Science.gov

Sample records for affect reaction rates

  1. An Experiment To Demonstrate How a Catalyst Affects the Rate of a Reaction.

    ERIC Educational Resources Information Center

    Copper, Christine L.; Koubeck, Edward

    1999-01-01

    Describes a chemistry experiment that allows students to calculate rates of reaction, orders of reaction, and activation energies. The activity demonstrates that to increase a reaction's rate, a catalyst need only provide any additional pathway for the reaction, not necessarily a pathway having lower activation energy. (WRM)

  2. Cybersickness provoked by head-mounted display affects cutaneous vascular tone, heart rate and reaction time.

    PubMed

    Nalivaiko, Eugene; Davis, Simon L; Blackmore, Karen L; Vakulin, Andrew; Nesbitt, Keith V

    2015-11-01

    Evidence from studies of provocative motion indicates that motion sickness is tightly linked to the disturbances of thermoregulation. The major aim of the current study was to determine whether provocative visual stimuli (immersion into the virtual reality simulating rides on a rollercoaster) affect skin temperature that reflects thermoregulatory cutaneous responses, and to test whether such stimuli alter cognitive functions. In 26 healthy young volunteers wearing head-mounted display (Oculus Rift), simulated rides consistently provoked vection and nausea, with a significant difference between the two versions of simulation software (Parrot Coaster and Helix). Basal finger temperature had bimodal distribution, with low-temperature group (n=8) having values of 23-29 °C, and high-temperature group (n=18) having values of 32-36 °C. Effects of cybersickness on finger temperature depended on the basal level of this variable: in subjects from former group it raised by 3-4 °C, while in most subjects from the latter group it either did not change or transiently reduced by 1.5-2 °C. There was no correlation between the magnitude of changes in the finger temperature and nausea score at the end of simulated ride. Provocative visual stimulation caused prolongation of simple reaction time by 20-50 ms; this increase closely correlated with the subjective rating of nausea. Lastly, in subjects who experienced pronounced nausea, heart rate was elevated. We conclude that cybersickness is associated with changes in cutaneous thermoregulatory vascular tone; this further supports the idea of a tight link between motion sickness and thermoregulation. Cybersickness-induced prolongation of reaction time raises obvious concerns regarding the safety of this technology. PMID:26340855

  3. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

    This article presents an assignment in which students are to research and report on a chemical reaction whose increased or decreased rate is of practical importance. Specifically, students are asked to represent the reaction they have chosen with an acceptable chemical equation, identify a factor that influences its rate and explain how and why it…

  4. TECHNIQUES AFFECTING PRECISION AND ACCURACY IN HYDROLYSIS RATE CONSTANT DETERMINATIONS OF VOLATILE ORGANIC COMPOUNDS USING JEFFERS' ZERO HEADSPACE REACTION BULBS

    EPA Science Inventory

    A recently published method for measurement of hydrolysis rate constants for volatile organic compounds in aqueous samples was adapted for use in our laboratory. n applying the method, we developed the capability to make the zero-headspace reaction bulbs and used them to measure ...

  5. What Is a Reaction Rate?

    ERIC Educational Resources Information Center

    Schmitz, Guy

    2005-01-01

    The definition of reaction rate is derived and demonstrations are made for the care to be taken while using the term. Reaction rate can be in terms of a reaction property, the extent of reaction and thus it is possible to give a definition applicable in open and closed systems.

  6. Renormalized reaction and relaxation rates

    NASA Astrophysics Data System (ADS)

    Gorbachev, Yuriy E.

    2016-06-01

    Impact of the non-equilibrium on the reaction and relaxation rates (called as generalized relaxation rates - GRR), for the spatially inhomogeneous gas mixture is considered. Discarding the assumption that the 'chemical' part of the collisional integral is a small correction to non-reactive part, the expression for the zero-order GRR is derived. They are represented as a renormalization of the traditional reaction and relaxation rates, which means mixing of all corresponding processes. Thus all reactions and relaxation processes are entangled.

  7. Nova reaction rates and experiments

    NASA Astrophysics Data System (ADS)

    Bishop, S.; Herlitzius, C.; Fiehl, J.

    2011-04-01

    Oxygen-neon novae form a subset of classical novae events known to freshly synthesize nuclei up to mass number A≲40. Because several gamma-ray emitters lie in this mass range, these novae are also interesting candidates for gamma-ray astronomy. The properties of excited states within those nuclei in this mass region play a critical role in determining the resonant (p,γ) reaction rates, themselves, largely unknown for the unstable nuclei. We describe herein a new Doppler shift lifetime facility at the Maier-Leibnitz tandem laboratory, Technische Universität München, with which we will map out important resonant (p,γ) nova reaction rates.

  8. The Rate Laws for Reversible Reactions.

    ERIC Educational Resources Information Center

    King, Edward L.

    1986-01-01

    Provides background information for teachers on the rate laws for reversible reactions. Indicates that although prediction of the form of the rate law for a reverse reaction given the rate law for the forward reaction is not certain, the number of possibilities is limited because of relationships described. (JN)

  9. Method of controlling fusion reaction rates

    DOEpatents

    Kulsrud, Russell M.; Furth, Harold P.; Valeo, Ernest J.; Goldhaber, Maurice

    1988-03-01

    A method of controlling the reaction rates of the fuel atoms in a fusion reactor comprises the step of polarizing the nuclei of the fuel atoms in a particular direction relative to the plasma confining magnetic field. Fusion reaction rates can be increased or decreased, and the direction of emission of the reaction products can be controlled, depending on the choice of polarization direction.

  10. Method of controlling fusion reaction rates

    DOEpatents

    Kulsrud, Russell M.; Furth, Harold P.; Valeo, Ernest J.; Goldhaber, Maurice

    1988-01-01

    A method of controlling the reaction rates of the fuel atoms in a fusion reactor comprises the step of polarizing the nuclei of the fuel atoms in a particular direction relative to the plasma confining magnetic field. Fusion reaction rates can be increased or decreased, and the direction of emission of the reaction products can be controlled, depending on the choice of polarization direction.

  11. Anticipated affective reactions and prevention of AIDS.

    PubMed

    Richard, R; van der Pligt, J; de Vries, N

    1995-03-01

    Controlling the AIDs epidemic may depend largely upon health education aimed at adolescents. A number of approaches have been applied to human immunodeficiency virus (HIV) preventive behaviour in adolescents, including the health belief model (Becker, 1974), protection motivation theory (Rogers, 1983), and the theory of planned behaviour (Ajzen, 1985, 1991). Since sexual behaviour is heavily influenced by emotions, a possible shortcoming of these models is that little attention is given to affective processes. In this study we investigated the role of anticipated, post-behavioural, affective reactions to (un)safe sexual behaviours in the context of the theory of planned behaviour (TPB). The results showed that anticipated affective reactions such as worry and regret predicted behavioural expectations over and above the components of the TPB. The implications for our understanding of adolescent sexual behaviour and for campaigns aimed at the reduction of risky sexual practices will be discussed. PMID:7735735

  12. Reaction Order Ambiguity in Integrated Rate Plots

    ERIC Educational Resources Information Center

    Lee, Joe

    2008-01-01

    Integrated rate plots are frequently used in reaction kinetics to determine orders of reactions. It is often emphasised, when using this methodology in practice, that it is necessary to monitor the reaction to a substantial fraction of completion for these plots to yield unambiguous orders. The present article gives a theoretical and statistical…

  13. Partial fuel stratification to control HCCI heat release rates : fuel composition and other factors affecting pre-ignition reactions of two-stage ignition fuels.

