, including BrCN + CH3, CH2CN + HBr, CH3CN + Br are likely. An upper limit of 0.01 was established for the HBr yield. These results are in qualitative agreement with recent ab initio calculations.
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.
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.
First and second order convex approximation strategies in structural optimization
NASA Technical Reports Server (NTRS)
Fleury, C.
1989-01-01
In this paper, various methods based on convex approximation schemes are discussed that have demonstrated strong potential for efficient solution of structural optimization problems. First, the convex linearization method (Conlin) is briefly described, as well as one of its recent generalizations, the method of moving asymptotes (MMA). Both Conlin and MMA can be interpreted as first-order convex approximation methods that attempt to estimate the curvature of the problem functions on the basis of semiempirical rules. Attention is next directed toward methods that use diagonal second derivatives in order to provide a sound basis for building up high-quality explicit approximations of the behavior constraints. In particular, it is shown how second-order information can be effectively used without demanding a prohibitive computational cost. Various first-order and second-order approaches are compared by applying them to simple problems that have a closed form solution.
On the second order spatiochromatic structure of natural images.
Provenzi, Edoardo; Delon, Julie; Gousseau, Yann; Mazin, Baptiste
2016-03-01
We provide a theoretical analysis of some empirical facts about the second order spatiochromatic structure of natural images in color. In particular, we show that two simple assumptions on the covariance matrices of color images yield eigenvectors made by the Kronecker product of Fourier features times the triad given by luminance plus color opponent channels. The first of these assumptions is second order stationarity while the second one is commutativity between color correlation matrices. The validity of these assumptions and the predicted shape of the PCA components of color images are experimentally observed on two large image databases. As a by-product of this experimental study, we also provide novel data to support an exponential decay law of the spatiochromatic covariance between pairs of pixels as a function of their spatial distance. PMID:26024561
Bounded solutions of a second order evolution equation and applications
NASA Astrophysics Data System (ADS)
Leiva, Hugo
2001-02-01
In this paper we study the following abstract second order differential equation with dissipation in a Hilbert space H: u?+cu'+dA u+kG(u)=P(t), u?H, t?R, where c, d and k are positive constants, G:H?H is a Lipschitzian function and P:R?H is a continuous and bounded function. A:D(A)?H?H is an unbounded linear operator which is self-adjoint, positive definite and has compact resolvent. Under these conditions we prove that for some values of d, c and k this system has a bounded solution which is exponentially asymptotically stable. Moreover; if P(t) is almost periodic, then this bounded solution is also almost periodic. These results are applied to a very well known second order system partial differential equations; such as the sine-Gordon equation, The suspension bridge equation proposed by Lazer and McKenna, etc.
Symmetries of second-order PDEs and conformal Killing vectors
NASA Astrophysics Data System (ADS)
Tsamparlis, Michael; Paliathanasis, Andronikos
2015-06-01
We study the Lie point symmetries of a general class of partial differential equations (PDE) of second order. An equation from this class naturally defines a second-order symmetric tensor (metric). In the case the PDE is linear on the first derivatives we show that the Lie point symmetries are given by the conformal algebra of the metric modulo a constraint involving the linear part of the PDE. Important elements in this class are the Klein-Gordon equation and the Laplace equation. We apply the general results and determine the Lie point symmetries of these equations in various general classes of Riemannian spaces. Finally we study the type II hidden symmetries of the wave equation in a Riemannian space with a Lorenzian metric.
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
Second-order closure models for supersonic turbulent flows
NASA Technical Reports Server (NTRS)
Speziale, Charles G.; Sarkar, Sutanu
1991-01-01
Recent work on the development of a second-order closure model for high-speed compressible flows is reviewed. This turbulent closure is based on the solution of modeled transport equations for the Favre-averaged Reynolds stress tensor and the solenoidal part of the turbulent dissipation rate. A new model for the compressible dissipation is used along with traditional gradient transport models for the Reynolds heat flux and mass flux terms. Consistent with simple asymptotic analyses, the deviatoric part of the remaining higher-order correlations in the Reynolds stress transport equations are modeled by a variable density extension of the newest incompressible models. The resulting second-order closure model is tested in a variety of compressible turbulent flows which include the decay of isotropic turbulence, homogeneous shear flow, the supersonic mixing layer, and the supersonic flat-plate turbulent boundary layer. Comparisons between the model predictions and the results of physical and numerical experiments are quite encouraging.
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.
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.
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.
Second order modeling of boundary-free turbulent shear flows
NASA Technical Reports Server (NTRS)
Shih, T.-H.; Chen, Y.-Y.; Lumley, J. L.
1991-01-01
A set of realizable second order models for boundary-free turbulent flows is presented. The constraints on second order models based on the realizability principle are re-examined. The rapid terms in the pressure correlations for both the Reynolds stress and the passive scalar flux equations are constructed to exactly satisfy the joint realizability. All other model terms (return-to-isotropy, third moments, and terms in the dissipation equations) already satisfy realizability. To correct the spreading rate of the axisymmetric jet, an extra term is added to the dissipation equation which accounts for the effect of mean vortex stretching on dissipation. The test flows used in this study are the mixing shear layer, plane jet, axisymmetric jet, and plane wake. The numerical solutions show that the unified model equations predict all these flows reasonably. It is expected that these models would be suitable for more complex and critical flows.
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.
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.
Second order filter response with series coupled silica microresonators
NASA Technical Reports Server (NTRS)
Savchenkov, A.; Iitchenko, V. S.; Handley, T.; Maleki, L.
2002-01-01
We have demonstrated an approach for fabricating a photonic filter with second order response function. The filter consists of two germania-doped silica microtoroidal or microspherical resonators cascaded in series. We use UV irradiation to tune the mode of one microcavity to bring it close to the mode of the second microcavity. This approach produces a filter function with much sharper rolloff than can be obtained with the individual microresonators.
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.
Efficient iterations for Gauss methods on second-order problems
NASA Astrophysics Data System (ADS)
Gonzalez-Pinto, S.; Perez-Rodriguez, S.; Rojas-Bello, R.
2006-05-01
We consider some important aspects about the implementation of high order implicit formulas (specially the Gauss methods) for solving second-order differential systems having high frequencies and small amplitudes superimposed. The choice of an appropriate iterative scheme is discussed in detail. Important topics about the predictors (initial guesses) are analyzed and a variable order strategy to select the best predictor at each integration step is supplied. A few numerical experiments on some standard test problems confirm the theory presented.
Differentiable solutions of the second order elliptic equation
NASA Astrophysics Data System (ADS)
Otelbaev, Mukhtarbay; Ospanov, Kordan Nauryzhanovich
2014-08-01
We study the second order elliptic equation with discontinuous intermediate coefficients. The variable coefficients and the right-hand side of this equation belong to some space M of type F. We find necessary and sufficient conditions on M for continuous differentiability of the solution to the above equation, when M is a space of type F or a symmetric space, or one of a Sobolev or a Besov space.
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.
A short note on the curvature perturbation at second order
NASA Astrophysics Data System (ADS)
Christopherson, Adam J.; Nalson, Ellie; Malik, Karim A.
2015-04-01
Working with perturbations about a Friedmann-Lemaître-Robertson-Walker spacetime, we compute the gauge-invariant curvature perturbation to second order solely in terms of scalar field fluctuations. Using the curvature perturbation on uniform density hypersurfaces as our starting point, we give our results in terms of field fluctuations in the flat gauge, incorporating both large and small scale behaviour. For ease of future numerical implementation, we give our result in terms of the scalar field fluctuations and their time derivatives.
Mechanisms and kinetics of reaction-bonded aluminium oxide ceramics
Wu, Suxing; Holz, D.; Claussen, N. . Advanced Ceramics Group)
1993-04-01
Reaction-bonded Al[sub 2]O[sub 3] (RBAO) ceramics were fabricated starting from mechanically alloyed Al[sub 2]O[sub 3]/Al, Al[sub 2]O[sub 3]/Al/ZrO[sub 2], and Al[sub 2]O[sub 3]/Al/ZrO[sub 2]/Zr mixtures. Isopressed compacts were heat-treated in air up to 1,550 C. Reaction-bonding mechanisms, kinetics, and the influence of ZrO[sub 2] and Zr additions are investigated. Independent of additive, oxidation of Al proceeds both as solid/gas and liquid/gas reaction, and the reaction kinetics follow a parabolic rate law. The reaction rate depends strongly on the particle size of Al. The activation energy of the reaction depends essentially on green density. Below the melting temperature of Al, in samples containing 45 vol% Al and 55 vol% Al[sub 2]O[sub 3], it is 112 and 152 kJ/mol at [approximately]64% and [approximately]74% TD, respectively, while above the melting temperature, it lies in the range [approximately]26--33 kJ/mol. Zr additions reduce the activation energy to some extent. Samples with only ZrO[sub 2] additions exhibit nearly the same activation energies as ZrO[sub 2]-free samples, though ZrO[sub 2] has a very positive effect on the microstructural development in RBAO ceramics. Microstructure evolution and some strength data of RBAO bodies are also reported.
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.
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.
Noise masking reveals channels for second-order letters
Oruç, ?pek; Landy, Michael S.; Pelli, Denis G.
2009-01-01
We investigate the channels underlying identification of second-order letters using a critical-band masking paradigm. We find that observers use a single 1–1.5 octave-wide channel for this task. This channel’s best spatial frequency (c/letter) did not change across different noise conditions (indicating the inability of observers to switch channels to improve signal-to-noise ratio) or across different letter sizes (indicating scale invariance), for a fixed carrier frequency (c/letter). However, the channel’s best spatial frequency does change with stimulus carrier frequency (both in c/letter); one is proportional to the other. Following Majaj et al. (Majaj, N. J., Pelli, D. G., Kurshan, P., & Palomares, M. (2002). The role of spatial frequency channels in letter identification. Vision Research, 42, 1165–1184), we define “stroke frequency” as the line frequency (strokes/deg) in the luminance image. That is, for luminance-defined letters, stroke frequency is the number of lines (strokes) across each letter divided by letter width. For second-order letters, letter texture stroke frequency is the number of carrier cycles (luminance lines) within the letter ink area divided by the letter width. Unlike the nonlinear dependence found for first-order letters (implying scale-dependent processing), for second-order letters the channel frequency is half the letter texture stroke frequency (suggesting scale-invariant processing). PMID:16203023
Local kinetics and thermodynamics of rapid electrochemical reactions
NASA Astrophysics Data System (ADS)
PÅ™ibyl, Michal; Å nita, Dalimil
2014-04-01
We introduce and discuss a local kinetic mechanism for an n-electron electrochemical reaction at the interface formed by an electrode and diluted electrolyte. We show that the suggested mechanism is in agreement with the Nernst equation in the thermal equilibrium. We also qualitatively characterize the structure of a flat electrode-diluted electrolyte boundary in the meaning of the spatial distribution of electrochemical reactants and electric potential. As the suggested kinetic mechanism is not limited by the duration of relaxation processes in electric double layers, it is suitable for the understanding and simulation of fast transient processes that appear in modern applications such as nanocolloid dielectrophoresis, AC electrospray, AC electroosmosis, or nanopore biosensing.
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.
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.
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
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.
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
Kinetic studies of cascade reactions in high-throughput systems.
Iron, David; Boelens, Hans F M; Westerhuis, Johan A; Rothenberg, Gadi
2003-12-01
The application of robotic systems to the study of complex reaction kinetics is considered, using the cascade reaction A --> B --> C as a working example. Practical problems in calculating the rate constants k1 and k2 for the reactions A --> B and B --> C from concentration measurements of CA, CB, or CC are discussed in the light of the symmetry and invertability of the rate equations. A D-optimal analysis is used to determine the points in time and the species that will give the best (i.e., most accurate) results. When exact data are used, the most robust solution results from measuring the pair of concentrations (CA, CC). The system's information function is computed using numeric methods. This function is then used to estimate the amount of information obtainable from a given cascade reaction at any given time. The theoretical findings are compared with experimental results from a set of two-stage cascade experiments monitored using UV-visible spectroscopy. Finally, the pros and cons of using a single reaction sample to estimate both k1 and k2 are discussed. PMID:16465720
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.
Kinetic study of Nafion degradation by Fenton reaction
NASA Astrophysics Data System (ADS)
Sugawara, Tomoko; Kawashima, Norimichi; Murakami, Takurou N.
2011-03-01
To predict the durability of polymer electrolyte membranes in fuel cells, the degradation reactions of Nafion 117 films were studied as oxidation reactions with hydroxyl radicals as oxidation accelerators. The radical species were generated by the Fenton reaction between hydrogen peroxide (H2O2) and iron ions (Fe2+). The Nafion degradation kinetics were estimated by fluorine ion (F-) generation. The H2O2 and Nafion degradation reactions fit a pseudo-first-order rate constant. The values of the activation energy and frequency factor are 85 kJ mol-1 and 3.97 × 108 s-1 for H2O2 decomposition in the presence of a Nafion film and 97 kJ mol-1 and 9.88 × 108 s-1 for F- generation. The Nafion surface morphology became rough after reaction for 12 h; small cracks, approximately 100 ?m in length, were observed at temperatures below 60 °C. These cracks connected to make larger gaps of approximately 1 mm at temperatures above 70 °C. We also found a linear relationship between H2O2 consumption and F- generation. The rate constant is temperature dependent and expressed as ln(d[F-]/d[decomposed H2O2]) = -19.5 × 103 K-1 + 42.8. F- generated and H2O2 consumed along with the Nafion degradation conditions can be predicted using this relation.
Reaction kinetic mechanism for methane hydrate formation in liquid water
Lekvam, K. ); Ruoff, P. )
1993-09-22
On the basis of experimental studies, we propose a reaction kinetic model for the formation of methane hydrate from liquid water and methane gas. The model consists of 5 pseudoelementary processes with the following three dynamic elements: (1) the dissolution of methane gas into the water phase, (2) the buildup of an oligomeric precursor of methane hydrate, and (3) the growth of methane hydrate by an autocatalytic process. The integrated rate equations of our model show close agreement to experimentally observed behavior. 20 refs., 6 figs., 2 tabs.
Xu, Enhua; Zhao, Dongbo; Li, Shuhua
2015-10-13
A multireference second order perturbation theory based on a complete active space configuration interaction (CASCI) function or density matrix renormalized group (DMRG) function has been proposed. This method may be considered as an approximation to the CAS/A approach with the same reference, in which the dynamical correlation is simplified with blocked correlated second order perturbation theory based on the generalized valence bond (GVB) reference (GVB-BCPT2). This method, denoted as CASCI-BCPT2/GVB or DMRG-BCPT2/GVB, is size consistent and has a similar computational cost as the conventional second order perturbation theory (MP2). We have applied it to investigate a number of problems of chemical interest. These problems include bond-breaking potential energy surfaces in four molecules, the spectroscopic constants of six diatomic molecules, the reaction barrier for the automerization of cyclobutadiene, and the energy difference between the monocyclic and bicyclic forms of 2,6-pyridyne. Our test applications demonstrate that CASCI-BCPT2/GVB can provide comparable results with CASPT2 (second order perturbation theory based on the complete active space self-consistent-field wave function) for systems under study. Furthermore, the DMRG-BCPT2/GVB method is applicable to treat strongly correlated systems with large active spaces, which are beyond the capability of CASPT2. PMID:26574254
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.
Protein thiyl radical reactions and product formation: a kinetic simulation.
Nauser, Thomas; Koppenol, Willem H; Schöneich, Christian
2015-03-01
Protein thiyl radicals are important intermediates generated in redox processes of thiols and disulfides. Thiyl radicals efficiently react with glutathione and ascorbate, and the common notion is that these reactions serve to eliminate thiyl radicals before they can enter potentially hazardous processes. However, over the past years increasing evidence has been provided for rather efficient intramolecular hydrogen transfer processes of thiyl radicals in proteins and peptides. Based on rate constants published for these processes, we have performed kinetic simulations of protein thiyl radical reactivity. Our simulations suggest that protein thiyl radicals enter intramolecular hydrogen transfer reactions to a significant extent even under physiologic conditions, i.e., in the presence of 30 µM oxygen, 1 mM ascorbate, and 10 mM glutathione. At lower concentrations of ascorbate and glutathione, frequently observed when tissue is exposed to oxidative stress, the extent of irreversible protein thiyl radical-dependent protein modification increases. PMID:25499854
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.
New implicitly solvable potential produced by second order shape invariance
NASA Astrophysics Data System (ADS)
Cannata, F.; Ioffe, M. V.; Kolevatova, E. V.; Nishnianidze, D. N.
2015-05-01
The procedure proposed recently by Bougie et al. (2010) to study the general form of shape invariant potentials in one-dimensional Supersymmetric Quantum Mechanics (SUSY QM) is generalized to the case of Higher Order SUSY QM with supercharges of second order in momentum. A new shape invariant potential is constructed by this method. It is singular at the origin, it grows at infinity, and its spectrum depends on the choice of connection conditions in the singular point. The corresponding Schrödinger equation is solved explicitly: the wave functions are constructed analytically, and the energy spectrum is defined implicitly via the transcendental equation which involves Confluent Hypergeometric functions.
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.
Universality in the Dynamics of Second-Order Phase Transitions.
Nikoghosyan, G; Nigmatullin, R; Plenio, M B
2016-02-26
When traversing a symmetry-breaking second-order phase transition at a finite rate, topological defects form whose number dependence on the quench rate is given by simple power laws. We propose a general approach for the derivation of such scaling laws that is based on the analytical transformation of the associated equations of motion to a universal form rather than employing plausible physical arguments. We demonstrate the power of this approach by deriving the scaling of the number of topological defects in both homogeneous and nonhomogeneous settings. The general nature and extensions of this approach are discussed. PMID:26967403
A simple second-order digital phase-locked loop.
NASA Technical Reports Server (NTRS)
Tegnelia, C. R.
1972-01-01
A simple second-order digital phase-locked loop has been designed for the Viking Orbiter 1975 command system. Excluding analog-to-digital conversion, implementation of the loop requires only an adder/subtractor, two registers, and a correctable counter with control logic. The loop considers only the polarity of phase error and corrects system clocks according to a filtered sequence of this polarity. The loop is insensitive to input gain variation, and therefore offers the advantage of stable performance over long life. Predictable performance is guaranteed by extreme reliability of acquisition, yet in the steady state the loop produces only a slight degradation with respect to analog loop performance.
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.
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.
Second order hydrodynamics for a special class of gravity duals
Springer, T.
2009-04-15
The sound mode hydrodynamic dispersion relation is computed up to order q{sup 3} for a class of gravitational duals which includes both Schwarzschild AdS and Dp-brane metrics. The implications for second order transport coefficients are examined within the context of Israel-Stewart theory. These sound mode results are compared with previously known results for the shear mode. This comparison allows one to determine the third order hydrodynamic contributions to the shear mode for the class of metrics considered here.