    SciTech Connect

    Dec, John E.; Sjoberg, Carl-Magnus G.; Cannella, William; Yang, Yi; Dronniou, Nicolas

    2010-11-01

    Homogeneous charge compression ignition (HCCI) combustion with fully premixed charge is severely limited at high-load operation due to the rapid pressure-rise rates (PRR) which can lead to engine knock and potential engine damage. Recent studies have shown that two-stage ignition fuels possess a significant potential to reduce the combustion heat release rate, thus enabling higher load without knock.

  14. pH & Rate of Enzymatic Reactions.

    ERIC Educational Resources Information Center

    Clariana, Roy B.

    1991-01-01

    A quantitative and inexpensive way to measure the rate of enzymatic reaction is provided. The effects of different pH levels on the reaction rate of an enzyme from yeast are investigated and the results graphed. Background information, a list of needed materials, directions for preparing solutions, procedure, and results and discussion are…

  15. Effective reaction rates for diffusion-limited reaction cycles

    NASA Astrophysics Data System (ADS)

    Nałecz-Jawecki, Paweł; Szymańska, Paulina; Kochańczyk, Marek; Miekisz, Jacek; Lipniacki, Tomasz

    2015-12-01

    Biological signals in cells are transmitted with the use of reaction cycles, such as the phosphorylation-dephosphorylation cycle, in which substrate is modified by antagonistic enzymes. An appreciable share of such reactions takes place in crowded environments of two-dimensional structures, such as plasma membrane or intracellular membranes, and is expected to be diffusion-controlled. In this work, starting from the microscopic bimolecular reaction rate constants and using estimates of the mean first-passage time for an enzyme-substrate encounter, we derive diffusion-dependent effective macroscopic reaction rate coefficients (EMRRC) for a generic reaction cycle. Each EMRRC was found to be half of the harmonic average of the microscopic rate constant (phosphorylation c or dephosphorylation d), and the effective (crowding-dependent) motility divided by a slowly decreasing logarithmic function of the sum of the enzyme concentrations. This implies that when c and d differ, the two EMRRCs scale differently with the motility, rendering the steady-state fraction of phosphorylated substrate molecules diffusion-dependent. Analytical predictions are verified using kinetic Monte Carlo simulations on the two-dimensional triangular lattice at the single-molecule resolution. It is demonstrated that the proposed formulas estimate the steady-state concentrations and effective reaction rates for different sets of microscopic reaction rates and concentrations of reactants, including a non-trivial example where with increasing diffusivity the fraction of phosphorylated substrate molecules changes from 10% to 90%.

  16. Astrophysical Reaction Rates Obtained By Indirect Techniques

    SciTech Connect

    Tribble, R. E.; Al-Abdullah, T.; Alharbi, A.; Banu, A.; Chen, X.; Clark, H. L.; Fu, C.; Gagliardi, C. A.; Hardy, J. C.; Iacob, V. E.; Lui, Y.-W.; McCleskey, M.; Mukhamedzhanov, A.; Nica, N.; Park, H. I.; Roeder, B.; Simmons, E.; Tabacaru, G.; Tokimoto, Y.; Trache, L.

    2010-08-12

    Indirect techniques have been used to obtain information about reaction rates for several proton capture reactions that occur on short-lived nuclei. The techniques used to carry out the measurements are reviewed and the results obtained are presented. Also future prospects for further measurements with a new facility, T-REX are discussed.

  17. The Kinetic Rate Law for Autocatalytic Reactions.

    ERIC Educational Resources Information Center

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

    1987-01-01

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

  18. Critical reaction rates in hypersonic combustion chemistry

    SciTech Connect

    Oldenborg, R.C.; Harradine, D.M.; Loge, G.W.; Lyman, J.L.; Schott, G.L.; Winn, K.R.

    1989-01-01

    High Mach number flight requires that the scramjet propulsion system operate at a relatively low static inlet pressure and a high inlet temperature. These two constraints can lead to extremely high temperatures in the combustor, yielding high densities of radical species and correspondingly poor chemical combustion efficiency. As the temperature drops in the nozzle expansion, recombination of these excess radicals can produce more product species, higher heat yield, and potentially more thrust. The extent to which the chemical efficiency can be enhanced in the nozzle expansion depends directly on the rate of the radical recombination reactions. A comprehensive assessment of the important chemical processes and an experimental validation of the critical rate parameters is therefore required if accurate predictions of scramjet performance are to be obtained. This report covers the identification of critical reactions, and the critical reaction rates in hypersonic combustion chemistry. 4 refs., 2 figs.

  19. Universal reaction rates for ultracold molecular collisions

    NASA Astrophysics Data System (ADS)

    Julienne, Paul; Idziaszek, Zbigniew

    2010-03-01

    We offer a simple yet general model of reactive collisions using a quantum defect framework based on the separation of the collision dynamics into long-range and a short-range parts [1]. Two dimensionless quantum defect parameters s and y are used to characterize the S-matrix for a given entrance channel; s represents a phase parameter and y the probability of short-range reaction. The simple analytic expressions we obtain give universal values for s-wave and p-wave collision rates for a van der Waals potential when y approaches unity. In this limit, reaction rates are governed entirely by the threshold laws governing the quantum transmission of the long range potential and depend only on the van der Waals coefficient. The universal rate constants explain the magnitude of the observed rate constants for reactive collisions of fermionic KRb + KRb or K + KRb [2]. In contrast, reaction rates will be non-universal and depend strongly on the phase parameter s if the short range reaction probability is low, y << 1. [1] Z. Idziaszek and P. S. Julienne, arXiv:0912.0370. [2] S. Ospelkaus, K.-K. Ni, D. Wang, M. H. G. de Miranda, B. Neyenhuis, G. Qu'em'ener, P. S. Julienne, J. L. Bohn, D. S. Jin, and J. Ye, arXiv:0912.3854.

  20. Affective Incoherence: When Affective Concepts and Embodied Reactions Clash

    PubMed Central

    Centerbar, David B.; Clore, Gerald L.; Schnall, Simone; Garvin, Erika

    2008-01-01

    In five studies, we examined the effects on cognitive performance of coherence and incoherence between conceptual and experiential sources of affective information. The studies crossed the priming of happy and sad concepts with affective experiences. In different experiments, these included: approach or avoidance actions, happy or sad feelings, and happy or sad expressive behaviors. In all studies, coherence between affective concepts and affective experiences led to better recall of a story than affective incoherence. We suggested that the experience of such experiential affective cues serves as evidence of the appropriateness of affective concepts that come to mind. The results suggest that affective coherence has epistemic benefits, and that incoherence is costly, for cognitive performance. PMID:18361672

  1. Enhanced aqueous photochemical reaction rates after freezing.

    PubMed

    Grannas, Amanda M; Bausch, Alexandra R; Mahanna, Kendell M

    2007-11-01

    Sunlit snow/ice is known to play an important role in the processing of atmospheric species, including photochemical production of NO(x), HONO, molecular halogens, alkyl halides, and carbonyl compounds, among others. It has been shown that a liquid-like (quasi-liquid or disordered) layer exists on the surface of pure ice and that this quasi-liquid layer is also found on the surface of ambient snow crystals and ice at temperatures similar to polar conditions. However, it is unclear what role the liquid-like fractions present in and on frozen water play in potential photochemical reactions, particularly with regard to organic substrates. Here, we report a detailed study of enhanced rates of photochemical nucleophilic substitution of p-nitroanisole (PNA) with pyridine, a well-characterized and commonly used actinometer system. Reaction rates were enhanced by a factor of up to approximately 40 when frozen at temperatures between 236 and 272 K. Reaction rates were dependent on temperature and solute concentration, both variables that control the nature of the liquid-like fraction in frozen water. The results obtained indicate that a major portion of the organic solutes is excluded to the liquid-like layer, significantly impacting the rate of the photochemical nucleophilic substitution reaction studied here. Also, the direct comparison of liquid-phase kinetics to reactions occurring in frozen water systems is drawn into question, indicating that a simple extrapolation of liquid-phase mechanisms to snow/ice may not be valid for certain reactions. PMID:17918916

  2. Reaction rates for a generalized reaction-diffusion master equation

    PubMed Central

    Hellander, Stefan; Petzold, Linda

    2016-01-01

    It has been established that there is an inherent limit to the accuracy of the reaction-diffusion master equation. Specifically, there exists a fundamental lower bound on the mesh size, below which the accuracy deteriorates as the mesh is refined further. In this paper we extend the standard reaction-diffusion master equation to allow molecules occupying neighboring voxels to react, in contrast to the traditional approach in which molecules react only when occupying the same voxel. We derive reaction rates, in two dimensions as well as three dimensions, to obtain an optimal match to the more fine-grained Smoluchowski model, and show in two numerical examples that the extended algorithm is accurate for a wide range of mesh sizes, allowing us to simulate systems that are intractable with the standard reaction-diffusion master equation. In addition, we show that for mesh sizes above the fundamental lower limit of the standard algorithm, the generalized algorithm reduces to the standard algorithm. We derive a lower limit for the generalized algorithm which, in both two dimensions and three dimensions, is on the order of the reaction radius of a reacting pair of molecules. PMID:26871190

  3. Reaction rates for a generalized reaction-diffusion master equation

    NASA Astrophysics Data System (ADS)

    Hellander, Stefan; Petzold, Linda

    2016-01-01

    It has been established that there is an inherent limit to the accuracy of the reaction-diffusion master equation. Specifically, there exists a fundamental lower bound on the mesh size, below which the accuracy deteriorates as the mesh is refined further. In this paper we extend the standard reaction-diffusion master equation to allow molecules occupying neighboring voxels to react, in contrast to the traditional approach, in which molecules react only when occupying the same voxel. We derive reaction rates, in two dimensions as well as three dimensions, to obtain an optimal match to the more fine-grained Smoluchowski model and show in two numerical examples that the extended algorithm is accurate for a wide range of mesh sizes, allowing us to simulate systems that are intractable with the standard reaction-diffusion master equation. In addition, we show that for mesh sizes above the fundamental lower limit of the standard algorithm, the generalized algorithm reduces to the standard algorithm. We derive a lower limit for the generalized algorithm which, in both two dimensions and three dimensions, is of the order of the reaction radius of a reacting pair of molecules.

  4. Motivated behavioral outcomes affect ratings of attractiveness.

    PubMed

    Bernard, Larry C; Hardy, David J

    2014-12-01

    A relatively new theory of motivation posits that purposeful human behavior may be partly explained by multidimensional individual differences "traits of action" (motives). Its 15 motives can be characterized according to their purpose: individual integrity, competitiveness, and cooperativeness. Existing evidence supports the model on which the motives are based and the reliability and validity of strategies to assess them. This experiment tested whether the hypothetical results of consistent, motivated cooperative and competitive behavior could affect ratings of attractiveness. Male and female participants (N = 98; M age = 18.8, SD = 1.4) were shown 24 opposite-sex facial photos ranging in attractiveness. The photos were paired with one of three conditions representing theoretical outcomes that would result from low, control, and high levels of cooperative and competitive motives. As predicted, outcome descriptions representing high motive strength of six motives statistically significantly affected ratings of attractiveness. This result was independent of sex of participant and consistent with the theory. PMID:25457092

  5. Thermodynamic limitations on microbially catalyzed reaction rates

    NASA Astrophysics Data System (ADS)

    LaRowe, Douglas E.; Dale, Andrew W.; Amend, Jan P.; Van Cappellen, Philippe

    2012-08-01

    Quantification of global biogeochemical cycles requires knowledge of the rates at which microorganisms catalyze chemical reactions. In order for models that describe these processes to capture global patterns of change, the underlying formulations in them must account for biogeochemical transformations over seasonal and millennial time scales in environments characterized by different energy levels. Building on existing models, a new thermodynamic limiting function is introduced. With only one adjustable parameter, this function that can be used to model microbial metabolism throughout the range of conditions in which organisms are known to be active. The formulation is based on a comparison of the amount of energy available from any redox reaction to the energy required to maintain a membrane potential, a proxy for the minimum amount of energy required by an active microorganism. This function does not require species- or metabolism-specific parameters, and can be used to model metabolisms that capture any amount of energy. The utility of this new thermodynamic rate limiting term is illustrated by applying it to three low-energy processes: fermentation, methanogenesis and sulfate reduction. The model predicts that the rate of fermentation will be reduced by half once the Gibbs energy of the catalyzed reaction reaches -12 kJ (mol e-)-1, and then slowing exponentially until the energy yield approaches zero. Similarly, the new model predicts that the low energy yield of methanogenesis, -4 to -0.5 kJ (mol e-)-1, for a partial pressure of H2 between 11 and 0.6 Pa decreases the reaction rate by 95-99%. Finally, the new function's utility is illustrated through its ability to accurately model sulfate concentration data in an anoxic marine sediment.

  6. Pycnonuclear reaction rates for binary ionic mixtures

    NASA Technical Reports Server (NTRS)

    Ichimaru, S.; Ogata, S.; Van Horn, H. M.