Universality in the Dynamics of Second-Order Phase Transitions
NASA Astrophysics Data System (ADS)
Nikoghosyan, G.; Nigmatullin, R.; Plenio, M. B.
2016-02-01
When traversing a symmetry-breaking second-order phase transition at a finite rate, topological defects form whose number dependence on the quench rate is given by simple power laws. We propose a general approach for the derivation of such scaling laws that is based on the analytical transformation of the associated equations of motion to a universal form rather than employing plausible physical arguments. We demonstrate the power of this approach by deriving the scaling of the number of topological defects in both homogeneous and nonhomogeneous settings. The general nature and extensions of this approach are discussed.
Octonic second-order equations of relativistic quantum mechanics
Mironov, Victor L.; Mironov, Sergey V.
2009-01-15
We demonstrate a generalization of relativistic quantum mechanics using eight-component value ''octons'' that generate an associative noncommutative spatial algebra. It is shown that the octonic second-order equation for the eight-component octonic wave function, obtained from the Einstein relation for energy and momentum, describes particles with spin 1/2. It is established that the octonic wave function of a particle in the state with defined spin projection has a specific spatial structure that takes the form of an octonic oscillator with two spatial polarizations: longitudinal linear and transverse circular.
Time regularity of the solutions to second order hyperbolic equations
NASA Astrophysics Data System (ADS)
Kinoshita, Tamotu; Taglialatela, Giovanni
2011-04-01
We consider the Cauchy problem for a second order weakly hyperbolic equation, with coefficients depending only on the time variable. We prove that if the coefficients of the equation belong to the Gevrey class ?^{s0} and the Cauchy data belong to ?^{s1}, then the Cauchy problem has a solution in ?^{s0}([0,T^{*}];?^{s1}({R})) for some T *>0, provided 1? s 1?2-1/ s 0. If the equation is strictly hyperbolic, we may replace the previous condition by 1? s 1? s 0.
Stochastic systems with delay: Perturbation theory for second order statistics
NASA Astrophysics Data System (ADS)
Frank, T. D.
2016-03-01
Within the framework of delay Fokker-Planck equations, a perturbation theoretical method is developed to determine second-order statistical quantities such as autocorrelation functions for stochastic systems with delay. Two variants of the perturbation theoretical approach are presented. The first variant is based on a non-local Fokker-Planck operator. The second variant requires to solve a Fokker-Planck equation with source term. It is shown that the two variants yield consistent results. The perturbation theoretical approaches are applied to study negative autocorrelations that are induced by feedback delays and mediated by the strength of the fluctuating forces that act on the feedback systems.
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)
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.
Dodd, Michael C; Buffle, Marc-Olivier; Von Gunten, Urs
2006-03-15
Ozone and hydroxyl radical (*OH) reaction kinetics were measured for 14 antibacterial compounds from nine structural families, to determine whether municipal wastewater ozonation is likely to result in selective oxidation of these compounds' biochemically essential moieties. Each substrate is oxidized by ozone with an apparent second-order rate constant, k''(O3,app) > 1 x 10(3) M(-1) s(-1), at pH 7, with the exception of N(4)-acetylsulfamethoxazole (K''(O3,app) is 2.5 x 102 M(-1) s(-1)). k''(O3,app) values (pH 7) for macrolides, sulfamethoxazole, trimethoprim, tetracycline, vancomycin, and amikacin appear to correspond directly to oxidation of biochemically essential moieties. Initial reactions of ozone with N(4)-acetylsulfamethoxazole, fluoroquinolones, lincomycin, and beta-lactams do not lead to appreciable oxidation of biochemically essential moieties. However, ozone oxidizes these moieties within fluoroquinolones and lincomycin via slower reactions. Measured k''(O3,app) values and second-order *OH rate constants, k''(*OH,app) were utilized to characterize pollutant losses during ozonation of secondary municipal wastewater effluent. These losses were dependent on k''(O3,app), but independent of k''(*OH,app). Ozone doses > or =3 mg/L yielded > or =99% depletion of fast-reacting substrates (K''(O3,app) > 5 x 10(4) M(-1) s(-1)) at pH 7.7. Ten substrates reacted predominantly with ozone; only four were oxidized predominantly by .OH. These results indicate that many antibacterial compounds will be oxidized in wastewater via moiety-specific reactions with ozone. PMID:16570623
Kinetic studies of the hydroxyl radical reaction with PAHs
NASA Astrophysics Data System (ADS)
Ananthula, Rajeshwar
An existing quartz optical reactor heating system was designed to permit higher temperature kinetic measurements more closely associated with post-combuston conditions (up to 1200 K). A pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique was then applied with this modified reactor to study the OH radical kinetics with polycyclic aromatic hydrocarbons (PAHs). The kinetics of the reaction of a surrogate three-ring PAH, anthracene (and its deuterated form) with hydroxyl (OH) radicals was investigated over the temperature range of 373 to 1200 K. This study represents the first examination of the OH kinetics for this class of reactions at elevated temperatures (>470 K). The results indicate a complex temperature dependence similar to that observed for simpler aromatic compounds, e.g., benzene. At low temperatures (373-498 K), the rate measurements exhibited Arrhenius behavior (1.82 x 10-11 exp(542.35/T) in units of cm3 molecule -1 s-1) and kinetic isotope effect (KIE) measurements were consistent with an OH addition mechanism. The low temperature results are extrapolated to atmospheric temperatures and compared with previous measurements. Rate measurements between 673 and 923 K exhibited a sharp decrease in the magnitude of the rate coefficients (a factor of 9). KIE measurements under these conditions were still consistent with an OH addition mechanism. The following modified Arrhenius equation is the best fit to our anthracene measurements between 373 and 923 K, 8.17 x 1014 T-8.3 exp(-3171.71/T) (in units of cm3 molecule-1 s-1). For a limited temperature range between 1000 and 1200 K, the rate measurements exhibited an apparent positive temperature dependence with the following Arrhenius equation the best fit to the data, 2.18 x 10-11*exp(-1734.11/T) (in units of cm3molecule-1s -1). KIE measurements above 999 K were slightly larger than unity, but inclusive regarding the mechanism of the reaction. Theoretical calculations of the KIE indicate the mechanism of reaction at these elevated temperatures is dominated by OH addition with H abstraction a minor contributor. The OH kinetic study was extended to the three-ring PAH, phenanthrene, (an isomer of anthracene) and its deuterated form. The rate measurements between 373 and 1000 K were best fit by the modified Arrhenius expression, 1.68 x 10-4 * T-2.46 * exp (-228.31/T) (in units of cm3molecule-1s-1). KIE measurements for phenanthrene indicated that the OH addition pathway dominated at temperature below 1000 K, in agreement with the anthracene results. The rate measurements on three ring PAHs are compared with available one and two ring PAHs to understand the effect of increasing molecule size on PAH reactivity with hydroxyl radicals.
KINETICS OF IRON - SODIUM DISILICATE REACTIONS AND WETTING
Tomsia, Antoni P.; Pask, Joseph A.
1980-01-01
Thermogravimetric and sessile drop measurements were used to study kinetics of redox reactions between sodium disilicate glass and iron. Two redox reaction sequences were identified; both introduced ferrous oxide into the glass at the interface. One consists of formation of ferrous oxide at the interface by reduction of sodium ions in the glass; this is primarily dependent on the a(FeO) in the metal being less than one. The second consists of oxidation of ferrous ions in the glass by the reduction of sodium ions to form ferric ions which subsequently react with the iron to form ferrous oxide. The reaction rates were shown to be sensitive to temperature, time, total ambient pressure, partial pressure of sodium and oxygen in the atmosphere, and the a(FeO) in the iron. Decrease of contact angles and spreading occur with the redox reaction in which the metal plays an active role, i.e. whose a(FeO) is less than one and whose composition undergoes a change.
Second-order closure models for supersonic turbulent flows
NASA Technical Reports Server (NTRS)
Speziale, Charles G.; Sarkar, Sutanu
1991-01-01
Recent work by the authors on the development of a second-order closure model for high-speed compressible flows is reviewed. This turbulence closure is based on the solution of modeled transport equations for the Favre-averaged Reynolds stress tensor and the solenoidal part of the turbulent dissipation rate. A new model for the compressible dissipation is used along with traditional gradient transport models for the Reynolds heat flux and mass flux terms. Consistent with simple asymptotic analyses, the deviatoric part of the remaining higher-order correlations in the Reynolds stress transport equation are modeled by a variable density extension of the newest incompressible models. The resulting second-order closure model is tested in a variety of compressible turbulent flows which include the decay of isotropic turbulence, homogeneous shear flow, the supersonic mixing layer, and the supersonic flat-plate turbulent boundary layer. Comparisons between the model predictions and the results of physical and numerical experiments are quite encouraging.
Classic reaction kinetics can explain complex patterns of antibiotic action
zur Wiesch, P. Abel; Abel, S.; Gkotzis, S.; Ocampo, P.; EngelstÃ¤dter, 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 â€˜chemical reaction kineticsâ€™-based approach may inform new strategies, that are based on rational design. PMID:25972005
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.
Ten-no, Seiichiro; Yamaki, Daisuke
2012-10-01
We propose explicitly correlated Ansatz for four-component relativistic methods within the framework of the no-pair approximation. Kinetically balanced geminal basis is derived to satisfy the cusp conditions in the non-relativistic limit based on the Le?vy-Leblend-like equation. Relativistic variants of strong-orthogonality projection operator (Ansa?tze 2? and 2?) suitable for practical calculations are introduced by exploiting the orthogonal complement of the large-component basis. A pilot implementation is performed for the second order Møller-Plesset perturbation theory. PMID:23039576
Chaotic properties of spin lattices near second-order phase transitions
NASA Astrophysics Data System (ADS)
de Wijn, A. S.; Hess, B.; Fine, B. V.
2015-12-01
We perform a numerical investigation of the Lyapunov spectra of chaotic dynamics in lattices of classical spins in the vicinity of second-order ferromagnetic and antiferromagnetic phase transitions. On the basis of this investigation, we identify a characteristic of the shape of the Lyapunov spectra, the "G -index," which exhibits a sharp peak as a function of temperature at the phase transition, provided the order parameter is capable of sufficiently strong dynamic fluctuations. As part of this work, we also propose a general numerical algorithm for determining the temperature in many-particle systems, where kinetic energy is not defined.
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.
Kinetics of the reaction of propargyl radical with nitric oxide
DeSain, J.D.; Hung, P.Y.; Thompson, R.I.; Glass, G.P.; Scuseria, G.; Curl, R.F.
2000-04-20
The reaction between the propargyl radical (C{sub 3}H{sub 3}) and NO has been investigated as a function of temperature (195--473 K) and pressure (3--100 Torr) by using color center laser infrared kinetic spectroscopy. At room temperature and below, the reaction rate was found to depend strongly on the helium buffer gas pressure and, at any fixed buffer gas density, to decrease with increasing temperature. This behavior is consistent with the reaction occurring by termolecular addition to produce C{sub 3}H{sub 3}NO. Data collected over a wide pressure range at 195 and 296 K were fitted to a semiempirical model developed by Troe for reactions of this type. The structure and energetics of the adduct were explored by performing both B3LYP 6-311++G(2df,2pd) and G2 calculations. The enthalpy change, {Delta}H, for addition of NO to the CH end of propargyl was determined as {minus}123 and {minus}138 kJ/mol, respectively, by using these two methods. The calculations also showed that NO can add at the CH{sub 2} end of propargyl but with a smaller binding energy. Estimates of the equilibrium constant for adduct formation, made using data obtained from these calculations, revealed that the addition reaction should shift from an equilibrium position strongly favoring the adduct to one strongly favoring free propargyl as the temperature is raised from 550 to 650 K. This temperature regime is higher than any of the temperatures reached experimentally.
The Reaction Kinetics of LiD with Water Vapor
Balooch, M; Dinh, L N; Calef, D F
2003-04-01
The interaction of LiD with water vapor in the partial pressure range of 10{sup -7} Torr to 20 Torr has been investigated. The reaction probability of water with pure LiD cleaved in an ultra high vacuum environment was obtained using the modulated molecular beam technique. This probability was 0.11 and independent of LiD surface temperature suggesting a negligible activation energy for the reaction in agreement with quantum chemical calculations. The value gradually reduced, however, to .007 as the surface concentration of oxygen containing product (LiOH), which was monitored in-situ by Auger electron spectroscopy on the reaction zone, approached full coverage. As the hydroxide film grew beyond a monolayer, the phase lag of hydrogen product increased from zero to 20 degrees and the reaction probability reduced further until it approached our detection limit ({approx} 10{sup -4}). This phase lag was attributed to a diffusion limited process in this regime. In separate experiments, the film growth has been studied in nitrogen atmosphere with 100% relative humidity using thermogravimetric analysis (TGA) and in air with 50% relative humidity utilizing scanning electron microscopy (SEM). For exposures to environment with high water concentrations and for micrometer thick films, the reaction probability reduced to 4 x 10{sup -7} and was independent of exposure time, The lattice diffusion through the film was no longer controlling the transport of water to the LiD/LiOH interface. Microcracks generated in the film to release stress provided easier pathways to the interface. A modified microscope, capable of both atomic force microscopy (AFM) and nanoindentation, was employed to investigate the surface morphology of LiOH.H{sub 2}O grown on LiOH at high water vapor partial pressures and the kinetics of this growth.
A second-order closure analysis of turbulent diffusion flames. [combustion physics
NASA Technical Reports Server (NTRS)
Varma, A. K.; Fishburne, E. S.; Beddini, R. A.
1977-01-01
A complete second-order closure computer program for the investigation of compressible, turbulent, reacting shear layers was developed. The equations for the means and the second order correlations were derived from the time-averaged Navier-Stokes equations and contain third order and higher order correlations, which have to be modeled in terms of the lower-order correlations to close the system of equations. In addition to fluid mechanical turbulence models and parameters used in previous studies of a variety of incompressible and compressible shear flows, a number of additional scalar correlations were modeled for chemically reacting flows, and a typical eddy model developed for the joint probability density function for all the scalars. The program which is capable of handling multi-species, multistep chemical reactions, was used to calculate nonreacting and reacting flows in a hydrogen-air diffusion flame.
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].
Invariant classification of second-order conformally flat superintegrable systems
NASA Astrophysics Data System (ADS)
Capel, J. J.; Kress, J. M.
2014-12-01
In this paper we continue the work of Kalnins et al in classifying all second-order conformally-superintegrable (Laplace-type) systems over conformally flat spaces, using tools from algebraic geometry and classical invariant theory. The results obtained show, through StÃ¤ckel equivalence, that the list of known nondegenerate superintegrable systems over three-dimensional conformally flat spaces is complete. In particular, a seven-dimensional manifold is determined such that each point corresponds to a conformal class of superintegrable systems. This manifold is foliated by the nonlinear action of the conformal group in three dimensions. Two systems lie in the same conformal class if and only if they lie in the same leaf of the foliation. This foliation is explicitly described using algebraic varieties formed from representations of the conformal group. The proof of these results rely heavily on GrÃ¶bner basis calculations using the computer algebra software packages Maple and Singular.
Regularized orbital-optimized second-order perturbation theory
Stück, David; Head-Gordon, Martin
2013-12-28
Orbital-optimized second-order perturbation theory (OOMP2) optimizes the zeroth order wave function in the presence of correlations, removing the dependence of the method on Hartree–Fock orbitals. This is particularly important for systems where mean field orbitals spin contaminate to artificially lower the zeroth order energy such as open shell molecules, highly conjugated systems, and organometallic compounds. Unfortunately, the promise of OOMP2 is hampered by the possibility of solutions being drawn into divergences, which can occur during the optimization procedure if HOMO and LUMO energies approach degeneracy. In this work, we regularize these divergences through the simple addition of a level shift parameter to the denominator of the MP2 amplitudes. We find that a large level shift parameter of 400 mE{sub h} removes divergent behavior while also improving the overall accuracy of the method for atomization energies, barrier heights, intermolecular interactions, radical stabilization energies, and metal binding energies.
Quadratically consistent nodal integration for second order meshfree Galerkin methods
NASA Astrophysics Data System (ADS)
Duan, Qinglin; Wang, Bingbing; Gao, Xin; Li, Xikui
2014-08-01
Robust and efficient integration of the Galerkin weak form only at the approximation nodes for second order meshfree Galerkin methods is proposed. The starting point of the method is the Hu-Washizu variational principle. The orthogonality condition between stress and strain difference is satisfied by correcting nodal derivatives. The corrected nodal derivatives are essentially linear functions which can exactly reproduce linear strain fields. With the known area moments, the stiffness matrix resulting from these corrected nodal derivatives can be exactly evaluated using only the nodes as quadrature points. The proposed method can exactly pass the quadratic patch test and therefore is named as quadratically consistent nodal integration. In contrast, the stabilized conforming nodal integration (SCNI) which prevails in the nodal integrations for meshfree Galerkin methods fails to pass the quadratic patch test. Better accuracy, convergence, efficiency and stability than SCNI are demonstrated by several elastostatic and elastodynamic examples.
Digital second-order phase-locked loop
NASA Technical Reports Server (NTRS)
Holes, J. K.; Carl, C.; Tegnelia, C. R. (inventors)
1973-01-01
A digital second-order phase-locked loop is disclosed in which a counter driven by a stable clock pulse source is used to generate a reference waveform of the same frequency as an incoming waveform, and to sample the incoming waveform at zero-crossover points. The samples are converted to digital form and accumulated over M cycles, reversing the sign of every second sample. After every M cycles, the accumulated value of samples is hard limited to a value SGN = + or - 1 and multiplied by a value delta sub 1 equal to a number of n sub 1 of fractions of a cycle. An error signal is used to advance or retard the counter according to the sign of the sum by an amount equal to the sum.
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.
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.
Nonoscillation for second order sublinear dynamic equations on time scales
NASA Astrophysics Data System (ADS)
Erbe, Lynn; Baoguo, Jia; Peterson, Allan
2009-10-01
Consider the Emden-Fowler sublinear dynamic equation x[Delta][Delta](t)+p(t)f(x([sigma](t)))=0, where , is a time scale, , where ai>0, 0<[beta]i<1, with [beta]i the quotient of odd positive integers, 1<=i<=m. When m=1, and , (0.1) is the usual sublinear Emden-Fowler equation which has attracted the attention of many researchers. In this paper, we allow the coefficient function p(t) to be negative for arbitrarily large values of t. We extend a nonoscillation result of Wong for the second order sublinear Emden-Fowler equation in the continuous case to the dynamic equation (0.1). As applications, we show that the sublinear difference equation has a nonoscillatory solution, for b>0, c>[alpha], and the sublinear q-difference equation has a nonoscillatory solution, for , q>1, b>0, c>1+[alpha].