    1992-01-01

    Through a combination of compositional scaling arguments and examinations of Monte Carlo simulation results for the interparticle separations in binary-ionic mixture (BIM) solids, we have derived parameterized expressions for the BIM pycnonuclear rates as generalizations of those in one-component solids obtained previously by Salpeter and Van Horn and by Ogata et al. We have thereby discovered a catalyzing effect of the heavier elements, which enhances the rates of reactions among the lighter elements when the charge ratio exceeds a critical value of approximately 2.3.

  7. An approximate classical unimolecular reaction rate theory

    NASA Astrophysics Data System (ADS)

    Zhao, Meishan; Rice, Stuart A.

    1992-05-01

    We describe a classical theory of unimolecular reaction rate which is derived from the analysis of Davis and Gray by use of simplifying approximations. These approximations concern the calculation of the locations of, and the fluxes of phase points across, the bottlenecks to fragmentation and to intramolecular energy transfer. The bottleneck to fragment separation is represented as a vibration-rotation state dependent separatrix, which approximation is similar to but extends and improves the approximations for the separatrix introduced by Gray, Rice, and Davis and by Zhao and Rice. The novel feature in our analysis is the representation of the bottlenecks to intramolecular energy transfer as dividing surfaces in phase space; the locations of these dividing surfaces are determined by the same conditions as locate the remnants of robust tori with frequency ratios related to the golden mean (in a two degree of freedom system these are the cantori). The flux of phase points across each dividing surface is calculated with an analytic representation instead of a stroboscopic mapping. The rate of unimolecular reaction is identified with the net rate at which phase points escape from the region of quasiperiodic bounded motion to the region of free fragment motion by consecutively crossing the dividing surfaces for intramolecular energy exchange and the separatrix. This new theory generates predictions of the rates of predissociation of the van der Waals molecules HeI2, NeI2 and ArI2 which are in very good agreement with available experimental data.

  8. Do organic ligands affect calcite dissolution rates?

    NASA Astrophysics Data System (ADS)

    Oelkers, Eric H.; Golubev, Sergey V.; Pokrovsky, Oleg S.; Bénézeth, Pascale

    2011-04-01

    Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO 2 sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA 4-, succinate, D-glucosaminate, L-glutamate, D-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA 4-. The presence of 0.05 mol/kg citrate and EDTA 4- increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.

  9. Fusion Reaction Rate in an Inhomogeneous Plasma

    SciTech Connect

    S. Son; N.J. Fisch

    2004-09-03

    The local fusion rate, obtained from the assumption that the distribution is a local Maxwellian, is inaccurate if mean-free-paths of fusing particles are not sufficiently small compared with the inhomogeneity length of the plasma. We calculate the first order correction of P0 in terms of the small spatial gradient and obtain a non-local modification of P(sub)0 in a shock region when the gradient is not small. Use is made of the fact that the fusion reaction cross section has a relatively sharp peak as a function of energy.

  10. Indirect techniques for astrophysical reaction rates determinations

    NASA Astrophysics Data System (ADS)

    Hammache, F.; Oulebsir, N.; Benamara, S.; De Séréville, N.; Coc, A.; Laird, A.; Stefan, I.; Roussel, P.

    2016-05-01

    Direct measurements of nuclear reactions of astrophysical interest can be challenging. Alternative experimental techniques such as transfer reactions and inelastic scattering reactions offer the possibility to study these reactions by using stable beams. In this context, I will present recent results that were obtained in Orsay using indirect techniques. The examples will concern various astrophysical sites, from the Big-Bang nucleo synthesis to the production of radioisotopes in massive stars.

  11. Representing Rate Equations for Enzyme-Catalyzed Reactions

    ERIC Educational Resources Information Center

    Ault, Addison

    2011-01-01

    Rate equations for enzyme-catalyzed reactions are derived and presented in a way that makes it easier for the nonspecialist to see how the rate of an enzyme-catalyzed reaction depends upon kinetic constants and concentrations. This is done with distribution equations that show how the rate of the reaction depends upon the relative quantities of…

  12. Abortion Rates Rising in Zika-Affected Countries, Study Shows

    MedlinePlus

    ... nlm.nih.gov/medlineplus/news/fullstory_159500.html Abortion Rates Rising in Zika-Affected Countries, Study Shows ... from mosquito-borne Zika may be driving up abortion rates in Latin American countries affected by the ...

  13. Impact of THM reaction rates for astrophysics

    NASA Astrophysics Data System (ADS)

    Lamia, L.; Spitaleri, C.; Tognelli, E.; Degl'Innocenti, S.; Pizzone, R. G.; Moroni, P. G. Prada; Puglia, S. M. R.; Romano, S.; Sergi, M. L.

    2015-10-01

    Burning reaction S(E)-factor determinations are among the key ingredients for stellar models when one has to deal with energy generation evaluation and the genesis of the elements at stellar conditions. To by pass the still present uncertainties in extrapolating low-energies values, S(E)-factor measurements for charged-particle induced reactions involving light elements have been made available by devote Trojan Horse Method (THM) experiments. The recent results are here discussed together with their impact in astrophysics.

  14. Factors affecting preference ratings of prohibitive symbols.

    PubMed

    Shieh, Kong-king; Huang, Shih-miao

    2003-11-01

    A sign consisting of a pictorial overlaid with a red circle-slash (i.e., a red circle with a red slash) is used ubiquitously to convey the message that some activity is prohibited. The purpose of this study was to investigate the effects of pictorial solidity, size, and direction of elongation (DE) of the pictorial and orientation and thickness of the red circle-slash on the preference ratings for prohibitive symbols. Solid (filled) pictorials were rated better than pictorials in outline form. Pictorials with a size equal to or greater than 75% of the length of the inner diameter of the circle-slash were rated higher than pictorials 50% in size. The effect of pictorial DE was not significant: pictorials with a greater vertical DE (i.e., tall/thin pictorials) did not differ from pictorials with a greater horizontal DE (i.e., short/wide pictorials), in terms of their preference ratings. However, pictorial DE interacted with slash orientation. Diagonal slashes were rated better than vertical or horizontal ones. Further, symbols were rated better when the thickness of the red circle-slash was such that its resulting area comprised 25% of the total area inside its outer circle at least. Moreover, the interaction of pictorial size and slash thickness indicated that the preference for prohibitive symbols of thicker slash and smaller pictorial size might be degraded drastically. Implications of the results for the design of prohibitive symbols were discussed. PMID:14559418

  15. Factors affecting production rates of cosmogenic nuclides in extraterrestrial matter

    NASA Astrophysics Data System (ADS)

    Reedy, R. C.