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
Perceptual learning of second order cues for layer decomposition
Dövencio?lu, Dicle N.; Welchman, Andrew E.; Schofield, Andrew J.
2013-01-01
Luminance variations are ambiguous: they can signal changes in surface reflectance or changes in illumination. Layer decomposition—the process of distinguishing between reflectance and illumination changes—is supported by a range of secondary cues including colour and texture. For an illuminated corrugated, textured surface the shading pattern comprises modulations of luminance (first order, LM) and local luminance amplitude (second-order, AM). The phase relationship between these two signals enables layer decomposition, predicts the perception of reflectance and illumination changes, and has been modelled based on early, fast, feed-forward visual processing (Schofield et al., 2010). However, while inexperienced viewers appreciate this scission at long presentation times, they cannot do so for short presentation durations (250 ms). This might suggest the action of slower, higher-level mechanisms. Here we consider how training attenuates this delay, and whether the resultant learning occurs at a perceptual level. We trained observers to discriminate the components of plaid stimuli that mixed in-phase and anti-phase LM/AM signals over a period of 5 days. After training, the strength of the AM signal needed to differentiate the plaid components fell dramatically, indicating learning. We tested for transfer of learning using stimuli with different spatial frequencies, in-plane orientations, and acutely angled plaids. We report that learning transfers only partially when the stimuli are changed, suggesting that benefits accrue from tuning specific mechanisms, rather than general interpretative processes. We suggest that the mechanisms which support layer decomposition using second-order cues are relatively early, and not inherently slow. PMID:23200744
Perceptual learning of second order cues for layer decomposition.
Dövencio?lu, Dicle N; Welchman, Andrew E; Schofield, Andrew J
2013-01-25
Luminance variations are ambiguous: they can signal changes in surface reflectance or changes in illumination. Layer decomposition-the process of distinguishing between reflectance and illumination changes-is supported by a range of secondary cues including colour and texture. For an illuminated corrugated, textured surface the shading pattern comprises modulations of luminance (first order, LM) and local luminance amplitude (second-order, AM). The phase relationship between these two signals enables layer decomposition, predicts the perception of reflectance and illumination changes, and has been modelled based on early, fast, feed-forward visual processing (Schofield et al., 2010). However, while inexperienced viewers appreciate this scission at long presentation times, they cannot do so for short presentation durations (250 ms). This might suggest the action of slower, higher-level mechanisms. Here we consider how training attenuates this delay, and whether the resultant learning occurs at a perceptual level. We trained observers to discriminate the components of plaid stimuli that mixed in-phase and anti-phase LM/AM signals over a period of 5 days. After training, the strength of the AM signal needed to differentiate the plaid components fell dramatically, indicating learning. We tested for transfer of learning using stimuli with different spatial frequencies, in-plane orientations, and acutely angled plaids. We report that learning transfers only partially when the stimuli are changed, suggesting that benefits accrue from tuning specific mechanisms, rather than general interpretative processes. We suggest that the mechanisms which support layer decomposition using second-order cues are relatively early, and not inherently slow. PMID:23200744
WEAK GALERKIN METHODS FOR SECOND ORDER ELLIPTIC INTERFACE PROBLEMS.
Mu, Lin; Wang, Junping; Wei, Guowei; Ye, Xiu; Zhao, Shan
2013-10-01
Weak Galerkin methods refer to general finite element methods for partial differential equations (PDEs) in which differential operators are approximated by their weak forms as distributions. Such weak forms give rise to desirable flexibilities in enforcing boundary and interface conditions. A weak Galerkin finite element method (WG-FEM) is developed in this paper for solving elliptic PDEs with discontinuous coefficients and interfaces. Theoretically, it is proved that high order numerical schemes can be designed by using the WG-FEM with polynomials of high order on each element. Extensive numerical experiments have been carried to validate the WG-FEM for solving second order elliptic interface problems. High order of convergence is numerically confirmed in both L 2 and L âˆž norms for the piecewise linear WG-FEM. Special attention is paid to solve many interface problems, in which the solution possesses a certain singularity due to the nonsmoothness of the interface. A challenge in research is to design nearly second order numerical methods that work well for problems with low regularity in the solution. The best known numerical scheme in the literature is of order [Formula: see text] to [Formula: see text] for the solution itself in L âˆž norm. It is demonstrated that the WG-FEM of the lowest order, i.e., the piecewise constant WG-FEM, is capable of delivering numerical approximations that are of order [Formula: see text] to [Formula: see text] in the L âˆž norm for C (1) or Lipschitz continuous interfaces associated with a C (1) or H (2) continuous solution. PMID:24072935
Second order closure modeling of turbulent buoyant wall plumes
NASA Technical Reports Server (NTRS)
Zhu, Gang; Lai, Ming-Chia; Shih, Tsan-Hsing
1992-01-01
Non-intrusive measurements of scalar and momentum transport in turbulent wall plumes, using a combined technique of laser Doppler anemometry and laser-induced fluorescence, has shown some interesting features not present in the free jet or plumes. First, buoyancy-generation of turbulence is shown to be important throughout the flow field. Combined with low-Reynolds-number turbulence and near-wall effect, this may raise the anisotropic turbulence structure beyond the prediction of eddy-viscosity models. Second, the transverse scalar fluxes do not correspond only to the mean scalar gradients, as would be expected from gradient-diffusion modeling. Third, higher-order velocity-scalar correlations which describe turbulent transport phenomena could not be predicted using simple turbulence models. A second-order closure simulation of turbulent adiabatic wall plumes, taking into account the recent progress in scalar transport, near-wall effect and buoyancy, is reported in the current study to compare with the non-intrusive measurements. In spite of the small velocity scale of the wall plumes, the results showed that low-Reynolds-number correction is not critically important to predict the adiabatic cases tested and cannot be applied beyond the maximum velocity location. The mean and turbulent velocity profiles are very closely predicted by the second-order closure models. but the scalar field is less satisfactory, with the scalar fluctuation level underpredicted. Strong intermittency of the low-Reynolds-number flow field is suspected of these discrepancies. The trends in second- and third-order velocity-scalar correlations, which describe turbulent transport phenomena, are also predicted in general, with the cross-streamwise correlations better than the streamwise one. Buoyancy terms modeling the pressure-correlation are shown to improve the prediction slightly. The effects of equilibrium time-scale ratio and boundary condition are also discussed.
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…
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 theâ€¦
Reaction Kinetics of Meteoric Sodium Reservoirs in the Upper Atmosphere.
GÃ³mez MartÃn, J C; Garraway, S A; Plane, J M C
2016-03-10
The gas-phase reactions of a selection of sodium-containing species with atmospheric constituents, relevant to the chemistry of meteor-ablated Na in the upper atmosphere, were studied in a fast flow tube using multiphoton ionization time-of-flight mass spectrometry. For the first time, unambiguous observations of NaO and NaOH in the gas phase under atmospheric conditions have been achieved. This enabled the direct measurement of the rate constants for the reactions of NaO with H2, H2O, and CO, and of NaOH with CO2, which at 300-310 K were found to be (at 2Ïƒ confidence level): k(NaO + H2O) = (2.4 Â± 0.6) Ã— 10(-10) cm(3) molecule (-1) s(-1), k(NaO + H2) = (4.9 Â± 1.2) Ã— 10(-12) cm(3) molecule (-1) s(-1), k(NaO + CO) = (9 Â± 4) Ã— 10(-11) cm(3) molecule (-1) s(-1), and k(NaOH + CO2 + M) = (7.6 Â± 1.6) Ã— 10(-29) cm(6) molecule (-2) s(-1) (P = 1-4 Torr). The NaO + H2 reaction was found to make NaOH with a branching ratio â‰¥99%. A combination of quantum chemistry and statistical rate theory calculations are used to interpret the reaction kinetics and extrapolate the atmospherically relevant experimental results to mesospheric temperatures and pressures. The NaO + H2O and NaOH + CO2 reactions act sequentially to provide the major atmospheric sink of meteoric Na and therefore have a significant impact on the underside of the Na layer in the terrestrial mesosphere: the newly determined rate constants shift the modeled peak to about 93 km, i.e., 2 km higher than observed by ground-based lidars. This highlights further uncertainties in the Na chemistry cycle such as the unknown rate constant of the NaOH + H reaction. The fast Na-recycling reaction between NaO and CO and a re-evaluated rate constant of the NaO + CO2 sink should be now considered in chemical models of the Martian Na layer. PMID:25723735
Reaction kinetics of the hydrothermal treatment of lignin.
Zhang, Bo; Huang, Hua-Jiang; Ramaswamy, Shri
2008-03-01
Lignins derived from abundant and renewable resources are nontoxic and extremely versatile in performance, qualities that have made them increasingly important in many industrial applications. We have shown recently that liquefaction of lignin extracted from aspen wood resulted in a 90% yield of liquid. In this paper, the hydrothermal treatment of five types of lignin and biomass residues was studied: Kraft pine lignin provided by MeadWestvaco, Kraft pine lignin from Sigma-Aldrich, organosolv lignin extracted from oat hull, the residues of mixed southern hardwoods, and switchgrass after hydrolysis. The yields were found dependent on the composition or structure of the raw materials, which may result from different pretreatment processes. We propose a kinetic model to describe the hydrothermal treatment of Kraft pine lignin and compare it with another model from the literature. The kinetic parameters of the presented model were estimated, including the reaction constants, the pre-exponential factor, and the activation energy of the Arrhenius equations. Results show that the presented model is well in agreement with the experiments. PMID:18401758
Reaction Kinetics of the Hydrothermal Treatment of Lignin
NASA Astrophysics Data System (ADS)
Zhang, Bo; Huang, Hua-Jiang; Ramaswamy, Shri
Lignins derived from abundant and renewable resources are nontoxic and extremely versatile in performance, qualities that have made them increasingly important in many industrial applications. We have shown recently that liquefaction of lignin extracted from aspen wood resulted in a 90% yield of liquid. In this paper, the hydrothermal treatment of five types of lignin and biomass residues was studied: Kraft pine lignin provided by MeadWestvaco, Kraft pine lignin from Sigma-Aldrich, organosolv lignin extracted from oat hull, the residues of mixed southern hardwoods, and switchgrass after hydrolysis. The yields were found dependent on the composition or structure of the raw materials, which may result from different pretreatment processes. We propose a kinetic model to describe the hydrothermal treatment of Kraft pine lignin and compare it with another model from the literature. The kinetic parameters of the presented model were estimated, including the reaction constants, the pre-exponential factor, and the activation energy of the Arrhenius equations. Results show that the presented model is well in agreement with the experiments.
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
Control of DNA replication by anomalous reaction-diffusion kinetics
NASA Astrophysics Data System (ADS)
Gauthier, Michel; Bechhoefer, John
2009-05-01
DNA replication requires two distinct processes: the initiation of pre-licensed replication origins and the propagation of replication forks away from the fired origins. Experiments indicate that these origins are triggered over the whole genome at a rate I(t) (the number of initiations per unreplicated length per time) that increases throughout most of the synthesis (S) phase, before rapidly decreasing to zero at the end of the replication process. We propose a simple model for the control of DNA replication in which the rate of initiation of replication origins is controlled by the interaction with a population of rate-limiting proteins. We find the time set by reaction-diffusion kinetics for such proteins to find, bind to, and trigger a potential origin. Analyzing data from Xenopus frog embryos, we find that the initiation rate is reaction limited until nearly the end of replication, when it becomes diffusion limited. Initiation of origins and hence I(t) is suppressed when the diffusion-limited search time dominates. We find that, in order to fit the experimental data, the interaction between DNA and the rate-limiting protein must be subdiffusive.
Kinetic analysis of the genome packaging reaction in bacteriophage lambda.
Yang, Qin; Catalano, Carlos E; Maluf, Nasib Karl
2009-11-17
Bacteriophage lambda is a double-stranded DNA virus that infects the Escherichia coli bacterium. lambda genomic DNA is replicated via rolling circle replication, resulting in multiple genomes linked head to tail at the cos site. To insert a single lambda genome into the viral capsid, the lambda terminase enzyme introduces symmetric nicks, 12 bp apart, at the cos site, and then promotes a strand separation reaction, releasing the tail end of the previous genome and leaving a binary complex consisting of lambda terminase bound to the head end of the adjacent genome. Next, the genome is translocated into the interior of the capsid particle, in a process that requires ATP hydrolysis by lambda terminase. Even though DNA packaging has been studied extensively, currently no bulk assays are available that have been optimized to report directly on DNA translocation. Rather, these assays are sensitive to assembly steps reflecting formation of the active, DNA packaging machine. In this work, we have modified the DNase protection assay commonly used to study DNA packaging in several bacteriophage systems, such that it reports directly on the kinetics of the DNA packaging reaction. We have analyzed our DNA packaging data according to an N-step sequential minimal kinetic model and have estimated an overall packaging rate of 119 +/- 8 bp/s, at 4 degrees C and 1 mM ATP. Furthermore, we have measured an apparent step size for the this reaction (m(obs)) of 410 +/- 150 bp. The magnitude of this value indicates that our assay is most likely sensitive to both mechanical steps associated with DNA insertion as well as occasional slow steps that are repeated every >410 bp. These slow steps may be reflective of the pausing events observed in recent single-molecule studies of DNA packaging in bacteriophage lambda [Fuller, D. N., et al. (2007) J. Mol. Biol. 373, 1113-1122]. Finally, we show that either ATP or ADP is required for terminase cutting at cos, to generate the active, DNA packaging complex. PMID:19788336
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.
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."
Second order statistics target-specified virtual dimensionality
NASA Astrophysics Data System (ADS)
Paylor, Drew; Chang, Chein-I.
2013-05-01
Virtual dimensionality (VD) has received considerable interest in its use of specifying the number of spectrally distinct signatures. So far all techniques are decomposition approaches which use eigenvalues, eigenvectors or singular vectors to estimate the virtual dimensionality. However, when eigenvalues are used to estimate VD such as Harsanyi-Farrand- Chang's method or hyperspectral signal subspace identification by minimum error (HySime), there will be no way to find what the spectrally distinct signatures are. On the other hand, if eigenvectors/singular vectors are used to estimate VD such as maximal orthogonal complement algorithm (MOCA), eigenvectors/singular vectors do not represent real signal sources. In this paper we introduce a new concept, referred to as target-specified VD (TSVD), which operates on the signal sources themselves to both determine the number of distinct sources and identify their signature. The underlying idea of TSVD was derived from that used to develop high-order statistics (HOS) VD where its applicability to second order statistics (2OS) was not explored. In this paper we investigate a 2OS-based target finding algorithm, called automatic target generation process (ATGP) to determine VD. Experiments are conducted in comparison with well-known and widely used eigen-based approaches.
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.
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 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 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
NASA Astrophysics Data System (ADS)
Felder, William; Fontijn, Arthur; Volltrauer, Hermannn N.; Voorhees, David R.
1980-02-01
A reactor suitable for kinetic measurements on photolytically initiated elementary free-radical reactions over approximately the 300-1900 K temperature range is described. Performance data are given for the O+CH4?OH+CH3 reaction.
Reaction kinetics of dual setting Î±-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 Î±-tricalcium phosphate (Î±-TCP) is a promising approach to improve the mechanical performance of Î±-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 Î±-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 Î±-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 Â± 1.8 wt% CDHA with 50 % HEMA compared to 54.1 Â± 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, Î±-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 spatial correlation in the far-field: Comparing entangled and classical light sources
NASA Astrophysics Data System (ADS)
Zhang, Erfeng; Liu, Weitao; Lin, Huizu; Chen, Pingxing
2016-02-01
We consider second-order spatial correlation with entangled and classical light in the far-field. The quantum theory of second-order spatial correlation is analyzed, and the role of photon statistics and detection mode in the second-order spatial correlation are discussed. Meanwhile, the difference of second-order spatial correlation with entangled and classical light sources is deduced.
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.
Second Order Lagrangian and Angular Momentum of Scalar Field
NASA Astrophysics Data System (ADS)
Günther, H.
The class of second order Lagrangian for the scalar field is including free divergence terms giving rise to new canonical conservation laws by means of Noethers theorem. The appearance of a spin like tensor S within angular momentum is nothing but a redefinition of orbital angular momentum. S is mainly giving a new definition of center of mass for the field, indicating that the variation for the motion of singularities is nothing but a redefinition for the motion, since the sum for the additional forces, coming from divergence part of Lagrangian, is zero. Thus, the physical content of the theory will not be affected by the divergence part of Lagrangian, is zero. Thus, the physical content of the theory will not be affected by the divergence termes; it is only an other formulation.Translated AbstractLagrangefunktion zweiter Ordnung und Drehimpulstensor des SkalarfeldesLäßt man für die Lagrangefunktion L des Skalarfeldes zweite Ableitungen zu, so bleiben in L additive Divergenzterme frei wählbar, die sich in der Definition der kanonischen Erhaltungsgrößen durch das Noethersche Theorem widerspiegeln. Der bei der Berechnung des Drehimpulstensors i. a. dann auftretende scheinbare Spintensor S erweist sich als Bestandteil des durch das Noethersche Theorem umdefinierten Bahndrehimpulstensors. S trägt maßgeblich zu einer Umdefinition der Massenmittelpunktsverteilung des Feldes bei. Das weist darauf hin, daß die durch die Divergenzterme in L induzierte scheinbare Änderung in der Bewegungsgleichung für die Singularitäten des Feldes lediglich das Ergebnis einer anders betrachteten Bewegung ist. Die Summe der tatsächlich auftretenden Zusatzkräfte verschwindet. Die physikalische Aussage der Theorie wird daher durch die Divergenzterme nicht verändert, sondern nur anders dargestellt.
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.
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 isâ€¦
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…
Cell population kinetic parameters for acute epidermal reactions in man
Cohen, L.
1986-11-01
Cell population kinetic parameters for acute reactions in squamous epithelium were estimated using available data on skin tolerance doses. Roughly equivalent doses for kilovoltage radiation delivered in equal daily fractions, as reported by F. Ellis (Br. J. Radiol. 15, 348-350 (1942)) and by R. Paterson (The Treatment of Malignant Disease by Radium and X-Rays. Edward Arnold, London, 1948), were combined with data for nonstandard fractionation at longer intervals of 1 or 2 weeks. By analyzing the combined data set, well-determined parameters could be derived. The data show that repopulation, with a potential cell doubling time of about 7 days, must occur in irradiated human skin, though this may possibly be limited to no more than seven doublings. The parameters derived are distinctly different from those associated with late-reacting dose-limiting tissues. The main difference is the steeper initial slope of the computed survival curve, that is a larger J parameter (multitarget model) or a larger alpha component (linear-quadratic model).
Kinetics of the ClO + NO2 + M reaction
NASA Technical Reports Server (NTRS)
Molina, M. J.; Molina, L. T.; Ishiwata, T.
1980-01-01
The ClO + NO2 + M reaction has been studied with two techniques: Fourier transform infrared spectroscopy of the products, and flash photolysis-ultraviolet absorption to monitor the decay of ClO in excess NO2. The measured third-order rate constant is 1.5 x 10 to the -31st cm to the 6th/molecule-squared per sec at 298 K with M = N2, in good agreement with previous literature values, but the rate constant appears to decrease by up to a factor of three in the presence of increasing amounts of OClO. For the infrared studies a stoichiometric mixture of ClO and NO2 was prepared in a flow system by mixing NO with OClO; at least as much NO2 as ClONO2 was produced under a variety of experimental conditions. These two sets of results are incompatible with the assumption made in previous kinetic studies that ClONO2 is the only recombination product; other isomers such as OClONO or ClOONO are likely to be formed three to four times faster. These results imply that potential stratospheric ozone depletion due to chlorofluoromethanes may be even larger than previously thought.
Wong, Kin-Yiu; Richard, John P; Gao, Jiali
2009-10-01
Primary kinetic isotope effects (KIEs) on a series of carboxylic acid-catalyzed protonation reactions of aryl-substituted alpha-methoxystyrenes (X-1) to form oxocarbenium ions have been computed using the second-order Kleinert variational 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 relatively 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 alpha-methoxystyrenes by chloroacetic acid, but for the reactions of the parent and 4-NO(2) substituted alpha-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, DeltaG(o) approximately 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, that is, the driving force DeltaG(o), along with a good correlation of Hammond shift in the transition state structure. PMID:19754046
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.
Fairweather, M.; Woolley, R.M.
2007-07-15
Presented are results obtained from the application of a first- and higher-order conditional moment closure (CMC) approach to the modeling of three methane diffusion flames at differing levels of local extinction. In addition to the analysis of higher-order chemistry applications, the results obtained from an elliptic formulation of the CMC equation are considered next to parabolic results presented in previous work. All predictions are based upon second-moment turbulence and scalar-flux closures, and the chemistry applied to represent mean production rates of species is a 16-step reduced mechanism. A second-order chemistry is implemented on the basis of a two-step kinetic representation of methane combustion, used to correct first-order rates. In general, predictions obtained using the second-order model improve significantly upon first-order results for both major and minor species under fuel-rich conditions. The simplified chemistry employed does not however fully capture the effects of local extinction, and suggestions are made regarding the further developments required to permit the accurate prediction of highly strained flames using CMC methods. (author)
Experimental and theoretical methods in kinetic studies of heterogeneously catalyzed reactions.
Reyniers, Marie-Françoise; Marin, Guy B
2014-01-01
This review aims to illustrate the potential of kinetic analysis in general and microkinetic modeling in particular for rational catalyst design. Both ab initio calculations and experiments providing intrinsic kinetic data allow us to assess the effects of catalytic properties and reaction conditions on the activity and selectivity of the targeted reactions. Three complementary approaches for kinetic analysis of complex reaction networks are illustrated, using select examples of acid zeolite-catalyzed reactions from the authors' recent work. Challenges for future research aimed at defining targets for synthesis strategies that enable us to tune zeolite properties are identified. PMID:24910922
Soil solid materials affect the kinetics of extracellular enzymatic reactions
NASA Astrophysics Data System (ADS)
Lammirato, C.; Miltner, A.; KÃ¤stner, 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 â†’change in activity) and substrate (adsorption â†’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, 25Â°C, 20 mg solid/ml buffer). The enzyme in an immobilized form (covalent bonding to oxirane groups on the surfaces of macroporous EupergitÂ® 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 solid materials tested, only activated charcoal may affect the reaction rate by limiting the substrate bioavailability while all the materials tested may affect the reaction rate by limiting the enzymatic activity. The results from the experiments on the effect of kaolinite on the reaction rate lead to the conclusion that even the degradation of substrates with unrestricted bioavailability can be affected by soil solid materials. The next experiments will show how much activity is lost by beta-glucosidase when adsorbed to bentonite and goethite and how activated carbon affects the reaction by limiting the substrate bioavailability and the enzymatic activity. In this last case beta-glucosidase will also be used in the immobilized form to eliminate the effect of activated carbon on the enzyme.
Pereira, JosÃ© Clayston Melo; Iretskii, Alexei V; Han, Rui-Min; Ford, Peter C
2015-01-14
Kinetics studies provide mechanistic insight regarding the formation of dinitrosyl iron complexes (DNICs) now viewed as playing important roles in the mammalian chemical biology of the ubiquitous bioregulator nitric oxide (NO). Reactions in deaerated aqueous solutions containing FeSO4, cysteine (CysSH), and NO demonstrate that both the rates and the outcomes are markedly pH dependent. The dinuclear DNIC Fe2(Î¼-CysS)2(NO)4, a Roussin's red salt ester (Cys-RSE), is formed at pH 5.0 as well as at lower concentrations of cysteine in neutral pH solutions. The mononuclear DNIC Fe(NO)2(CysS)2(-) (Cys-DNIC) is produced from the same three components at pH 10.0 and at higher cysteine concentrations at neutral pH. The kinetics studies suggest that both Cys-RSE and Cys-DNIC are formed via a common intermediate Fe(NO)(CysS)2(-). Cys-DNIC and Cys-RSE interconvert, and the rates of this process depend on the cysteine concentration and on the pH. Flash photolysis of the Cys-RSE formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 5.0 solution led to reversible NO dissociation and a rapid, second-order back reaction with a rate constant kNO = 6.9 Ã— 10(7) M(-1) s(-1). In contrast, photolysis of the mononuclear-DNIC species Cys-DNIC formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 10.0 solution did not labilize NO but instead apparently led to release of the CysS(â€¢) radical. These studies illustrate the complicated reaction dynamics interconnecting the DNIC species and offer a mechanistic model for the key steps leading to these non-heme iron nitrosyl complexes. PMID:25479566
Complex kinetics of a Landolt-type reaction: the later phase of the thiosulfate-iodate reaction.
Varga, Dénes; Nagypál, István; Horváth, Attila K
2010-05-13
The thiosulfate-iodate reaction has been studied spectrophotometrically in slightly acidic medium at 25.0 +/- 0.1 degrees C in acetate/acetic acid buffer by monitoring the absorbance at 468 nm at the isosbestic point of iodine-triiodide ion system. The formation of iodine after the Landolt time follows a rather complex kinetic behavior depending on the pH and on the concentration of the reactants as well. It is shown that the key intermediate of the reaction is I(2)O(2), its equilibrium formation from the well-known Dushman reaction along with their further reactions followed by subsequent reactions of HOI, HIO(2), S(2)O(3)OH(-), and S(2)O(3)I(-) adequately accounts for all the experimentally measured characteristics of the kinetic curves. A 19-step kinetic model is proposed and discussed with 13 fitted and 7 fixed parameters in detail. PMID:20397669
A G-quadruplex based platform for label-free monitoring of DNA reaction kinetics.
Nie, Ji; Cai, Liang-Yuan; Zhang, Fang-Ting; Zhao, Ming-Zhe; Zhou, Ying-Lin; Zhang, Xin-Xiang
2014-12-21
Research on the kinetic characteristics and mechanisms of DNA reactions is crucial for bioengineering and biosensing. A G-quadruplex, which can form a peroxidase-mimicking DNAzyme with hemin, was for the first time used to establish a versatile platform for kinetic investigations on DNA reactions. G-quadruplex sequence EAD2 was incorporated into the corresponding nucleic acid reaction as product. The kinetic curves can be obtained rapidly and simply via the quantification of created DNAzyme. In this paper, the kinetics of isothermal linear strand displacement amplification reactions with different DNA lengths and isothermal exponential amplification reactions were successfully elucidated via the G-quadruplex based monitoring platform. As a safe and accessible alternative to the traditional methods, this robust, label-free, time-saving and high-throughput platform shows great potential for the exploration of more novel DNA reactions or circuits in an ingenious manner. PMID:25349990
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.
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. PMID:25240361
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.
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)
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.
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.
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.
Lee, Y.; Shen, J.; Klotz, P.J.; Schwartz, S.E.; Newman, L.
1986-11-20
The kinetics of the reaction of dissolved S(IV) with H/sub 2/O/sub 2/ was studied in freshly collected precipitation samples in order to examine whether there exist any important influences on this reaction from trace constituents present in natural atmospheric liquid water, that is, rainwater and snowmelt. The kinetic study was carried out on over 300 freshly collected precipitation samples obtained at Brookhaven National Laboratory, Long Island, New York, during the period from October 1983 to September 1985. The second-order rate constant k/sup (2)/, defined as -d(H/sub 2/O/sub 2/)/dt = k/sup (2)/(H/sub 2/O/sub 2/)(S(IV)), which was determined using the precipitation samples covering pH range 3.3--5.6, was found to be linearly dependent on H/sup +/ concentration, conforming to results previously obtained with purified water. The observed scatter in rate constant ( +- 30%, standard deviation) is comparable to interlaboratory scatter observed for purified water; the average rate constant is 15% less than values obtained in our laboratory using purified water at the same pH and ionic strength. The scatter and the systematic bias of the data were examined in terms of experimental techniques employed as well as chemical composition of the samples. Sample scatter is attributed in large part to uncertainty in measured pH. The difference in the average rate constant is small compared to the large scatter exhibited by the data. Causes of the negative bias were not clearly identified, but pH uncertainty, ionic strength, and the presence of formaldehyde were ruled out.
Effects of Deception on Children's Understanding of Second-Order False Belief
ERIC Educational Resources Information Center
Miller, Scott A.
2013-01-01
This research examined two questions: effects of deception on children's understanding of second-order false belief, and possible effects of number of siblings on second-order performance. Kindergarten children responded to 3 second-order problems that varied in the presence and the nature of deception. Performance was better on the problems…
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.
Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang
2016-06-01
This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H2O2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H2O2 concentration, while the optimal pH and H2O2 concentration were 7.0 and 8Î¼M, respectively. 98% TCS was removed with only 0.1UmL(-1) SBP in 30min reaction time, while an HRP dose of 0.3UmL(-1) was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (KCAT) and catalytic efficiency (KCAT/KM) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via CC and CO coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment. PMID:26921508
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.
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
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.
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 isâ€¦
A hot-atom reaction kinetic model for H abstraction from solid surfaces
NASA Astrophysics Data System (ADS)
Kammler, Th.; Kolovos-Vellianitis, D.; Küppers, J.
2000-07-01
Measurements of the abstraction reaction kinetics in the interaction of gaseous H atoms with D adsorbed on metal and semiconductor surfaces, H(g)+D(ad)/S? products, have shown that the kinetics of the HD products are at variance with the expectations drawn from the operation of Eley-Rideal mechanisms. Furthermore, in addition to HD product molecules, D 2 products were observed which are not expected in an Eley-Rideal scenario. Products and kinetics of abstraction reactions on Ni(100), Pt(111), and Cu(111) surfaces were recently explained by a random-walk model based solely on the operation of hot-atom mechanistic steps. Based on the same reaction scenario, the present work provides numerical solutions of the appropriate kinetic equations in the limit of the steady-state approximation for hot-atom species. It is shown that the HD and D 2 product kinetics derived from global kinetic rate constants are the same as those obtained from local probabilities in the random walk model. The rate constants of the hot-atom kinetics provide a background for the interpretation of measured data, which was missing up to now. Assuming that reconstruction affects the competition between hot-atom sticking and hot-atom reaction, the application of the present model at D abstraction from Cu(100) surfaces reproduces the essential characteristics of the experimentally determined kinetics.
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…
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)
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.
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.
Benzenium-ethene complex: a fundamental problem for standard second-order Møller-Plesset theory.
Schwabe, Tobias; Grimme, Stefan
2009-04-01
Recently, Kolboe and Svelle pointed out that second-order Møller-Plesset perturbation theory (MP2) incorrectly predicts a barrierless reaction of the benzenium-ethene complex to the ethyl-1H-benzene cation in contrast to other considered quantum chemical methods [J. Phys. Chem. A 2008, 112, 6399]. In a subsequent Letter in this Journal, van Mourik related this behavior to the basis set superposition error [J. Phys. Chem. A 2008, 112, 11017]. Here we can show that this is not the case but that the failure is due to an intrinsic (overcorrelation) problem of MP2. Improved perturbation methods (SCS-MP2 and B2PLYP double-hybrid functionals) provide correct results. PMID:19320511
JaÅ¡ÃkovÃ¡, Lucie; Anania, Mariarosa; HybelbauerovÃ¡, Simona; RoithovÃ¡, Jana
2015-10-28
A new method to investigate the reaction kinetics of intermediates in solution by electrospray ionization mass spectrometry is presented. The method, referred to as delayed reactant labeling, allows investigation of a reaction mixture containing isotopically labeled and unlabeled reactants with different reaction times. It is shown that we can extract rate constants for the degradation of reaction intermediates and investigate the effects of various reaction conditions on their half-life. This method directly addresses the problem of the relevance of detected gaseous ions toward the investigated reaction solution. It is demonstrated for geminally diaurated intermediates formed in the gold mediated addition of methanol to alkynes. Delayed reactant labeling allows us to directly link the kinetics of the diaurated intermediates with the overall reaction kinetics determined by NMR spectroscopy. It is shown that the kinetics of protodeauration of these intermediates mirrors the kinetics of the addition of methanol demonstrating they are directly involved in the catalytic cycle. Formation as well as decomposition of diaurated intermediates can be drastically slowed down by employing bulky ancillary ligands at the gold catalyst; the catalytic cycle then proceeds via monoaurated intermediates. The reaction is investigated for 1-phenylpropyne (Ph-CC-CH3) using [AuCl(PPh3)]/AgSbF6 and [AuCl(IPr)]/AgSbF6 as model catalysts. Delayed reactant labeling is achieved by using a combination of CH3OH and CD3OH or Ph-CC-CH3 and Ph-CC-CD3. PMID:26430872
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
SECOND-ORDER SOLUTIONS OF COSMOLOGICAL PERTURBATION IN THE MATTER-DOMINATED ERA
Hwang, Jai-chan; Noh, Hyerim; Gong, Jinn-Ouk
2012-06-10
We present the growing mode solutions of cosmological perturbations to the second order in the matter-dominated era. We also present several gauge-invariant combinations of perturbation variables to the second order in the most general fluid context. Based on these solutions, we study the Newtonian correspondence of relativistic perturbations to the second order. In addition to the previously known exact relativistic/Newtonian correspondence of density and velocity perturbations to the second order in the comoving gauge, here we show that in the sub-horizon limit we have the correspondences for density, velocity, and potential perturbations in the zero-shear gauge and in the uniform-expansion gauge to the second order. Density perturbation in the uniform-curvature gauge also shows the correspondence to the second order in the sub-horizon scale. We also identify the relativistic gravitational potential that shows exact correspondence to the Newtonian one to the second order.
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.
Kinetic measurements on elementary fossil fuel combustion reactions over wide temperature ranges
Fontijn, A.
1991-01-01
The goals of this work 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. In this reporting period our work on the O + Hcl reaction was published, experimental work on the O + benzene and O + 1-butene reactions was completed, and measurements on the O + isobutene reaction were initiated.
NASA Astrophysics Data System (ADS)
Lumbiny, B. J.; Hui, Z.; Islam, M. A.; Quader, M. A.; Rahman, M.
2014-04-01
Tetracoordinated organophosphorous compounds were synthesized, characterized and nucleophilic substitution reaction were investigated by varying substituents around phosphorous centre or in nucleophile considering its utility in biological and environmental system. The reactivity is expressed in terms of second-order rate constant, k2 and measured conductometrically. Linear Free Energy Relationship (LFER) tools mainly Hammett (?), Brönsted (?) LFER coefficients and deuterium kinetic isotope effects (KIEs) being determined for the pyridinolysis of 4 - chlorophenyl 4 - methoxy phenyl chlorophosphate, 1 in acetonitrile at 5.0 °C. The experimental data's were compared with those of structurally similar organophosphorous compounds reported earlier in quest for the mechanistic information. Nice linear correlation being found for Hammett (logk2 vs ?x), having negative value of the ?X = -5.85 and Brönsted (logk2 vs pKa(x)) plots having large positive value for ?X = 1.18 for 1 can be interpreted as SN2 process with greater extent of bond formation in transition state (TS) of 1. The observed kH/kD values of 1 is 1.00 ± 0.05 and net KIE, 1.32 suggests the primary KIE and indicates frontside nucleophilic attack through the partial deprotonation of pyridine occurs by the hydrogen bonding in the rate-determining step.
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.
A New Perspective on Kinetic and Thermodynamic Control of Reactions.
ERIC Educational Resources Information Center
Snadden, R. B.
1985-01-01
Kinetic versus thermodynamic control of product formation is discussed in undergraduate textbooks, and journal papers suggest suitable experiments to illustrate this concept. In rationalizing experimental observations, this paper offers a new alternative to that conventionally employed and provides students with an interesting exercise in…
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.â€¦
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
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. Theâ€¦
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…
Kinetics of a Substitution Reaction of Sulfitopentaaminecobalt(III).
ERIC Educational Resources Information Center
Richards, Lynne
1988-01-01
Describes a laboratory experiment to determine the rate law for a substitution reaction of a transition metal. Derives the corresponding rate law from the accepted mechanism for the reaction using the steady state approximation and determines the conditions under which the two agree. (CW)
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.
Systematic study of the reaction kinetics for HMX.
Long, Yao; Chen, Jun
2015-05-01
The reaction process of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in wide temperature and pressure ranges is simulated by molecular dynamics. A set of postprocessing programs is written to evaluate the intermediate molecules and chemical reactions. On the basis of these evaluations, the reaction rates, reactive Hugoniot curves, and detonation wave profile are calculated. The detonation velocity and detonation pressure are determined as 9984 m/s and 38.3349 GPa, in agreement with the experimental results, 9110 m/s and 39.5 GPa. The width of the reaction zone is 10 ?m, and the main products are N2, H2O, and CO2. We find some molecules play an important role in intermediate reactions but are not exhibited in final products, such as N2O2, N2O5, and C3H3N3. PMID:25866915
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
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...
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
Kinetics of electron transfer reactions in hydrothermal and supercritical water.
Cline, J. A.; Takahashi, K.; Marin, T. W.; Jonah, C. D.; Bartels, D. M.