    2015-10-01

    Good production rates are needed for cosmic-ray-produced nuclides to interpret their measurements. Rates depend on many factors, especially the pre-atmospheric object's size, the location of the sample in that object (such as near surface or deep inside), and the object's bulk composition. The bulk composition affects rates, especially in objects with very low and very high iron contents. Extraterrestrial materials with high iron contents usually have higher rates for making nuclides made by reactions with energetic particles and lower rates for the capture of thermal neutrons. In small objects and near the surface of objects, the cascade of secondary neutrons is being developed as primary particles are being removed. Deep in large objects, that secondary cascade is fully developed and the fluxes of primary particles are low. Recent work shows that even the shape of an object in space has a small but measureable effect. Work has been done and continues to be done on better understanding those and other factors. More good sets of measurements in meteorites with known exposure geometries in space are needed. With the use of modern Monte Carlo codes for the production and transport of particles, the nature of these effects have been and is being studied. Work needs to be done to improve the results of these calculations, especially the cross sections for making spallogenic nuclides.

  16. Typewriting rate as a function of reaction time.

    PubMed

    Hayes, V; Wilson, G D; Schafer, R L

    1977-12-01

    This study was designed to determine the relationship between reaction time and typewriting rate. Subjects were 24 typists ranging in age from 19 to 39 yr. Reaction times (.001 sec) to a light were recorded for each finger and to each alphabetic character and three punctuation marks. Analysis of variance yielded significant differences in reaction time among subjects and fingers. Correlation between typewriting rate and average reaction time to the alphabetic characters and three punctuation marks was --.75. Correlation between typewriting rate and the difference between the reaction time of the hands was --.42. Factors influencing typewriting rate may include reaction time of the fingers, difference between the reaction time of the hands, and reaction time to individual keys on the typewriter. Implications exist for instructional methodology and further research. PMID:604897

  17. Gender Differences in Affective Reactions to First Coitus.

    ERIC Educational Resources Information Center

    Guggino, Julie M.; Ponzetti, James J., Jr.

    1997-01-01

    Examined 87 college men's and 122 college women's affective reactions to first sexual intercourse. Results show that women were significantly more likely to report less pleasure, satisfaction, and excitement than men, and more sadness, guilt, nervousness, tension, embarrassment, and fear. Used factor analysis to group emotions into coherent…

  18. Primordial lithium: New reaction rates, new abundances, new constraints

    SciTech Connect

    Kawano, L.; Schramm, D.; Steigman, G.

    1986-12-01

    Newly measured nuclear reaction rates for /sup 3/H(..cap alpha..,..gamma..)/sup 7/Li (higher than previous values) and /sup 7/Li(p,..cap alpha..)/sup 4/He (lower than previous values) are shown to increase the /sup 7/Li yield from big bang nucleosynthesis for lower baryon to photon ratio (eta less than or equal to 4 x 10/sup -10/); the yield for higher eta is not affected. New, independent determinations of Li abundances in extreme Pop II stars are in excellent agreement with the earlier work of the Spites and give continued confidence in the use of /sup 7/Li in big bang baryon density determinations. The new /sup 7/Li constraints imply a lower limit on eta of 2 x 10/sup -10/ and an upper limit of 5 x 10/sup -10/. This lower limit to eta is concordant with that obtained from considerations of D + /sup 3/He. The upper limit is consistent with, but even more restrictive than, the D bound. With the new rates, any observed primordial Li/H ratio below 10/sup -10/ would be inexplicable by the standard big bang nucleosynthesis. A review is made of the strengths and possible weaknesses of utilizing conclusions drawn from big bang lithium considerations. An appendix discusses the null effect of a factor of 32 increase in the experimental rate for the D(d,..gamma..)/sup 4/He reaction. 28 refs., 1 fig.

  19. Do cluster properties affect the quenching rate?

    NASA Astrophysics Data System (ADS)

    Raichoor, A.; Andreon, S.

    2014-10-01

    The quenching rate is known to depend on galaxy stellar mass and environment, however, possible dependences on the hosting halo properties, such as mass, richness, and dynamical status, are still debated. The determination of these dependences is hampered by systematics, induced by noisy estimates of cluster mass or by the lack of control on galaxy stellar mass, which may mask existing trends or introduce fake trends. We studied a sample of local clusters (20 with 0.02 < z < 0.1 and log (M200/M⊙) ≳ 14), selected independent of the galaxy properties under study, having homogeneous optical photometry and X-ray estimated properties. Using those top quality measurements of cluster mass, hence of cluster scale, richness, iron abundance, and cooling time/presence of a cool-core, we study the simultaneous dependence of quenching on these cluster properties on galaxy stellar mass M and normalised cluster-centric distance r/r200. We found that the quenching rate can be completely described by two variables only, galaxy stellar mass and normalised cluster-centric distance, and is independent of halo properties (mass, richness, iron abundance, and central cooling time/presence of a cool-core). These halo properties change, in most cases, by less than 3% the probability that a galaxy is quenched, once the mass-size (M200 - r200) scaling relation is accounted for through cluster-centric distance normalisation. Appendix A is available in electronic form at http://www.aanda.org

  20. Floral symmetry affects speciation rates in angiosperms.

    PubMed Central

    Sargent, Risa D.

    2004-01-01

    Despite much recent activity in the field of pollination biology, the extent to which animal pollinators drive the formation of new angiosperm species remains unresolved. One problem has been identifying floral adaptations that promote reproductive isolation. The evolution of a bilaterally symmetrical corolla restricts the direction of approach and movement of pollinators on and between flowers. Restricting pollinators to approaching a flower from a single direction facilitates specific placement of pollen on the pollinator. When coupled with pollinator constancy, precise pollen placement can increase the probability that pollen grains reach a compatible stigma. This has the potential to generate reproductive isolation between species, because mutations that cause changes in the placement of pollen on the pollinator may decrease gene flow between incipient species. I predict that animal-pollinated lineages that possess bilaterally symmetrical flowers should have higher speciation rates than lineages possessing radially symmetrical flowers. Using sister-group comparisons I demonstrate that bilaterally symmetric lineages tend to be more species rich than their radially symmetrical sister lineages. This study supports an important role for pollinator-mediated speciation and demonstrates that floral morphology plays a key role in angiosperm speciation. PMID:15156918

  1. Multidimensional reaction rate theory with anisotropic diffusion

    NASA Astrophysics Data System (ADS)

    Berezhkovskii, Alexander M.; Szabo, Attila; Greives, Nicholas; Zhou, Huan-Xiang

    2014-11-01

    An analytical expression is derived for the rate constant that describes diffusive transitions between two deep wells of a multidimensional potential. The expression, in contrast to the Kramers-Langer formula for the rate constant, is valid even when the diffusion is highly anisotropic. Our approach is based on a variational principle for the reactive flux and uses a trial function for the splitting probability or commitor. The theoretical result is validated by Brownian dynamics simulations.

  2. DSMC predictions of non-equilibrium reaction rates.

    SciTech Connect

    Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

    2010-04-01

    A set of Direct Simulation Monte Carlo (DSMC) chemical-reaction models recently proposed by Bird and based solely on the collision energy and the vibrational energy levels of the species involved is applied to calculate nonequilibrium chemical-reaction rates for atmospheric reactions in hypersonic flows. The DSMC non-equilibrium model predictions are in good agreement with theoretical models and experimental measurements. The observed agreement provides strong evidence that modeling chemical reactions using only the collision energy and the vibrational energy levels provides an accurate method for predicting non-equilibrium chemical-reaction rates.

  3. On the rate of relativistic surface chemical reactions.

    PubMed

    Veitsman, E V

    2004-07-15

    On the basis of special relativity and the classical theory of chemical reaction rates it is shown how the surface chemical reaction rates vary as v --> c, where v is the velocity of the object under study and c is the velocity of light. PMID:15178286

  4. Abortion Rates Rising in Zika-Affected Countries, Study Shows

    MedlinePlus

    ... news/fullstory_159500.html Abortion Rates Rising in Zika-Affected Countries, Study Shows Brazil, Ecuador have seen ... News) -- Fears over birth defects from mosquito-borne Zika may be driving up abortion rates in Latin ...

  5. Empirical rate equation for association reactions and ion-molecule reactions

    NASA Astrophysics Data System (ADS)

    Sato, Shin

    2016-05-01

    Temperature dependence of the rate constants of many association reactions is now available. In order to express the rate constants at temperatures from very low to high, we tried to use the sum of new empirical rate equations for association reactions and Arrhenius equations. Temperature dependence of a number of radical-molecule and some ion-molecule reactions could be successfully demonstrated. A new procedure to analyze ion-molecule reactions was proposed. This might suggest a new viewpoint to understanding chemical reactions.

  6. Estimating the Backup Reaction Wheel Orientation Using Reaction Wheel Spin Rates Flight Telemetry from a Spacecraft

    NASA Technical Reports Server (NTRS)

    Rizvi, Farheen

    2013-01-01

    A report describes a model that estimates the orientation of the backup reaction wheel using the reaction wheel spin rates telemetry from a spacecraft. Attitude control via the reaction wheel assembly (RWA) onboard a spacecraft uses three reaction wheels (one wheel per axis) and a backup to accommodate any wheel degradation throughout the course of the mission. The spacecraft dynamics prediction depends upon the correct knowledge of the reaction wheel orientations. Thus, it is vital to determine the actual orientation of the reaction wheels such that the correct spacecraft dynamics can be predicted. The conservation of angular momentum is used to estimate the orientation of the backup reaction wheel from the prime and backup reaction wheel spin rates data. The method is applied in estimating the orientation of the backup wheel onboard the Cassini spacecraft. The flight telemetry from the March 2011 prime and backup RWA swap activity on Cassini is used to obtain the best estimate for the backup reaction wheel orientation.

  7. Affective psychotherapy in post-traumatic reactions guided by affective neuroscience: memory reconsolidation and play.

    PubMed

    Högberg, Göran; Nardo, Davide; Hällström, Tore; Pagani, Marco

    2011-01-01

    This paper reviews the affective neuroscience dealing with the effects of traumatic events. We give an overview of the normal fear reactions, the pathological fear reaction, and the character of emotional episodic memories. We find that both emotions and emotional memories are a tripartite unit of sensory information, autonomic reaction, and motor impulse (the PRM complex). We propose that emotions and movements are part and parcel of the same complex. This is our main finding from the review of affective neuroscience, and from here we focus on psychotherapy with post-trauma reactions. The finding of the process of memory reconsolidation opens up a new treatment approach: affective psychotherapy focused on reconsolidation. The meaning of reconsolidation is that an emotional memory, when retrieved and being active, will rest in a labile form, amenable to change, for a brief period of time, until it reconsolidates in the memory. This leads us to the conclusion that emotions, affects, must be evoked during the treatment session and that positive emotion must come first, because safety must be part of the new memories. In the proposed protocol of affective psychotherapy based on reconsolidation the emotional episodic memory is relived in a safe and positive setting, focused in turn on the sensory experience, the autonomic reaction, and the motor impulse. Then it is followed by a fantasy of a different positive version of the same event. All in all treatment should provide a series of new memories without fear related to the original event. With the focus on the motor program, and the actions, there is a natural link to art therapy and to the mode of play, which can rehearse and fantasize new positive actions. PMID:22114539

  8. Affective psychotherapy in post-traumatic reactions guided by affective neuroscience: memory reconsolidation and play

    PubMed Central

    Högberg, Göran; Nardo, Davide; Hällström, Tore; Pagani, Marco

    2011-01-01

    This paper reviews the affective neuroscience dealing with the effects of traumatic events. We give an overview of the normal fear reactions, the pathological fear reaction, and the character of emotional episodic memories. We find that both emotions and emotional memories are a tripartite unit of sensory information, autonomic reaction, and motor impulse (the PRM complex). We propose that emotions and movements are part and parcel of the same complex. This is our main finding from the review of affective neuroscience, and from here we focus on psychotherapy with post-trauma reactions. The finding of the process of memory reconsolidation opens up a new treatment approach: affective psychotherapy focused on reconsolidation. The meaning of reconsolidation is that an emotional memory, when retrieved and being active, will rest in a labile form, amenable to change, for a brief period of time, until it reconsolidates in the memory. This leads us to the conclusion that emotions, affects, must be evoked during the treatment session and that positive emotion must come first, because safety must be part of the new memories. In the proposed protocol of affective psychotherapy based on reconsolidation the emotional episodic memory is relived in a safe and positive setting, focused in turn on the sensory experience, the autonomic reaction, and the motor impulse. Then it is followed by a fantasy of a different positive version of the same event. All in all treatment should provide a series of new memories without fear related to the original event. With the focus on the motor program, and the actions, there is a natural link to art therapy and to the mode of play, which can rehearse and fantasize new positive actions. PMID:22114539

  9. Theory of Crowding Effects on Bimolecular Reaction Rates.

    PubMed

    Berezhkovskii, Alexander M; Szabo, Attila

    2016-07-01

    An analytical expression for the rate constant of a diffusion-influenced bimolecular reaction in a crowded environment is derived in the framework of a microscopic model that accounts for: (1) the slowdown of diffusion due to crowding and the dependence of the diffusivity on the distance between the reactants, (2) a crowding-induced attractive short-range potential of mean force, and (3) nonspecific reversible binding to the crowders. This expression spans the range from reaction to diffusion control. Crowding can increase the reaction-controlled rate by inducing an effective attraction between reactants but decrease the diffusion-controlled rate by reducing their relative diffusivity. PMID:27096470

  10. An Improved Reaction Rate Equation for Simulating the Ignition and Growth of Reaction in High Explosives

    SciTech Connect

    Murphy, M J

    2010-03-08

    We describe an improved reaction rate equation for simulating ignition and growth of reaction in high explosives. It has been implemented into CALE and ALE3D as an alternate to the baseline the Lee-Tarver reactive flow model. The reactive flow model treats the explosive in two phases (unreacted/reactants and reacted/products) with a reaction rate equation to determine the fraction reacted, F. The improved rate equation has fewer parameters, is continuous with continuous derivative, results in a unique set of reaction rate parameters for each explosive while providing the same functionality as the baseline rate equation. The improved rate equation uses a cosine function in the ignition term and a sine function in the growth and completion terms. The improved rate equation is simpler with fewer parameters.