2001-11-20
The rates of several radiation-induced reactions are assessed via pulse radiolysis in order to extend a model for nuclear reactor coolant radiolysis to supercritical conditions. They find changes in radiolysis yields and significant deviations from Arrhenius behavior at 250 bar as the temperature approaches and exceeds the critical temperature of pure water. At 380 C they also observe a strong pressure dependence of the reaction rates of ions and hydrophobic species. Using a homogeneous chemistry model, they find by 350 C that the relatively mild changes in these reaction rates increase the predicted critical hydrogen concentration relative to 325 C.
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...
Surface reactions kinetics between nanocrystalline magnetite and uranyl.
Missana, Tiziana; Maffiotte, César; García-Gutiérrez, Miguel
2003-05-01
Magnetite is the most important end member of iron corrosion products under reducing environment, which is the condition expected in a deep geological high level radioactive waste disposal. Nanocrystalline magnetite was synthesized in the laboratory and its physicochemical properties were analyzed in detail. The kinetics of the adsorption of U(VI) and the kinetics of the actinide reduction to a lower oxidation state, in presence of the oxide, were studied by means of batch sorption techniques and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the uranium sorption and reduction processes on the magnetite surface have very fast kinetics (hours), the reduction process being triggered by sorption. XPS measurements showed that the speciation of uranium at the surface does not show significant changes with time (from 1 day to 3 months), as well as the quantity of uranium detected at the surface. The surface speciation depended on the initial pH of the contact solution. Considering that the Eh of equilibrium between magnetite and the solution, under our experimental conditions, is slightly positive (50-100 mV), the uranium reduction would also be thermodynamically possible within the liquid phase. However, the kinetics of reduction in the liquid occur at a much slower rate which, in turn, has to depend on the attainment of the magnetite/solution equilibrium. The decrease of uranium in solution, observed after the uranyl adsorption stage, and particularly at acidic pH, is most probably due to the precipitation of U(IV) formed in the solution. PMID:12725835
NASA Astrophysics Data System (ADS)
Jung, Byungki; Ober, Christopher K.; Thompson, Michael O.
2012-03-01
Chemically amplified photoresists require a post exposure bake (PEB) to induce deprotection using a UV generated acid-catalyst. While reaction pathways for deprotection have been proposed, key challenges remain in modeling the reaction kinetics. In this work, we used a scanning line-focused laser beam as an alternate PEB method, to quantify the deprotection reaction kinetics of an ESCAP-type and a 193 nm model resist system at high temperatures in millisecond time frames. Results were compared with conventional PEB at 115°C for seconds time frames. Results show that the deprotection kinetics follow simple first-order reaction models only under laser PEB conditions, with more complex kinetics observed under hot plate PEB. FT-IR and NMR spectroscopies were used to characterize the reaction byproducts. Results suggest potential differences in deprotection mechanisms between the two PEB temperature and time regimes. The deprotection behavior obtained using this l-PEB technique enables a deeper understanding of the reaction kinetics of photoresists, critical for current DUV and future EUV technologies.
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.
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.
Kinetics and mechanism of the IO + IO reaction
NASA Technical Reports Server (NTRS)
Sander, S. P.
1986-01-01
The flash photolysis-absorption technique has been used to measure the rate constant for the reaction IO + IO over the temperature range 250-373 K and pressure range 20-700 torr of N2. The rate constant for the overall reaction was found to be independent of pressure and equal to 1.73 x 10 to the -12th exp (1020 + or - 200)/T cu cm/molecule s. Branching ratios for the reaction channels forming 2I + O2, I2 + O2, and I2O2, were found to be pressure dependent, with the I2 channel accounting for less than 5 percent of the total reaction over the observed pressure range. A stable reaction product was observed between 230 and 300 nm which was formed on a long time scale compared to IO disappearance. The rate constant for the reaction I + O3 + yields to IO + O2 was measured at 298 K and found to be (9.5 + or - 1.5) x 10 to the -13th cu cm/molecule s.
Carrasquillo-Flores, Ronald; Gallo, Jean Marcel R.; Hahn, Konstanze; Dumesic, James A.; Mavrikakis, Manos
2013-11-05
Periodic, self-consistent density functional theory calculations (DFT-GGA-PW91) on Pt(111) and Pt_{3}Re(111) surfaces, reaction kinetics measurements, and microkinetic modeling are employed to study the mechanism of the water–gas shift (WGS) reaction over Pt and Pt–Re catalysts. The values of the reaction rates and reaction orders predicted by the model are in agreement with the ones experimentally determined; the calculated apparent activation energies are matched to within 6% of the experimental values. The primary reaction pathway is predicted to take place through adsorbed carboxyl (COOH) species, whereas formate (HCOO) is predicted to be a spectator species. We conclude that the clean Pt(111) is a good representation of the active site for the WGS reaction on Pt catalysts, whereas the active sites on the Pt–Re alloy catalyst likely contain partially oxidized metal ensembles.
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. PMID:24832250
General theory of multistage geminate reactions of isolated pairs of reactants. I. Kinetic equations
NASA Astrophysics Data System (ADS)
Doktorov, Alexander B.; Kipriyanov, Alexey A.
2014-05-01
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.
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.
NASA Astrophysics Data System (ADS)
Ismagilov, Timur Z.
2013-10-01
A second order finite volume scheme for numerical solution of Maxwell's equations with discontinuous dielectric permittivity on structured meshes is suggested. The scheme is based on approaches of Godunov, Lax-Wendroff and Van Leer. The distinctive feature of the suggested scheme is calculation and limitation of derivatives that ensures second order of approximation even in the cells adjacent to dielectric permittivity discontinuity. Numerical tests for problems with linear and curvilinear dielectric permittivity discontinuities confirm second order of approximation.
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.
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.
Second-order sideband effects mediated by microwave in hybrid electro-optomechanical systems
NASA Astrophysics Data System (ADS)
Chen, Bin; Wang, Lei-Dong; Zhang, Jie; Zhai, Ai-Ping; Xue, Hai-Bin
2016-02-01
We theoretically investigate the second-order sideband effects in a hybrid electro-optomechanical system, and mainly focus on the influence of the microwave signal on the second-order sideband generation. The numerical results show that just by tuning the power and the detuning of the microwave signal, the second-order sideband can be significantly modified. More importantly, while driving this hybrid system by a blue detuned microwave with suitable power, strong second-order sideband effect can be induced. These results can find potential applications in optical frequency converters in the quantum information processing.
Snodgrass, Michael; Kalaida, Natasha; Winer, E Samuel
2009-06-01
Access can either be first-order or second-order. First order access concerns whether contents achieve representation in phenomenal consciousness at all; second-order access concerns whether phenomenally conscious contents are selected for metacognitive, higher order processing by reflective consciousness. When the optional and flexible nature of second-order access is kept in mind, there remain strong reasons to believe that exclusion failure can indeed isolate phenomenally conscious stimuli that are not so accessed. Irvine's [Irvine, E. (2009). Signal detection theory, the exclusion failure paradigm and weak consciousness-Evidence for the access/phenomenal distinction? Consciousness and Cognition.] partial access argument fails because exclusion failure is indeed due to lack of second-order access, not insufficient phenomenally conscious information. Further, the enable account conforms with both qualitative differences and subjective report, and is simpler than the endow account. Finally, although first-order access may be a distinct and important process, second-order access arguably reflects the core meaning of access generally. PMID:19243977
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
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
Second-order structure function analysis of scatterometer winds over the Tropical Pacific
NASA Astrophysics Data System (ADS)
King, Gregory P.; Vogelzang, Jur; Stoffelen, Ad
2015-01-01
second-order structure functions are used to quantify and compare the small-scale information contained in near-surface ocean wind products derived from measurements by ASCAT on MetOp-A and SeaWinds on QuikSCAT. Two ASCAT and three SeaWinds products are compared in nine regions (classified as rainy or dry) in the tropical Pacific between 10°S and 10°N and 140° and 260°E for the period November 2008 to October 2009. Monthly and regionally averaged longitudinal and transverse structure functions are calculated using along-track samples. To ease the analysis, the following quantities were estimated for the scale range 50 to 300 km and used to intercompare the wind products: (i) structure function slopes, (ii) turbulent kinetic energies (TKE), and (iii) vorticity-to-divergence ratios. All wind products are in good qualitative agreement, but also have important differences. Structure function slopes and TKE differ per wind product, but also show a common variation over time and space. Independent of wind product, longitudinal slopes decrease when sea surface temperature exceeds the threshold for onset of deep convection (about 28°C). In rainy areas and in dry regions during rainy periods, ASCAT has larger divergent TKE than SeaWinds, while SeaWinds has larger vortical TKE than ASCAT. Differences between SeaWinds and ASCAT vortical TKE and vorticity-to-divergence ratios for the convectively active months of each region are large.
Yoon, In-Ho; Yoo, Gursong; Hong, Hye-Jin; Kim, Jungmin; Kim, Min Gyu; Choi, Wang-Kyu; Yang, Ji-Won
2016-02-01
In this study, we investigated phenol degradation via zero-valent iron (ZVI)-assisted Fenton reaction through kinetic and spectroscopic analysis. In batch experiments, 100Â mg/L of phenol was completely degraded, and 75% of TOC was removed within 3Â min under an optimal hydrogen peroxide (H2O2) concentration (50Â mM) via the Fenton reaction. In the absence of H2O2, oxygen (O2) was dissolved into the solution and produced H2O2, which resulted in phenol degradation. However, phenol removal efficiency was not very high compared to external H2O2 input. The Fenton reaction rapidly occurred at the surface of ZVI, and then phenol mobility from the solution to the ZVI surface was the rate determining step of the whole reaction. The pseudo-second order adsorption kinetic model well describes phenol removal, and its rate increased according to the H2O2 concentration. X-ray absorption spectroscopic analysis revealed that iron oxide (Fe-O bonding) was formed on ZVI with [H2O2]Â >Â 50Â mM. A high concentration of H2O2 led to rapid degradation of phenol and caused corrosion on the ZVI surface, indicating that Fe(2+) ions were rapidly oxidized to Fe(3+) ions due to the Fenton reaction and that Fe(3+) was precipitated as iron oxide on the ZVI surface. However, ZVI did not show corroded characteristics in the absence of H2O2 due to the insufficient ZVI-assisted Fenton reaction and oxidation of Fe(2+) to Fe(3+). PMID:26692518
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.
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.
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.
Reaction kinetics, molecular action, and mechanisms of cellulolytic proteins.
Mosier, N S; Hall, P; Ladisch, C M; Ladisch, M R
1999-01-01
Cellulolytic proteins form a complex of enzymes that work together to depolymerize cellulose to the soluble products cellobiose and glucose. Fundamental studies on their molecular mechanisms have been facilitated by advances in molecular biology. These studies have shown homology between cellulases from different microorganisms, and common mechanisms between enzymes whose modes of action have sometimes been viewed as being different, as suggested by the distribution of soluble products. A more complete picture of the cellulolytic action of these proteins has emerged and combines the physical and chemical characteristics of solid cellulose substrates with the specialized structure and function of the cellulases that break it down. This chapter combines the fundamentals of cellulose structure with enzyme function in a manner that relates the cellulose binding and biochemical kinetics at the catalytic site of the proteins to the macroscopic behavior of cellulase enzyme systems. PMID:10533433
ERIC Educational Resources Information Center
Coull, Greig J.; Leekam, Susan R.; Bennett, Mark
2006-01-01
This study investigated how 4- to 7-year-old children's second-order belief attribution might be facilitated by either reducing information processing or varying the sequence of task questions. In Experiment 1, compared with Perner and Wimmer's (1985) original second-order false-belief task, a new task with reduced information-processing demands…
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)
Operator Factorization and the Solution of Second-Order Linear Ordinary Differential Equations
ERIC Educational Resources Information Center
Robin, W.
2007-01-01
The theory and application of second-order linear ordinary differential equations is reviewed from the standpoint of the operator factorization approach to the solution of ordinary differential equations (ODE). Using the operator factorization approach, the general second-order linear ODE is solved, exactly, in quadratures and the resultingâ€¦
Having a Second-Order Mind while Doing First-Order Therapy.
ERIC Educational Resources Information Center
Simon, George M.
1992-01-01
Contends that overemphasis in literature on distinguishing first- and second-order therapeutic perspectives has produced schism within field of family therapy. Attempts to bridge that schism, using view of language that informs dialectical psychology to construct both-order, and framing of first- and second-order, perspectives. Such framingâ€¦
Operator Factorization and the Solution of Second-Order Linear Ordinary Differential Equations
ERIC Educational Resources Information Center
Robin, W.
2007-01-01
The theory and application of second-order linear ordinary differential equations is reviewed from the standpoint of the operator factorization approach to the solution of ordinary differential equations (ODE). Using the operator factorization approach, the general second-order linear ODE is solved, exactly, in quadratures and the resulting…
Reaction kinetics of resveratrol with tert-butoxyl radicals
NASA Astrophysics Data System (ADS)
DÅ¾eba, Iva; Pedzinski, Tomasz; MihaljeviÄ‡, Branka
2012-09-01
The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5Ã—108 M-1s-1. This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol.
Reaction Mechanism and Kinetics of Enargite Oxidation at Roasting Temperatures
NASA Astrophysics Data System (ADS)
Padilla, Rafael; Aracena, Alvaro; Ruiz, Maria C.
2012-10-01
Roasting of enargite (Cu3AsS4) in the temperature range of 648 K to 898 K (375 °C to 625 °C) in atmospheres containing variable amounts of oxygen has been studied by thermogravimetric methods. From the experimental results of weight loss/gain data and X-ray diffraction (XRD) analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was determined, which occurred in three sequential stages:
Kinetics of diffusion-controlled enzymatic reactions with charged substrates.
Lu, Benzhuo; McCammon, J Andrew
2010-01-01
The Debye-Hückel limiting law (DHL) has often been used to estimate rate constants of diffusion-controlled reactions under different ionic strengths. Two main approximations are adopted in DHL: one is that the solution of the linearized Poisson-Boltzmann equation for a spherical cavity is used to estimate the excess electrostatic free energy of a solution; the other is that details of electrostatic interactions of the solutes are neglected. This makes DHL applicable only at low ionic strengths and dilute solutions (very low substrate/solute concentrations). We show in this work that through numerical solution of the Poisson-Nernst-Planck equations, diffusion-reaction processes can be studied at a variety of conditions including realistically concentrated solutions, high ionic strength, and certainly with non-equilibrium charge distributions. Reaction rate coefficients for the acetylcholine-acetylcholinesterase system are predicted to strongly depend on both ionic strength and substrate concentration. In particular, they increase considerably with increase of substrate concentrations at a fixed ionic strength, which is open to experimental testing. This phenomenon is also verified on a simple model, and is expected to be general for electrostatically attracting enzyme-substrate systems.PACS Codes: 82.45.Tv, 87.15.VvMSC Codes: 92C30. PMID:20157429
Low temperature kinetics of the CH3OH + OH reaction.
Gómez Martín, J C; Caravan, R L; Blitz, M A; Heard, D E; Plane, J M C
2014-04-17
The rate constant of the reaction between methanol and the hydroxyl radical has been studied in the temperature range 56-202 K by pulsed laser photolysis-laser induced fluorescence in two separate experiments using either a low temperature flow tube coupled to a time-of-flight mass spectrometer or a pulsed Laval nozzle apparatus. The two independent techniques yield rate constants that are in mutual agreement and consistent with the results reported previously below 82 K [Shannon et al. Nat. Chem. 2013, 5, 745-749] and above 210 K [Dillon et al. Phys. Chem. Chem. Phys. 2005, 7, 349-355], showing a very sharp increase with decreasing temperature with an onset around 180 K. This onset is also signaled by strong chemiluminescence tentatively assigned to formaldehyde, which is consistent with the formation of the methoxy radical at low temperature by quantum tunnelling, and its subsequent reaction with H and OH. Our results add confidence to the previous low temperature rate constant measurements and consolidate the experimental reference data set for further theoretical work required to describe quantitatively the tunnelling mechanism operating in this reaction. An additional measurement of the rate constant at 56 K yielded a value of (4.9 ± 0.8) × 10(-11) cm(3) molecule(-1) s(-1) (2?), showing that the rate constant is increasing less rapidly at temperatures below 70 K. PMID:24669816
Low Temperature Kinetics of the CH3OH + OH Reaction
Martín, J. C. Gómez; Caravan, R. L.; Blitz, M. A.; Heard, D. E.; Plane, J. M. C.
2014-01-01
The rate constant of the reaction between methanol and the hydroxyl radical has been studied in the temperature range 56-202 K by pulsed laser photolysis-laser induced fluorescence in two separate experiments using either a low temperature flow tube coupled to a time of flight mass spectrometer or a pulsed Laval nozzle apparatus. The two independent techniques yield rate constants which are in mutual agreement and consistent with the results reported previously below 82 K [Shannon et al., Nature Chemistry, 2013, 5, 745-749] and above 210 K [Dillon et al., Phys. Chem. Chem. 2005, 7, 349-355], showing a very sharp increase with decreasing temperature with an onset around 180 K. This onset is also signalled by strong chemiluminescence tentatively assigned to formaldehyde, which is consistent with the formation of the methoxy radical at low temperature by quantum tunnelling, and its subsequent reaction with H and OH. Our results add confidence to the previous low temperature rate constant measurements and consolidate the experimental reference dataset for further theoretical work required to describe quantitatively the tunnelling mechanism operating in this reaction. An additional measurement of the rate constant at 56 K yielded a value of (4.9 ± 0.8) × 10?11 cm3 molecule?1 s?1 (2?), showing that the rate constant is increasing less rapidly at temperatures below 70 K. PMID:24669816
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.
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.
Optimality Conditions in Differentiable Vector Optimization via Second-Order Tangent Sets
Jimenez, Bienvenido Novo, Vicente
2004-03-15
We provide second-order necessary and sufficient conditions for a point to be an efficient element of a set with respect to a cone in a normed space, so that there is only a small gap between necessary and sufficient conditions. To this aim, we use the common second-order tangent set and the asymptotic second-order cone utilized by Penot. As an application we establish second-order necessary conditions for a point to be a solution of a vector optimization problem with an arbitrary feasible set and a twice Frechet differentiable objective function between two normed spaces. We also establish second-order sufficient conditions when the initial space is finite-dimensional so that there is no gap with necessary conditions. Lagrange multiplier rules are also given.
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.
New Colorimetric reaction for end-point, continuous-flow, and kinetic measurement of urea.
Jung, D; Biggs, H; Erikson, J; Ledyard, P U
1975-07-01
A reaction of urea, o-phthalaldehyde and N-(1-naphthyl)ethylenediamine is described for measurement of urea by manual, continuous-flow, and kinetic methods. The continuous-flow system requires 25 mu-l of sample; 40 samples can be analyzed per hour. The kinetic method requires no enzymes, has no lag phase, and has good sensitivity. A major advantage of the reaction is that it occurs at a temperature of 37 degrees C or lower. The results obtained by all three methods agree well with those for a continuous-flow procedure in which diacetyl is a reagent. PMID:1137920
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)
Control of DNA Replication by Anomalous Reaction-Diffusion Kinetics
NASA Astrophysics Data System (ADS)
Gauthier, Michel G.; Bechhoefer, John
2009-04-01
We propose a simple model for the control of DNA replication in which the rate of initiation of replication origins is controlled by protein-DNA interactions. Analyzing recent data from Xenopus frog embryos, we find that the initiation rate is reaction limited until nearly the end of replication, when it becomes diffusion limited. Initiation of origins is suppressed when the diffusion-limited search time dominates. To fit the experimental data, we find that the interaction between DNA and the rate-limiting protein must be subdiffusive.
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.
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
Kinetics of 1,5-hydrogen migration in alkyl radical reaction class.
Ratkiewicz, Artur; Bankiewicz, Barbara
2012-01-12
Kinetics of the 1,5-intramolecular hydrogen migration in the alkyl radicals reaction class has been studied using the reaction class transition state theory combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approach. The high pressure limits of the rate constants for the reference reaction of 1-pentyl ? 1-pentyl, calculated by the Canonical Variational Transition State Theory (CVT) with the Small Curvature Tunneling (SCT), are taken from the literature. Direct comparison with available experimental data indicates that the RC-TST/LER, where only reaction energy is needed, can predict rate constants for any reaction in this reaction class with excellent accuracy. Specifically for this reaction class, the RC-TST/LER method has less than 65% systematic errors in the predicted rate constants when compared to explicit rate calculations. PMID:22129072
Semitsoglou-Tsiapou, Sofia; Templeton, Michael R; Graham, Nigel J D; HernÃ¡ndez Leal, LucÃa; Martijn, Bram J; Royce, Alan; Kruithof, Joop C
2016-03-15
The degradation kinetics of three pesticides - metaldehyde, clopyralid and mecoprop - by ultraviolet photolysis and hydroxyl radical oxidation by low pressure ultraviolet hydrogen peroxide (LP-UV/H2O2) advanced oxidation was determined. Mecoprop was susceptible to both LP-UV photolysis and hydroxyl radical oxidation, and exhibited the fastest degradation kinetics, achieving 99.6% (2.4-log) degradation with a UV fluence of 800Â mJ/cm(2) and 5Â mg/L hydrogen peroxide. Metaldehyde was poorly degraded by LP-UV photolysis while 97.7% (1.6-log) degradation was achieved with LP-UV/H2O2 treatment at the maximum tested UV fluence of 1000Â mJ/cm(2) and 15Â mg/L hydrogen peroxide. Clopyralid was hardly susceptible to LP-UV photolysis and exhibited the lowest degradation by LP-UV/H2O2 among the three pesticides. The second-order reaction rate constants for the reactions between the pesticides and OH-radicals were calculated applying a kinetic model for LP-UV/H2O2 treatment to be 3.6Â Ã—Â 10(8), 2.0Â Ã—Â 10(8) and 1.1Â Ã—Â 10(9)Â M(-1)Â s(-1) for metaldehyde, clopyralid and mecoprop, respectively. The main LP-UV photolysis reaction product from mecoprop was 2-(4-hydroxy-2-methylphenoxy) propanoic acid, while photo-oxidation by LP-UV/H2O2 treatment formed several oxidation products. The photo-oxidation of clopyralid involved either hydroxylation or dechlorination of the ring, while metaldehyde underwent hydroxylation and produced acetic acid as a major end product. Based on the findings, degradation pathways for the three pesticides by LP-UV/H2O2 treatment were proposed. PMID:26803264
Control of DNA replication by anomalous reaction-diffusion kinetics
NASA Astrophysics Data System (ADS)
Bechhoefer, John; Gauthier, Michel
2010-03-01
DNA replication requires two distinct processes: the initiation of pre-licensed replication origins and the propagation of replication forks away from the fired origins. Experiments indicate that these origins are triggered over the whole genome at a rate I(t) (the number of initiations per unreplicated length per time) that increases throughout most of the synthesis (S) phase, before rapidly decreasing to zero at the end of the replication process. We propose a simple model for the control of DNA replication in which the rate of initiation of replication origins is controlled by protein-DNA interactions. Analyzing recent data from Xenopus frog embryos, we find that the initiation rate is reaction limited until nearly the end of replication, when it becomes diffusion limited. Initiation of origins is suppressed when the diffusion-limited search time dominates. To fit the experimental data, we find that the interaction between DNA and the rate-limiting protein must be subdiffusive.
Kinetics of the reaction Cl + NO2 + M
NASA Technical Reports Server (NTRS)
Leu, M.-T.
1984-01-01
Using atomic chlorine resonance fluorescence at 140 nm to detect the decay of atomic chlorine in the presence of an excess of NO2, the rate constant for the reaction Cl + NO2 + M, where M is the total gas concentration, is measured over the temperature range 264 to 417 K and at a pressure 1 to 7 torr in a discharge flow system. The rate constants for M= He and M= N2 are measured and the results are summarized in a table. The systematic error of the rate constants is estimated to be about 15 percent. A static photolysis system coupled with an FTIR spectrophotometer is used to determine the branching ratio for the formation of two possible isomers. The ratio is concluded to be ClONO (greater than or equal 75 percent) and ClNO2 (less than or equal 25 percent) which is in agreement with the results of Niki et al. (1978).
Application of Gaussian-type geminals in local second-order Møller-Plesset perturbation theory
NASA Astrophysics Data System (ADS)
Polly, Robert; Werner, Hans-Joachim; Dahle, Pa?L.; Taylor, Peter R.
2006-06-01
In this work Gaussian-type Geminals (GTGs) are applied in local second-order Møller-Plesset perturbation theory to improve the basis set convergence. Our implementation is based on the weak orthogonality functional of Szalewicz et al., [Chem. Phys. Lett. 91, 169 (1982); J. Chem. Phys. 78, 1420 (1983)] and a newly developed program for calculating the necessary many-electron integrals. The local approximations together with GTGs in the treatment of the correlation energy are introduced and tested. First results for correlation energies of H2O, CH4, CO, C2H2, C2H4, H2CO, and N2H4 as well as some reaction and activation energies are presented. More than 97% of the valence-shell correlation energy is recovered using aug-cc-pVDZ basis sets and six GTGs per electron pair. The results are compared with conventional calculations using correlation-consistent basis sets as well as with MP2-R12 results.
Design, synthesis and polymerization of novel second-order nonlinear optical materials
NASA Astrophysics Data System (ADS)
Ghosn, Rima Kamal
1997-10-01
This dissertation focuses on the design, synthesis and nonlinear optical properties of large second-order nonlinearity chromophores. A review of the fundamentals of nonlinear optics and polymeric materials is provided in the first chapter. The second chapter focuses on the optimization of reaction conditions of asymmetric diphenyl diacetylene liquid crystals. The third chapter deals with the design and synthesis of chromophores derived from thiobarbituric acids. Conventional nonlinear optical organic materials employ chromophores possessing a large transition dipole moment between the ground and first excited states. This requirement is fulfilled using conjugated molecules containing optimally balanced electron donor and acceptor moieties. Barbituric acid is a strong electron acceptor that yields molecules with a large first hyperpolarizabilities. There are two classes of chromophores investigated, both capable of covalent polymer incorporation, which include the main chain and double-end crosslinkable chromophores. These chromophores, high in both nonlinearity and thermal stability, are regarded as ideal candidates for electrooptical devices. The fourth chapter investigates polyimides as stable NLO polymeric materials.
NASA Astrophysics Data System (ADS)
Montero, María A.; Gennero de Chialvo, María R.; Chialvo, Abel C.
2015-06-01
The hydrogen oxidation reaction was studied on a nanostructured rhodium electrode at different rotation rates in alkaline solution. The electrode was prepared via sputtering on a glassy carbon disc support and it was characterized by atomic force microscopy and cyclic voltammetry. The real surface area was evaluated by CO stripping voltammetry. Experimental current density (j) - overpotential (?) curves of the hydrogen oxidation reaction were obtained in the range -0.015 ? ?/V ? 0.40 at different rotation rates (900 ? ?/rpm ? 4900). The resulting curves were correlated by kinetic expressions derived from the Tafel-Heyrovsky-Volmer mechanism with a Frumkin type adsorption of the reaction intermediate and the kinetic parameters were evaluated. It was verified that over this overpotential region the reaction in alkaline solution proceeds mainly through the Tafel-Volmer route. These results were compared with those previously obtained in acid solutions.
Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle
NASA Technical Reports Server (NTRS)
Fegley, Bruce, Jr.
1997-01-01
The purpose of this project was to experimentally measure the rates of several thermochemical gas-solid reactions between sulfur gases in the Venus atmosphere and reactive minerals on the hot Venus surface. Despite the great importance of these reactions for the maintenance of significant amounts of sulfur gases (and thus for the maintenance of the global cloud cover) in the atmosphere of Venus, essentially no kinetic data are currently available for them.
How to draw kinetic barrier diagrams for enzyme-catalysed reactions.
Südi, J
1991-01-01
A modified way to construct kinetic barrier diagrams is presented. Although the diagram superficially resembles a free-energy profile, it is independent of any conception derived from transition-state theory. Some simple calculations referring to the lactate dehydrogenase turnover reaction at equilibrium demonstrate self-consistency of the diagram and its direct relevance to the results of numerical simulations of the detailed course of enzyme-catalysed reactions. PMID:2039478
Form and motion processing of second-order stimuli in color vision.
Garcia-Suarez, Luis; Mullen, Kathy T
2013-01-01
We investigate whether there are second-order form and motion mechanisms in human color vision. Second-order stimuli are contrast modulations of a noise carrier. The contrast envelopes are static Gabors of different spatial frequencies (0.125-1 cycles/°) or drifting Gabors of different temporal frequencies (0.25 cycles/°, 0.5-4 Hz). Stimuli are isoluminant red-green or achromatic. Second-order form processing is measured using a simultaneous 2IFC (two-interval forced-choice) detection and orientation identification task, and direction identification is used for second-order motion processing. We find that for simple detection thresholds, chromatic performance is as good or better than achromatic performance, whereas for both motion and form tasks, chromatic performance is poorer than achromatic. Chromatic second-order form perception is very poor across all spatial and temporal frequencies measured and has a lowpass contrast modulation sensitivity function with a spatial cutoff of 1 cycle/° and temporal cutoff of 4 Hz. Chromatic second-order motion sensitivity is even poorer than for form and typically is limited to 1-2 Hz. To determine whether this residual motion processing might be based on feature tracking, we used the pedestal paradigm of Lu and Sperling (1995). We find that adding a static pedestal of the same spatial frequency as the drifting Gabor envelope, with its contrast set to 1-2 times its detection threshold, impairs motion direction performance for the chromatic stimuli but not the achromatic. This suggests that the motion of second-order chromatic stimuli is not processed by a second-order system but by a third-order, feature-tracking system, although a genuine second-order motion system exists for achromatic stimuli. PMID:23766541
Kinetics of Single-Enzyme Reactions on Vesicles: Role of Substrate Aggregation
NASA Astrophysics Data System (ADS)
Zhdanov, Vladimir P.
2015-03-01
Enzymatic reactions occurring in vivo on lipid membranes can be influenced by various factors including macromolecular crowding in general and substrate aggregation in particular. In academic studies, the role of these factors can experimentally be clarified by tracking single-enzyme kinetics occurring on individual lipid vesicles. To extend the conceptual basis for such experiments, we analyze herein the corresponding kinetics mathematically with emphasis on the role of substrate aggregation. In general, the aggregation may occur on different length scales. Small aggregates may e.g. contain a few proteins or peptides while large aggregates may be mesoscopic as in the case of lipid domains which can be formed in the membranes composed of different lipids. We present a kinetic model describing comprehensively the effect of aggregation of the former type on the dependence of the reaction rate on substrate membrane concentration. The results obtained with physically reasonable parameters indicate that the aggregation-related deviations from the conventional Michaelis-Menten kinetics may be appreciable. Special Issue Comments: This theoretical article is focused on single-enzyme reactions occurring in parallel with substrate aggregation on individual vesicles. This subject is related to a few Special Issue articles concerning enzyme dynamics6,7 and function8 and mathematical aspects of stochastic kinetics.9
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
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Tungatarov, Aliaskar; Rzayeva, Gulnar
2015-09-01
The main purpose of the present paper consists an investigation of an elliptic system in the plane with Laplace operator in differential part. Within the scope of this target, investigation of the continuous solutions of a class of complex partial second order differential equations in the plane in explicit form are constructed. Robin boundary value problem for second order elliptic system in the plane with singular coefficients in unbounded angular domain is solved. In this article, a new method for construction of the general solution of second order ordinary differential equation with variable coefficients developed by A. Tungatarov is used.
NASA Astrophysics Data System (ADS)
Luo, T.; Khursheed, A.
2006-04-01
At present transmission electron energy loss spectrum (EELS) analysis is only carried out in dedicated research instruments such as transmission electron microscopes (TEMs) or scanning transmission electron microscopes. This article presents a new design of second-order geometric aberration corrected EELS spectrometer attachment using split plates, which enables conventional scanning electron microscopes (SEMs) to provide TEM-like EELS spectra. Correction to a third-order dominant geometric aberration pattern has been achieved, which indicates that most of the second-order geometric aberration component is eliminated. This second-order aberration corrected spectrometer attachment design can enable SEMs to provide transmission EELS spectrums.
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.
Second-order Born effect in coplanar doubly symmetric (e,2e) collisions for sodium
NASA Astrophysics Data System (ADS)
Wang, Yang; Jiao, Liguang; Zhou, Yajun
2012-06-01
The second-order distorted wave Born approximation (DWBA) method is employed to investigate the triple differential cross sections (TDCS) of coplanar doubly symmetric (e,2e) collisions for alkali target sodium at excess energies of 6-60 eV. Comparing with the first-order DWBA calculations, the inclusion of second-order Born term in the scattering amplitude improves the degree of agreement with experiments, especially for backward scattering region of TDCS. This indicates the present second-order Born term is capable to give a reasonable correction to DWBA model in studying coplanar symmetric (e,2e) problems in low and intermediate energy range.
Second-Order Born Effect in Single Ionization of Argon by Electron Impact
NASA Astrophysics Data System (ADS)
Wang, Yang; Zhou, Ya-Jun; Jiao, Li-Guang
2012-01-01
We extend the standard distorted wave Born approximation (DWBA) to include the second-order Born amplitude in order to describe the multiple interactions between a projectile and an atomic target. Both the first- and second- order DWBA models are used to calculate triply differential cross sections (TDCS) of coplanar (e, 2e) on atomic argon with the scattered electron energy fixed at 500 eV, the scattering angle at 6° and the ejected electron energies at 37, 74 and 205 eV. Overall agreements with experimental measurements have been obtained in shape, and the second-order DWBA model improves the calculations as expected, especially for recoil peak of TDCS.
[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 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)
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 making of an Alfvenic fluctuation: The resolution of a second-order analysis
NASA Technical Reports Server (NTRS)
Vasquez, Bernard J.; Hollweg, Joseph V.
1995-01-01
Ulysses observations of the high speed polar streams show that they are largely occupied by very large amplitude Alfvenic fluctuations accompanied by many rotational discontinuities. These fluctuations have a nearly constant magnetic intensity or amplitude, and the magnetic field direction per wave cycle sweeps only through a limited arc, much as a car wiperblade would do. Barnes and Hollweg (JGR, 79, 2302, 1974) suggested that this unusual waveform could arise from an obliquely propagating and linearly polarized Alfven wave of finite amplitude. From a second-order analysis, they showed that the existence of a particular solution with a constant amplitude but could not resolve the outcome of the homogeneous solution which consisted of fast waves. They suggested that Landau damping of these fast waves may be needed to get the observed waveform. We present a 1 1/2 D hybrid simulation which is fully nonlinear and correctly describes the ion kinetics for an initially monochromatic and linearly polarized Alfven wave propagating obliquely to the background magnetic field. The wave has a large amplitude and a wavelength so long that it can be considered dispersionless for simulation times. At early times, the second harmonic in density and in magnetic field transverse to the initial wave magnetic field are generated and have more power than other harmonics. Steepening is observed with a weak fast shock emerging, but no rotational discontinuity is left behind, and instead a constant amplitude and an arc-shaped waveform is made. The compressional component which develops after the shocks have dissipated is to zeroth order better described as a pure acoustic wave than as a fast wave. This might be explained by the relaxing of the Alfven wave to a state where its ponderomotive force vanishes so that the compressional component can travel almost independently of it.
Thermodynamics and kinetics of reactions in protective coating systems
NASA Technical Reports Server (NTRS)
Gupta, B.; Sarkhel, A.; Sivakumar, R.; Seigle, L.
1974-01-01
Investigations of fluoride activated packs with Al:Ni ratios greater than 50 a/o prove that the specimen surface is not in equilibrium with the pack at high Al:Ni ratios but that an activity gradient exists between pack and specimen. Therefore, gaseous diffusion and possibly surface reactions play a role in determining the overall rate of Al deposition in such packs. Noticeable differences in coating behavior have been obtained in packs activated with chloride and iodide, and it appears that poorest results are obtained with iodides, better with chlorides, and best with fluorides. A numerical method has been perfected for calculating rates of solid-state diffusion controlled coating formation, allowing for the variation of diffusivity with composition in the NiAl phase. Layer growth rates can now be accurately predicted from a knowledge of the surface and substrate compositions. Furthermore, the correct diffusion profiles are obtained by this method. These differ substantially from the profile obtained when the diffusivity is assumed constant.
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.
Hanson, R.K.; Bowman, C.T.
1985-01-01
This report summarizes progress during the past 8 months of an ongoing program on the reaction kinetics of cyano compounds at high temperatures. The objectives of this research program are threefold: (1) to obtain high temperature kinetic data on elementary oxidation reactions involving the cyano compounds HCN, CN and NCO; (2) to develop improved procedures for preparing the reactants 0 and 0H in shock tube studies; and (3) to develop improved measurement techniques for the species NCO, CN, NH, OH and H. During this reporting period work has been focussed on the design, assembly and initial testing of an atomic resonance absorption spectroscopy (ARAS) system for monitoring H in shock tube kinetics experiments. 1 fig.