  11. Gas-solid reaction-rate enhancement by pressure cycling

    NASA Astrophysics Data System (ADS)

    Sohn, H. Y.; Aboukheshem, M. B.

    1992-06-01

    An experimental study and mathematical modeling of the effects of external pressure cycling on gas-solid reactions have been conducted using the reduction of nickel oxide pellets by hy-drogen. Experiments were carried out in two phases: In the first phase, the intrinsic kinetic parameters were measured, and in the second phase, the gas-solid reaction was carried out under a constant or cycling external pressure. The effects of the frequency and amplitude of pressure cycling were studied at various reaction conditions. Pressure cycling substantially increases the overall rate of the reaction. A mathematical model was developed from the first principles to establish the extent of the overall reaction-rate enhancement and subsequently to analyze the experimental observations. The calculated values from the mathematical model are in good agreement with the experimental results. The effects are most pronounced when the overall rate under a constant pressure is controlled by diffusion. Depending on the reaction condition, a very large degree of rate enhancement could be achieved. Furthermore, low-amplitude pressure waves, like acoustic waves, could significantly increase the rates of gas-solid reactions.

  12. Brain Activity, Personality Traits and Affect: Electrocortical Activity in Reaction to Affective Film Stimuli

    NASA Astrophysics Data System (ADS)

    Makvand Hosseini, Sh.; Azad Fallah, P.; Rasoolzadeh Tabatabaei, S. K.; Ghannadyan Ladani, S. H.; Heise, C.

    We studied the patterns of activation over the cerebral cortex in reaction to affective film stimuli in four groups of extroverts, introverts, neurotics and emotionally stables. Measures of extraversion and neuroticism were collected and resting EEG was recorded from 40 right handed undergraduate female students (19-23) on one occasion for five 30s periods in baseline condition and in affective states. Mean log-transformed absolute alpha power was extracted from 12 electrode sites and analyzed. Patterns of activation were different in personality groups. Different patterns of asymmetries were observed in personality groups in reaction to affective stimuli. Results were partly consistent with approach and withdrawal model and provided supportive evidence for the role of right frontal asymmetry in negative affects in two groups (introverts and emotionally stables) as well as the role of right central asymmetry (increase on right and decrease on left) in active affective states (anxiety and happiness) in all personality groups. Results were also emphasized on the role of decrease activity relative to baseline in cortical regions (bilaterally in frontal and unilaterally in left parietal and temporal regions) in moderating of positive and negative emotion.

  13. Non-resonant triple alpha reaction rate at low temperature

    SciTech Connect

    Itoh, T.; Tamii, A.; Aoi, N.; Fujita, H.; Hashimoto, T.; Miki, K.; Ogata, K.; Carter, J.; Donaldson, L.; Sideras-Haddad, E.; Furuno, T.; Kawabata, T.; Kamimura, M.; Nemulodi, F.; Neveling, R.; Smit, F. D.; Swarts, C.

    2014-05-02

    Our experimental goal is to study the non-resonant triple alpha reaction rate at low temperture (T < 10{sup 8} K). The {sup 13}C(p,d) reaction at 66 MeV has been used to probe the alpha-unbound continuum state in {sup 12}C just below the 2{sup nd} 0{sup +} state at 7.65 MeV. The transition strength to the continuum state is predicted to be sensitive to the non-resonant triple alpha reaction rate. The experiment has been performed at iThemba LABS. We report the present status of the experiment.

  14. Coupling of hydrologic transport and chemical reactions in a stream affected by acid mine drainage

    USGS Publications Warehouse

    Kimball, B.A.; Broshears, R.E.; Bencala, K.E.; McKnight, Diane M.

    1994-01-01

    Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-??m filtered and particulate Fe were reactive over most of the stream reach. Filtered Al partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of SO4, Mn, Fe, and Al with first-order reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologie transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.

  15. Rate of reaction between molecular hydrogen and molecular oxygen

    NASA Technical Reports Server (NTRS)

    Brokaw, R. S.

    1973-01-01

    The shock tube data of Jachimowski and Houghton were rigorously analyzed to obtain rate constants for the candidate initiation reactions H2 + O2 yields H + HO2, H2 + O2 yields H2O + O, and H2 + O2 yields OH + OH. Reaction (01) is probably not the initiation process because the activation energy obtained is less than the endothermicity and because the derived rates greatly exceed values inferred in the literature from the reverse of reaction (01). Reactions (02) and (03) remain as possibilities, with reaction (02) slightly favored on the basis of steric and statistical considerations. The solution of the differential equations is presented in detail to show how the kinetics of other ignition systems may be solved.

  16. Analysis of reaction schemes using maximum rates of constituent steps.

    PubMed

    Motagamwala, Ali Hussain; Dumesic, James A

    2016-05-24

    We show that the steady-state kinetics of a chemical reaction can be analyzed analytically in terms of proposed reaction schemes composed of series of steps with stoichiometric numbers equal to unity by calculating the maximum rates of the constituent steps, rmax,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of rmax,i to calculate degrees of rate control for each step to determine the extent to which each step controls the rate of the overall stoichiometric reaction. The values of rmax,i can be used to predict the rate of the overall stoichiometric reaction, making it possible to estimate the observed reaction kinetics. This approach can be used for catalytic reactions to identify transition states and adsorbed species that are important in controlling catalyst performance, such that detailed calculations using electronic structure calculations (e.g., density functional theory) can be carried out for these species, whereas more approximate methods (e.g., scaling relations) are used for the remaining species. This approach to assess the feasibility of proposed reaction schemes is exact for reaction schemes where the stoichiometric coefficients of the constituent steps are equal to unity and the most abundant adsorbed species are in quasi-equilibrium with the gas phase and can be used in an approximate manner to probe the performance of more general reaction schemes, followed by more detailed analyses using full microkinetic models to determine the surface coverages by adsorbed species and the degrees of rate control of the elementary steps. PMID:27162366

  17. Analysis of reaction schemes using maximum rates of constituent steps

    NASA Astrophysics Data System (ADS)

    Hussain Motagamwala, Ali; Dumesic, James A.

    2016-05-01

    We show that the steady-state kinetics of a chemical reaction can be analyzed analytically in terms of proposed reaction schemes composed of series of steps with stoichiometric numbers equal to unity by calculating the maximum rates of the constituent steps, rmax,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of rmax,i to calculate degrees of rate control for each step to determine the extent to which each step controls the rate of the overall stoichiometric reaction. The values of rmax,i can be used to predict the rate of the overall stoichiometric reaction, making it possible to estimate the observed reaction kinetics. This approach can be used for catalytic reactions to identify transition states and adsorbed species that are important in controlling catalyst performance, such that detailed calculations using electronic structure calculations (e.g., density functional theory) can be carried out for these species, whereas more approximate methods (e.g., scaling relations) are used for the remaining species. This approach to assess the feasibility of proposed reaction schemes is exact for reaction schemes where the stoichiometric coefficients of the constituent steps are equal to unity and the most abundant adsorbed species are in quasi-equilibrium with the gas phase and can be used in an approximate manner to probe the performance of more general reaction schemes, followed by more detailed analyses using full microkinetic models to determine the surface coverages by adsorbed species and the degrees of rate control of the elementary steps.