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 andâ€¦
Shaozeng Sun; Juwei Zhang; Xidong Hu; Shaohua Wu; Jiancheng Yang; Yang Wang; Yukun Qin
2009-01-15
Four coal chars were prepared in a flat flame flow reactor (FFR), which can simulate the temperature and gas composition of a real pulverized coal combustion environment. The pore structure of chars was measured by mercury porosimetry and nitrogen adsorption, and the Hg and Brunauer-Emmett-Teller (BET) surface areas were obtained. The kinetics of NO-char was studied in a drop-tube furnace (DTF) and thermogravimetric analyzer (TGA). In the TGA experiments, the random pore model (RPM) was applied to describe the NO-char reactions and obtain the intrinsic kinetics. By presenting the data of DTF and TGA experiments on the same Arrhenius plot, it can be concluded that TGA is an available tool to study the kinetics of a high-temperature NO-char reaction. With respect to the DTF experiments, in comparison to the BET surface area, the Hg surface area is a better basis for normalizing the reactivity of different coal chars because of less scatter in the measured values, better agreement with TGA experimental data, and more stable values during the process of reaction. Moreover, by comparing the Hg surface area of chars before and after reactions, it is believed that the Hg surface area basis is more appropriate for high-rank coal chars. The determined kinetic rate constants are in good agreement with other data in the literature, and a new rate constant expression is proposed. 30 refs., 8 figs., 7 tabs.
Kinetic model for Eley-Rideal and hot atom reactions between H atoms on metal surfaces
NASA Astrophysics Data System (ADS)
Jackson, Bret; Sha, Xianwei; Guvenc, Ziya B.
2002-02-01
A simple kinetic model is used to describe the interaction of H and D atomic beams with H- and D-covered metal surfaces. The atoms incident from the gas phase can have a direct Eley-Rideal reaction with an adsorbate, reflect, penetrate into the bulk, knock an adsorbate out of its binding site, or trap to form a hot atom. These hot mobile atoms can go on to react with other adsorbates, or eventually relax and stick. A coarse-graining approach, which takes advantage of the large difference between the time scales for the kinetics experiments and the reaction dynamics, allows us to derive relatively simple kinetic equations for reaction rates and coverages. The approach is similar to a kinetic random walk model developed by Küppers and co-workers [J. Phys. Chem. 109, 4071 (1998)] except that our equations can be used to derive analytical expressions for saturation coverages, rates, and yields. The model is applied to the case of H atom reactions on a Ni(100) surface, and a detailed comparison is made with both experimental and quasiclassical studies.
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.
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.
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…
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.
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…
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…
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 theâ€¦
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…
Andujar-De Sanctis, Ivonne L.
2012-01-01
Intramolecular 13C 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. Theâ€¦
Kevill, D.N.; Shen, B.W.
1981-07-29
The reactions in benzene of methyl, ethyl, and isopropyl perchlorates with N,N-dimethylanilines, to yield precipitates of the quaternary anilinium perchlorate, proceed with second-order kinetics and exhibit a large negative entropy of activation. At 25.0/sup 0/C, Hammett rho values of -3.05, -2.86, and -2.78, respectively, indicate appreciable bonding to the nitrogen within the transition state. In reaction with methyl perchlorate, the p-cyano and p-nitro derivatives require values intermediate between sigma/sup n/ and sigma/sup -/ and a rho/sup r/ parameter (as defined by Young and Jencks) of -1.58 is indicated. The p-nitroso derivative reacts considerably faster than one would predict, and it is proposed that the nucleophilic center is the oxygen rather than the nitrogen. In reaction wth N,N-dimethylaniline at 25.0/sup 0/C, comparison of methyl perchlorate with methyl-d/sub 3/ perchlorate leads to a k/sub H//k/sub D/ value of 0.942, and comparison with methyl iodide leads to a k/sub MeOClO3//k/sub MeI/ ratio of 1170. The present results are considered together with earlier studies using methyl iodide, and mechanistic implications are discussed. 8 tables.
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
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.
NASA Astrophysics Data System (ADS)
Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian
2015-05-01
The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2]3+ (1), cis-[Co(dp)2(C12H25NH2)2]3+ (2), cis-[Co(trien)(C12H25NH2)2]3+ (3), cis-[Co(bpy)2(C12H25NH2)2]3+ (4) and cis-[Co(phen)2(C12H25NH2)2]3+ (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2â€§-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe2+ ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323 K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation Î”Hâ€¡ and entropy of activation Î”Sâ€¡) of the reaction have been calculated which substantiate the kinetics of the reaction.
Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian
2015-05-15
The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2](3+) (1), cis-[Co(dp)2(C12H25NH2)2](3+) (2), cis-[Co(trien)(C12H25NH2)2](3+) (3), cis-[Co(bpy)2(C12H25NH2)2](3+) (4) and cis-[Co(phen)2(C12H25NH2)2](3+) (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2'-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe(2+) ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation Î”H(â€¡) and entropy of activation Î”S(â€¡)) of the reaction have been calculated which substantiate the kinetics of the reaction. PMID:25721780
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.
NASA Astrophysics Data System (ADS)
Nayak, Rajesh Kumar
Nucleic acid hairpins play pivotal roles in biological and cellular processes. The functions of the DNA and RNA hairpins depend upon the conformational changes they adopt during the biological process. Therefore, a clear understanding of their conformational dynamics such as folding and unfolding kinetics, reaction mechanism as well as thermodynamic stability is essential to understand their biological functions. This dissertation describes folding kinetics, reaction mechanism and thermodynamic stability of stem-loop nucleic acid hairpins by using rapid-mixing stopped-flow kinetics and other spectroscopic techniques. Firstly, the folding kinetics and reaction mechanism of a five base-paired stem and twenty one polythymidine loop DNA hairpin as a function of varying monovalent counter ion concentrations have been discussed. The important observation of this investigation is that the DNA hairpin folding is not simply a two-state process, and based on our experiments and kinetic modeling, we proposed a three-state reaction mechanism, wherein, the intermediate formation occurs on microsecond time scale and the complete hairpin formation occurs on millisecond time scale. Secondly, the loop length and counter ion dependent thermodynamic stability and folding of DNA hairpins have been described. This investigation provides a detailed understanding of how the stability and folding changes as a function of loop length and counter ion concentrations. The most important conclusion of this part of the investigation is that the thermodynamic stability of tetraloop hairpins depend upon counter ion concentration regimes and we explained the exceptional stability of a tetraloop hairpin in the higher concentration regime, compared to longer loop length hairpins on the basis of base-stacking effect. Finally, the folding and unfolding kinetics of RNA hairpins with identical four base-paired stem but different nucleotide loop sequence is discussed. Here we observed that the RNA hairpin folding and unfolding can be much more complex than previously thought and also RNA hairpin folding process can be different than DNA hairpin folding process.
Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs
NASA Astrophysics Data System (ADS)
Chia, A.; Tan, K. C.; Pawela, Å.; KurzyÅ„ski, P.; Paterek, T.; Kaszlikowski, D.
2016-03-01
Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013), 10.1063/1.4844355], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010), 10.1016/j.cplett.2010.01.063]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.
Oxygen exchange reaction kinetics for cerium(IV) oxide at 1000 Â°C
Whiting, Christofer E. Douglas, John M.; Cremeans, Bethany M.; Barklay, Chadwick D.; Kramer, Daniel P.
2014-10-15
Bulk oxygen exchange rate kinetics on CeO{sub 2} at 1000 Â°C were observed to have a first order dependence on the fraction of reaction remaining and to be independent of oxygen partial pressure, total pressure, particle size, and specific surface area. This suggests that the exchange reaction is dominated by an internal chemical reaction that is occurring throughout the bulk of the material, and not at the material surface. Oxygen exchange rates were limited by this internal chemical reaction for all CeO{sub 2} powders studied (15 nm to âˆ’325 mesh), and had a rate constant of 1.19Ã—10{sup âˆ’2} s{sup âˆ’1} with a time to completion of 617 s. These results are similar to the exchange rates observed previously on PuO{sub 2}, suggesting that oxygen exchange on PuO{sub 2} may also be dominated by an internal chemical reaction under similar conditions. This work will help guide future experiments on {sup 238}PuO{sub 2} oxygen exchange reactions. - Graphical abstract: Oxygen exchange kinetics on CeO{sub 2} at 1000 Â°C are independent of a wide range of experimental conditions and exhibit first-order chemical reaction kinetics. - Highlights: â€¢ Stable oxygen exchange rates obtained on a variety of CeO{sub 2} powders at 1000 Â°C. â€¢ Exchange rates are independent of atmospheric composition and specific surface area. â€¢ Exchange rates are limited by an internal chemical reaction, not a surface reaction. â€¢ CeO{sub 2} exchange rates appear similar to the rates observed on PuO{sub 2} at 1000 Â°C.
On Picard boundary value problem for second order asymptotically homogeneous equations
NASA Astrophysics Data System (ADS)
Dong, Y.
Using the Leray-Schauder continuation principle we give some existence results for the Picard boundary value problem of second order asymptotically homogeneous equations. Some previous results by Tippett, Gaines-Mawhin, Lazer-Leach will be extended.
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.
NASA Astrophysics Data System (ADS)
Huang, Juntao; Hu, Zexi; Yong, Wen-An
2016-04-01
In this paper, we present a kind of second-order curved boundary treatments for the lattice Boltzmann method solving two-dimensional convection-diffusion equations with general nonlinear Robin boundary conditions. The key idea is to derive approximate boundary values or normal derivatives on computational boundaries, with second-order accuracy, by using the prescribed boundary condition. Once the approximate information is known, the second-order bounce-back schemes can be perfectly adopted. Our boundary treatments are validated with a number of numerical examples. The results show the utility of our boundary treatments and very well support our theoretical predications on the second-order accuracy thereof. The idea is quite universal. It can be directly generalized to 3-dimensional problems, multiple-relaxation-time models, and the Navier-Stokes equations.
NASA Astrophysics Data System (ADS)
Sasaki, Ryu; Takemura, Kouichi
2012-11-01
Infinitely many explicit solutions of certain second-order differential equations with an apparent singularity of characteristic exponent -2 are constructed by adjusting the parameter of the multi-indexed Laguerre polynomials.
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.
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.
Chen, Xiaoshuang; Xiao, Yingyi; Zhou, Bingju; Wu, Lingxi; Liu, Xiaojuan; Gao, Yongyi; Zhan, Jie
2014-01-01
We have studied the excitation second-order nonlinearity through a triangular lattice perforated gold film instead of square lattice in many papers. Under the excitation of surface plasmas resonance effect, the second order nonlinearity exists in the noncentrosymmetric split-ring resonators arrays. Reflection of fundamental frequency wave through a triangular lattice perforated gold film is obtained. We also described the second harmonic conversion efficiencies in the second order nonlinear optical process with the spectra. Moreover, the electric field distributions of fundamental frequency above the gold film region are calculated. The light propagation through the holes results in the enhancement of the second order nonlinearity including second harmonic generation as well as the sum (difference) frequency generation. PMID:24693233
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.
Second-Order Phase Transition Induced by the Quenched Random Dilution in 3D
NASA Astrophysics Data System (ADS)
Uzelac, Katarina; Ani?i?, Ante; Bariši?, Osor S.
The effect of the quenched random dilution on the ferromagnetic transitions, in particular, the conversion from the first- to second-order transition is discussed. The new results are presented for the diluted three-dimensional three-state Potts model. The critical exponents of the disorder-induced second-order phase transition are derived by the finite-size scaling analysis of the moments of the energy and the largest cluster, obtained from the Monte Carlo simulations.
Algorithms and design for a second-order automatic differentiation module
Abate, J.; Bischof, C.; Roh, L.; Carle, A.
1997-07-01
This article describes approaches to computing second-order derivatives with automatic differentiation (AD) based on the forward mode and the propagation of univariate Taylor series. Performance results are given that show the speedup possible with these techniques relative to existing approaches. The authors also describe a new source transformation AD module for computing second-order derivatives of C and Fortran codes and the underlying infrastructure used to create a language-independent translation tool.
Second-order dynamics in the collective temporal evolution of complex systems
NASA Astrophysics Data System (ADS)
Binder, P.-M.; Privman, V.
1992-06-01
Dynamics involving a discrete second-order time derivative captures many essential, previously unexplained features of the collective behavior of complex, spatially extended systems such as cellular automata and coupled-map lattices. We argue that irrational frequencies can emerge from discrete-time dynamics, and that the second-order dynamics makes previous droplet-type arguments irrelevant for these models. These findings are supported by numerical examples.
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.
Blitz, M A; Seakins, P W
2012-10-01
This review seeks to bring together a selection of recent laboratory work on gas phase photochemistry, kinetics and reaction dynamics of radical species relevant to the understanding of planetary atmospheres other than that of Earth. A majority of work focuses on the rich organic chemistry associated with photochemically initiated reactions in the upper atmospheres of the giant planets. Reactions relevant to Titan, the largest moon of Saturn and with a nitrogen/methane dominated atmosphere, have also received much focus due to potential to explain the chemistry of Earth's prebiotic atmosphere. Analogies are drawn between the approaches of terrestrial and non-terrestrial atmospheric chemistry. PMID:22880207
Use of fiber optic technology to measure the effects of anesthesia on luciferase reaction kinetics.
Semprini, Sabrina; Saunter, Christopher D; Ludwig, Mike; Girkin, John M; Mullins, John J
2012-11-01
In vivo bioluminescent imaging (BLI) is a sensitive and reliable technique for studying gene expression, although experiments must be controlled tightly to obtain reproducible and quantitative measurements. The luciferase reaction depends on the availability of the reaction substrate, oxygen, and ATP, the distribution of which can vary markedly in different tissues. Here we used in vivo fiber optic technology, combined with stereotaxis-assisted surgery, to assess luciferase reaction kinetics in response to 2 anesthetic regimens, isoflurane and ketamine-xylazine. Transgenic rats that expressed luciferase under the control of the human prolactin promoter were used as a model organism. Anesthesia had a marked effect on luciferase reaction kinetics. The rise time to peak emission differed by 20 min between isoflurane and ketamine-xylazine. Optical imaging using a charge-coupled-device camera confirmed this delay. These results demonstrate that different anesthetics can have substantial effects on luciferase reaction kinetics and suggest that the timing of image acquisition after substrate injection should be optimized in regard to experimental conditions and the tissues of interest. PMID:23294890
First-order and second-order spectral 'motion' mechanisms in the human auditory system.
Huddleston, Wendy E; DeYoe, Edgar A
2003-01-01
Light energy displaced along the retinal photoreceptor array leads to a perception of visual motion. In audition, displacement of mechanical energy along the cochlear hair cell array is conceptually similar but leads to a perception of 'movement' in frequency space (spectral motion)--a rising or falling pitch. In vision there are other types of stimuli that also evoke a percept of motion but do not involve a displacement of energy across the photoreceptors (second-order stimuli). In this study, we used psychophysical methods to determine if such second-order stimuli also exist in audition, and if the resulting percept would rival that of first-order spectral motion. First-order auditory stimuli consisted of a frequency sweep of sixteen non-harmonic tones between 297 and 12123 Hz. Second-order stimuli consisted of the same tones, but with a random subset turned on at the beginning of a trial. During the trial, each tone in sequence randomly changed state (ON-to-OFF, or OFF-to-ON). Thus, state transitions created a 'sweep' having no net energy displacement correlated to the sweep direction. At relatively slow sweep speeds, subjects readily identified the sweep direction for both first-order and second-order stimuli, though accuracy decreased for second-order stimuli as the sweep speed increased. This latter characteristic is also true of some second-order visual stimuli. These results suggest a stronger parallelism between auditory and visual processing than previously appreciated. PMID:14651326
Second-Order accurate volume-of-fluid algorithms for TrackingMaterial Interfaces
Pilliod Jr., James E.; Puckett, Elbridge Gerry
1997-08-26
We introduce two new volume-of-fluid interface reconstruction algorithms and compare the accuracy of these algorithms to four other widely used volume-of-fluid interface reconstruction algorithms. We find that when the interface is smooth (e.g., continuous with two continuous derivatives) the new methods are second-order accurate and the other algorithms are first-order accurate. We propose a design criteria for a volume-of-fluid interface reconstruction algorithm to be second-order accurate. Namely, that it reproduce lines in two space dimensions or planes in three space dimensions exactly. We also introduce a second-order, unsplit, volume-of-fluid advection algorithm that is based on a second-order, finite difference method for scalar conservation laws due to Bell, Dawson and Shubin. We test this advection algorithm by modeling several different interface shapes propagating in two simple incompressible flows and compare the results with the standard second-order, operator-split advection algorithm. Although both methods are second-order accurate when the interface is smooth, we find that the unsplit algorithm exhibits noticeably better resolution in regions where the interface has discontinuous derivatives, such as at corners.
A stable second-order mass-weighted upwind scheme for unstructured meshes
NASA Astrophysics Data System (ADS)
Dung Tran, Luu; Masson, Christian; SmaÃ¯li, Arezki
2006-07-01
In this paper, an original second-order upwind scheme for convection terms is described and implemented in the context of a Control-Volume Finite-Element Method (CVFEM).The proposed scheme is a second-order extension of the first-order MAss-Weighted upwind (MAW) scheme proposed by Saabas and Baliga (Numer. Heat Transfer 1994; 26B:381-407). The proposed second-order scheme inherits the well-known stability characteristics of the MAW scheme, but exhibits less artificial viscosity and ensures much higher accuracy. Consequently, and in contrast with nearly all second-order upwind schemes available in the literature, the proposed second-order MAW scheme does not need limiters.Some test cases including two pure convection problems, the driven cavity and steady and unsteady flows over a circular cylinder, have been undertaken successfully to validate the new scheme.The verification tests show that the proposed scheme exhibits a low level of artificial viscosity in the pure convection problems; exhibits second-order accuracy for the driven cavity; gives accurate reattachment lengths for low-Reynolds steady flow over a circular cylinder; and gives constant-amplitude vortex shedding for the case of high-Reynolds unsteady flow over a circular cylinder.
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 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).
Wang, Xu; Ding, Jie; Guo, Wan-Qian; Ren, Nan-Qi
2010-12-01
Investigating how a bioreactor functions is a necessary precursor for successful reactor design and operation. Traditional methods used to investigate flow-field cannot meet this challenge accurately and economically. Hydrodynamics model can solve this problem, but to understand a bioreactor in sufficient depth, it is often insufficient. In this paper, a coupled hydrodynamics-reaction kinetics model was formulated from computational fluid dynamics (CFD) code to simulate a gas-liquid-solid three-phase biotreatment system for the first time. The hydrodynamics model is used to formulate prediction of the flow field and the reaction kinetics model then portrays the reaction conversion process. The coupled model is verified and used to simulate the behavior of an expanded granular sludge bed (EGSB) reactor for biohydrogen production. The flow patterns were visualized and analyzed. The coupled model also demonstrates a qualitative relationship between hydrodynamics and biohydrogen production. The advantages and limitations of applying this coupled model are discussed. PMID:20727741
Carbon kinetic isotope effect in the reaction of CH4 with HO
NASA Technical Reports Server (NTRS)
Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.
1987-01-01
The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.
NASA Astrophysics Data System (ADS)
Montero, María A.; Fernández, José L.; Gennero de Chialvo, María R.; Chialvo, Abel C.
2014-05-01
The hydrogen oxidation reaction was studied on a nanostructured rhodium electrode at different rotation rates. The electrode was prepared via sputtering on a glassy carbon disc support and it was characterized by X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and cyclic voltammetry, which allowed verifying the nanostructured morphology and the absence of any phase other than metallic rhodium. The real surface area was evaluated by CO stripping voltammetry. Experimental current density (j) - overpotential (?) curves of the hydrogen oxidation reaction were obtained in the range -0.015 V ? ? ? 0.25 V at different rotation rates in sulphuric acid solution. They were correlated by kinetic expressions derived from the Tafel-Heyrovsky-Volmer mechanism and thus the kinetic parameters were evaluated. It was verified that over this overpotential region the reaction proceeds through the simultaneous occurrence of the Tafel-Volmer and the Heyrovsky-Volmer route.
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 onâ€¦
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…
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
A test of the parallel reaction model using kinetic measurements on hydrous pyrolysis residues
Schmidt, B.; Braun, R.; Burnham, A.
1995-12-01
Open-system kinetics are measured on extracted residues from hydrous pyrolysis to test aspects of the parallel reaction model and the assumption of a single frequency factor for all energies. The absolute rates of the residues form a series supporting the concept that the hydrous pyrolysis primarily removes the more reactive components at lower temperature. The parallel reaction model works well for the kerogen except for the highest temperature residue, which is a small amount of refractory material not adequately represented in the initial kinetics. The kinetic parameters derived from the unreacted coal predict too much remaining reactive material. The discrepancy may be due either to a weakness in the parallel reaction model or the fact that the open-system kinetics are not intended to predict the generation and subsequent removal of extractable organic matter. The constant frequency factor approximation works fairly well. The frequency factor shifts about ten-fold over the activation energy range in the kerogen and about 100-fold the activation energy range in the coals.
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.
Determination of reaction kinetics of rice husks in air using thermogravimetric analysis
Mansaray, K.G.; Ghaly, A.E.
1999-12-01
Rice husk is produced in large quantities as a by-product of rice milling in rice-producing countries and has posed disposal problems in these countries. Disposal of or energy recovery from rice husk can be accomplished by thermochemical conversion processes (pyrolysis, combustion, and gasification). However, it appears that the kinetics of rice husk, which can contribute to the accurate modeling and design of thermochemical conversion processes, have not been studied extensively. In this paper the technique of thermogravimetric analysis (TGA) was used to study the thermochemical behavior of four varieties of rice husk (Lemont LG, ROK 14, CP 4, and Pa Potho). The thermal degradation of rice husk was studied in an air atmosphere (21% oxygen and 79% nitrogen) from ambient temperature to 700 C at the heating rate of 20 C/min. The thermograms showed two distinct reaction zones. The kinetic parameters (activation energy, preexponential factor, and order of reaction) were determined for the two reaction zones by applying thermoanalytical techniques to the reaction kinetics. Higher thermal degradation rates were observed in the first reaction zone due to rapid release of volatiles as compared to those in the second reaction zone. In the first reaction zone the activation energies ranged from 37.0 to 54.7 kJ/mol. Relatively lower activation energies (18.0--21.0 kJ/mol) were obtained in the second reaction zone. The preexponential factors were in the range of 4.3 x 10{sup 4} to 6.4 x 10{sup 6} min{sup {minus}1} in the first reaction zone and 4.5 x 10{sup 2} to 1.5 x 10{sup 3} min{sup {minus}1} in the second reaction zone. The orders of reaction were in the range of 1.2--1.6 and 0.4--0.5 for the first and second reaction zones, respectively. The predicted thermal degradations were in good agreement with the experimental data in both the first and second reaction zones.
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.
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.
Kinetics of HO2 reactions in the upper troposphere and lower stratosphere
NASA Astrophysics Data System (ADS)
Ploeger, J. M.; Herndon, S. C.; Zahniser, M. S.; Kolb, C. E.
2007-12-01
Reaction kinetics of HO2 complexes with small organic molecules are investigated at conditions relevant to the upper troposphere and lower stratosphere (UTLS). At the lower temperatures associated with higher altitudes, these HO2 adduct species can play a significant role in kinetic mechanisms. Using a turbulent flow tube reactor capable of operating at temperatures as low as 200 K and pressures ranging from 60 to 200 Torr we have been able to improve the understanding of HO2 kinetics in the UTLS. An elementary reaction rate mechanism for HOx and single carbon species has been constructed to both guide experiments and interpret the results. Previous ab initio studies have determined that there is a potentially significant pathway from the reaction of the HO2•H2O adduct with HO2 to form O3 and 2 H2O. An upper bound on this proposed ozone branching ratio has been measured at conditions relevant to the UTLS. The reaction network of HO2 + HCHO has been explored as well and the rate of HCOOH formation has been measured at a range of temperatures and pressures.
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.
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.
Michaelis-Menten kinetics in shear flow: Similarity solutions for multi-step reactions
Ristenpart, W. D.; Stone, H. A.
2012-01-01
Models for chemical reaction kinetics typically assume well-mixed conditions, in which chemical compositions change in time but are uniform in space. In contrast, many biological and microfluidic systems of interest involve non-uniform flows where gradients in flow velocity dynamically alter the effective reaction volume. Here, we present a theoretical framework for characterizing multi-step reactions that occur when an enzyme or enzymatic substrate is released from a flat solid surface into a linear shear flow. Similarity solutions are developed for situations where the reactions are sufficiently slow compared to a convective time scale, allowing a regular perturbation approach to be employed. For the specific case of Michaelis-Menten reactions, we establish that the transversally averaged concentration of product scales with the distance x downstream as x5/3. We generalize the analysis to n-step reactions, and we discuss the implications for designing new microfluidic kinetic assays to probe the effect of flow on biochemical processes. PMID:22662093
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
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
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
Gul, Sheraz; Mellor, Geoffrey W.; Thomas, Emrys W.; Brocklehurst, Keith
2006-01-01
The temperature-dependences of the second-order rate constants (k) of the reactions of the catalytic site thiol groups of two cysteine peptidases papain (EC 3.4.22.2) and actinidin (EC 3.4.22.14) with a series of seven 2-pyridyl disulphide reactivity probes (R-S-S-2-Py, in which R provides variation in recognition features) were determined at pH 6.7 at temperatures in the range 4–30 °C by stopped-flow methodology and were used to calculate values of ?S‡, ?H‡ and ?G‡. The marked changes in ?S‡ from negative to positive in the papain reactions consequent on provision of increase in the opportunities for key non-covalent recognition interactions may implicate microsite desolvation in binding site–catalytic site signalling to provide a catalytically relevant transition state. The substantially different behaviour of actinidin including apparent masking of changes in ?H‡ by an endothermic conformational change suggests a difference in mechanism involving kinetically significant conformational change. PMID:16445383
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.
NASA Astrophysics Data System (ADS)
Espinosa-García, J.
2002-08-01
The gas-phase hydrogen abstraction title reaction was carefully investigated. First, ab initio molecular orbital theory was used to study the stationary points along the reaction path: reactants, hydrogen-bonded complex, saddle point, and products. Optimized geometries and harmonic vibrational frequencies were calculated at the second-order Møller-Plesset perturbation theory level, and then single-point calculations were performed at a higher level of calculation: coupled-cluster with triple-zeta basis set. The effects of the level of calculation, zero-point energy (ZPE), thermal corrections [TC (298.15 K)], spin-orbit coupling, and basis set superposition error (BSSE) on the energy changes were analyzed. It was concluded that at room temperature (i.e., with ZPE and TC), when the BSSE was included, the complex disappears and the activation enthalpy is +0.39 kcal mol-1 above the reactants. Second, an analytical potential energy surface was constructed with suitable functional forms to represent vibrational modes, and was calibrated by using experimental and theoretical stationary point properties and the tendency of the kinetic isotope effects. On this surface, the forward and reverse thermal rate constants were calculated using variational transition state theory with semiclassical transmission coefficients over a wide temperature range. In both cases, we found a direct dependence on temperature and, therefore, positive activation energies. The influence of the tunneling factor was very small due to the flattening of the surface in the entrance valley. This surface was also used to analyze dynamical features, such as reaction-path curvature, the coupling between the reaction coordinate and vibrational modes, and the effect of vibrational excitation on the rate constants. It was found that excitation of the BrH stretching mode enhances the forward reaction, whereas the excitation of the CH3 umbrella mode has the opposite effect.
Kinetics and mechanism of surface reaction of salicylate on alumina in colloidal aqueous suspension
Wang, Z.; Ainsworth, C.C.; Friedrich, D.M.; Gassman, P.L.; Joly, A.G.
2000-04-01
The reaction kinetics of salicylate with Al(III) in aqueous solution and at the colloidal alumina-water interface was studied by stopped-flow laser fluorescence spectroscopy. Temporal evolution of the fluorescence spectra suggests that formation of a carboxylate monodentate complex was the reaction intermediate that occurs transiently at the beginning of the reaction in aqueous salicylate-Al(III) solution. However, by lowering the pH to 2.0, the formation of such an intermediate can be directly observed as it is the only species formed. The reaction of salicylate with aqueous Al{sup 3+} is completed within 10 min at pH 3.3 but is significantly slower at pH 2.0. At both pH the aqueous reaction follows a single pseudo-first order rate law. in Alumina suspension the reaction was initially fast but slowed down after {approximately}30 s. Completion of the reaction took up to 12 h, depending on pH and ionic strength. The formation of a carboxylate monodentate surface complex as a transient species is clearly observed in alumina suspensions at near neutral pH. The initial rapid reaction (<30 s), accounting for {approximately}70{degree} of the total reaction, can be best described by the Elovich rate equation and the slower reaction, accounting for {approximately}30% of the total reaction, obeys pseudo-first order kinetics. These results are consistent with a sorption reaction mechanism that is controlled by the leaving group lability at the surface sites (Al-OH{sub 2}{sup +} and Al-OH). The pseudo-first order rate constant varies little with initial salicylate concentration, ionic strength, or pH > 4, suggesting that the slow reaction pathway involves ligand substitution reactions between salicylate and the hydroxyl groups for which the Al-O binding and activation energy are affected by site heterogeneity or site density to a lesser degree than Al-OH{sub 2}{sup +} sites.
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.
Reaction kinetic parameters for ion transport from steady-state current-voltage curves.
Gradmann, D; Klieber, H G; Hansen, U P
1987-01-01
This study demonstrates possible ways to estimate the rate constants of reaction kinetic models for ion transport from steady-state current-voltage data as measured at various substrate concentrations. This issue is treated theoretically by algebraic reduction and extension of a reaction kinetic four-state model for uniport. Furthermore, an example for application is given; current-voltage data from an open K+ selective channel (Schroeder, J.I., R. Hedrich, and J.M. Fernandez, 1984, Nature (Lond.), 312:361-362) supplemented by some new data have been evaluated. The analysis yields absolute numerical estimates of the 14 rate constants of a six-state model, which is discussed in a wider context. PMID:2437973
Kinetic modeling of propane aromatization reaction over HZSM-5 and GaHZSM-5
Lukyanov, D.B.; Gnep, N.S.; Guisnet, M.R. . Catalyse en Chimie Organique)
1995-02-01
A detailed kinetic model for a propane aromatization reaction over HZSM-5 and GaHZSM-5 is developed. Kinetic modeling results show that propane transformation over HZSM-5 occurs via protolytic cracking and hydrogen transfer routes. The contributions of both routes in propane conversion are established. Rate constants of propane transformation steps are found to be at least 1,000 times lower than the rate constants of diene formation steps, which, in turn, are the slowest among the acid-catalyzed olefin aromatization steps. Gallium introduced into ZSM-5 catalyst is active in dehydrogenation of propane into propene, of olefins into dienes, and of naphthenes into aromatics. At the same time, gallium species catalyze propane transformation into methane and ethene hydrogenation into ethane. Both latter reactions appear to be the main reasons for the limit to aromatics selectivity over GaHZSM-5 catalysts.
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.
Samadi, F.R.; Hill, G.A. )
1988-06-01
A heavy crude oil produced using conventional techniques from a Saskatchewan reservoir was subjected to thermal stresses under both closed and opened operating conditions. Measurements were made of the oil's permanent viscosity as a function of time at several different operating temperatures ranging from 220 to 425{degree}C. The experimental results clearly showed that previous crude oill kinetic models for thermal degradation reactions were not valid. As such, several new kinetic models were hypothesized and compared to the experimental data. The results showed that a three product model could closely simulate the experimental data under both closed and opened operating condition. The reaction rate constants varied from extremely large values of 1 hr{sup {minus}1} for the production of viscous products to very low values around 0.01 hr{sup {minus}1} for the production of low viscosity products.
Sahoo, Chittaranjan; Gupta, Ashok K; Pillai, Indu M Sasidharan
2012-01-01
Real textile wastewater collected from the cotton dyeing bath of a fabric dyeing and finishing plant was subjected to heterogeneous photocatalysis using Ag(+) doped TiO(2) under UV irradiation in a batch reactor. The photocatalysts were characterized by FESEM, XRD, EDS, FTIR, DRS and BET analyses. The kinetics of the reaction was also evaluated. Colour removal was more than 88%, 94% and 99%, respectively for undiluted, 2 times diluted and 5 times diluted wastewater with Ag(+) doped TiO(2) (2.5 g/L) after UV irradiation for 360 minutes. The COD removal for undiluted, 2 times diluted and 5 times diluted wastewater was 47%, 70% and 92%, respectively under similar conditions. The reaction followed Langmuir-Hinshelwood pseudo first order kinetic model and the data fitted well to polynomial regression analysis. PMID:22871009
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, {{Î³ }(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.
Second-order systematic errors in Mueller matrix dual rotating compensator ellipsometry.
Broch, Laurent; En Naciri, Aotmane; Johann, Luc
2010-06-10
We investigate the systematic errors at the second order for a Mueller matrix ellipsometer in the dual rotating compensator configuration. Starting from a general formalism, we derive explicit second-order errors in the Mueller matrix coefficients of a given sample. We present the errors caused by the azimuthal inaccuracy of the optical components and their influences on the measurements. We demonstrate that the methods based on four-zone or two-zone averaging measurement are effective to vanish the errors due to the compensators. For the other elements, it is shown that the systematic errors at the second order can be canceled only for some coefficients of the Mueller matrix. The calibration step for the analyzer and the polarizer is developed. This important step is necessary to avoid the azimuthal inaccuracy in such elements. Numerical simulations and experimental measurements are presented and discussed. PMID:20539341
Spectral methods for the wave equation in second-order form
Taylor, Nicholas W.; Teukolsky, Saul A.; Kidder, Lawrence E.
2010-07-15
Current spectral simulations of Einstein's equations require writing the equations in first-order form, potentially introducing instabilities and inefficiencies. We present a new penalty method for pseudospectral evolutions of second order in space wave equations. The penalties are constructed as functions of Legendre polynomials and are added to the equations of motion everywhere, not only on the boundaries. Using energy methods, we prove semidiscrete stability of the new method for the scalar wave equation in flat space and show how it can be applied to the scalar wave on a curved background. Numerical results demonstrating stability and convergence for multidomain second-order scalar wave evolutions are also presented. This work provides a foundation for treating Einstein's equations directly in second-order form by spectral methods.
NASA Astrophysics Data System (ADS)
Pathak, Pallabi; Sharma, S. K.; Nakamura, Y.; Bailung, H.
2016-02-01
The experimental observation of second order ion acoustic Peregrine breathers in multicomponent plasma with negative ions is reported. A long wavelength initial perturbation on a continuous carrier frequency Ëœ0.5 Ï‰pi (where Ï‰pi is the ion plasma frequency) of finite amplitude is found to undergo self-modulation due to the interplay between nonlinear dispersive effect and group velocity dispersion because of modulational instability. Wave energy focusses to a smaller localized and isolated group of waves within the packet with amplitude amplification up to 5 times of the background carrier wave. The experimental results are compared with second order breather solution of nonlinear Schrodinger equation. The wavelet analysis and fast Fourier transform analysis of the experimental time series data indicate strong nonlinear evolution (wave energy focusing and spectral broadening) conforming to the formation of second order Peregrine solitons.
Time-dependent Second Order Scattering Theory for Weather Radar with a Finite Beam Width
NASA Technical Reports Server (NTRS)
Kobayashi, Satoru; Tanelli, Simone; Im, Eastwood; Ito, Shigeo; Oguchi, Tomohiro
2006-01-01
Multiple scattering effects from spherical water particles of uniform diameter are studied for a W-band pulsed radar. The Gaussian transverse beam-profile and the rectangular pulse-duration are used for calculation. An second-order analytical solution is derived for a single layer structure, based on a time-dependent radiative transfer theory as described in the authors' companion paper. When the range resolution is fixed, increase in footprint radius leads to increase in the second order reflectivity that is defined as the ratio of the second order return to the first order one. This feature becomes more serious as the range increases. Since the spaceborne millimeter-wavelength radar has a large footprint radius that is competitive to the mean free path, the multiple scattering effect must be taken into account for analysis.
Encoding and estimation of first- and second-order binocular disparity in natural images.
Hibbard, Paul B; Goutcher, Ross; Hunter, David W
2016-03-01
The first stage of processing of binocular information in the visual cortex is performed by mechanisms that are bandpass-tuned for spatial frequency and orientation. Psychophysical and physiological evidence have also demonstrated the existence of second-order mechanisms in binocular processing, which can encode disparities that are not directly accessible to first-order mechanisms. We compared the responses of first- and second-order binocular filters to natural images. We found that the responses of the second-order mechanisms are to some extent correlated with the responses of the first-order mechanisms, and that they can contribute to increasing both the accuracy, and depth range, of binocular stereopsis. PMID:26731646
Second-order Born calculation of coplanar symmetric (e, 2e) process on Mg
NASA Astrophysics Data System (ADS)
Zhang, Yong-Zhi; Wang, Yang; Zhou, Ya-Jun
2014-06-01
The second-order distorted wave Born approximation (DWBA) method is employed to investigate the triple differential cross sections (TDCS) of coplanar doubly symmetric (e, 2e) collisions for magnesium at excess energies of 6 eV-20 eV. Comparing with the standard first-order DWBA calculations, the inclusion of the second-order Born term in the scattering amplitude improves the degree of agreement with experiments, especially for backward scattering region of TDCS. This indicates that the present second-order Born term is capable to give a reasonable correction to DWBA model in studying coplanar symmetric (e, 2e) problems of two-valence-electron target in low energy range.