  18. Nonlinear dynamical effects on reaction rates in thermally fluctuating environments.

    PubMed

    Kawai, Shinnosuke; Komatsuzaki, Tamiki

    2010-07-21

    A framework to calculate the rate constants of condensed phase chemical reactions of manybody systems is presented without relying on the concept of transition state. The theory is based on a framework we developed recently adopting a multidimensional underdamped Langevin equation in the region of a rank-one saddle. The theory provides a reaction coordinate expressed as an analytical nonlinear functional of the position coordinates and velocities of the system (solute), the friction constants, and the random force of the environment (solvent). Up to moderately high temperature, the sign of the reaction coordinate can determine the final destination of the reaction in a thermally fluctuating media, irrespective of what values the other (nonreactive) coordinates may take. In this paper, it is shown that the reaction probability is analytically derived as the probability of the reaction coordinate being positive, and that the integration with the Boltzmann distribution of the initial conditions leads to the exact reaction rate constant when the local equilibrium holds and the quantum effect is negligible. Because of analytical nature of the theory taking into account all nonlinear effects and their combination with fluctuation and dissipation, the theory naturally provides us with the firm mathematical foundation of the origin of the reactivity of the reaction in a fluctuating media. PMID:20544104

  19. Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

    NASA Technical Reports Server (NTRS)

    Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

    1999-01-01

    Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

  20. Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

    NASA Technical Reports Server (NTRS)

    Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

    1999-01-01

    Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

  1. Affective Rating of Color and Black-and-White Pictures.

    ERIC Educational Resources Information Center

    Winn, William; Everett, Richard J.

    1979-01-01

    This study explored the effect of grade level and sex on affective ratings of color and black-and-white pictures by having 148 students from grades 4, 7, and 12 rate color and black-and-white slides on nine semantic differential scales. (JEG)

  2. Factors affecting the development of adverse drug reactions (Review article)

    PubMed Central

    Alomar, Muaed Jamal

    2013-01-01

    Objectives To discuss the effect of certain factors on the occurrence of Adverse Drug Reactions (ADRs). Data Sources A systematic review of the literature in the period between 1991 and 2012 was made based on PubMed, the Cochrane database of systematic reviews, EMBASE and IDIS. Key words used were: medication error, adverse drug reaction, iatrogenic disease factors, ambulatory care, primary health care, side effects and treatment hazards. Summary Many factors play a crucial role in the occurrence of ADRs, some of these are patient related, drug related or socially related factors. Age for instance has a very critical impact on the occurrence of ADRs, both very young and very old patients are more vulnerable to these reactions than other age groups. Alcohol intake also has a crucial impact on ADRs. Other factors are gender, race, pregnancy, breast feeding, kidney problems, liver function, drug dose and frequency and many other factors. The effect of these factors on ADRs is well documented in the medical literature. Taking these factors into consideration during medical evaluation enables medical practitioners to choose the best drug regimen. Conclusion Many factors affect the occurrence of ADRs. Some of these factors can be changed like smoking or alcohol intake others cannot be changed like age, presence of other diseases or genetic factors. Understanding the different effects of these factors on ADRs enables healthcare professionals to choose the most appropriate medication for that particular patient. It also helps the healthcare professionals to give the best advice to patients. Pharmacogenomics is the most recent science which emphasizes the genetic predisposition of ADRs. This innovative science provides a new perspective in dealing with the decision making process of drug selection. PMID:24648818

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

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

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

  4. A Transition in the Cumulative Reaction Rate of Two Species Diffusion with Bimolecular Reaction

    NASA Astrophysics Data System (ADS)

    Rajaram, Harihar; Arshadi, Masoud

    2015-04-01

    Diffusion and bimolecular reaction between two initially separated reacting species is a prototypical small-scale description of reaction induced by transverse mixing. It is also relevant to diffusion controlled transport regimes as encountered in low-permeability matrix blocks in fractured media. In previous work, the reaction-diffusion problem has been analyzed as a Stefan problem involving a distinct moving boundary (reaction front), which predicts that front motion scales as √t, and the cumulative reaction rate scales as 1/√t-. We present a general non-dimensionalization of the problem and a perturbation analysis to show that there is an early time regime where the cumulative reaction rate scales as √t- rather than 1/√t. The duration of this early time regime (where the cumulative rate is kinetically rather than diffusion controlled) depends on the rate parameter, in a manner that is consistently predicted by our non-dimensionalization. We also present results on the scaling of the reaction front width. We present numerical simulations in homogeneous and heterogeneous porous media to demonstrate the limited influence of heterogeneity on the behavior of the reaction-diffusion system. We illustrate applications to the practical problem of in-situ chemical oxidation of TCE and PCE by permanganate, which is employed to remediate contaminated sites where the DNAPLs are largely dissolved in the rock matrix.

  5. Benchmark calculations of thermal reaction rates. I - Quantal scattering theory

    NASA Technical Reports Server (NTRS)

    Chatfield, David C.; Truhlar, Donald G.; Schwenke, David W.

    1991-01-01

    The thermal rate coefficient for the prototype reaction H + H2 yields H2 + H with zero total angular momentum is calculated by summing, averaging, and numerically integrating state-to-state reaction probabilities calculated by time-independent quantum-mechanical scattering theory. The results are very carefully converged with respect to all numerical parameters in order to provide high-precision benchmark results for confirming the accuracy of new methods and testing their efficiency.

  6. Diagrammatic algorithm for evaluating finite-temperature reaction rates

    NASA Astrophysics Data System (ADS)

    Ashida, Naoki; Nakkagawa, Hisao; Niégawa, Akira; Yokota, Hiroshi

    1992-05-01

    In this paper, by following the procedure of statistical mechanics we present the systematic calculational rules for evaluating the reaction rate of a generic dynamical process taking place in a heat bath. These rules are formulated within the framework of real-time thermal field theory (RTFT), in terms of the Feynman-like diagrams, the so-called circled diagrams. With the machinery developed in this paper we can establish the finite temperature generalization of the Cutkosky, or the cutting rules in quantum field theory at zero temperature. We have also studied the relation between the imaginary part of forward RTFT amplitude and the reaction rates; the imaginary part consists of various reaction rates. This is a finite temperature generalization of the optical theorem.

  7. Viscosity Dependence of Some Protein and Enzyme Reaction Rates: Seventy-Five Years after Kramers.

    PubMed

    Sashi, Pulikallu; Bhuyan, Abani K

    2015-07-28

    Kramers rate theory is a milestone in chemical reaction research, but concerns regarding the basic understanding of condensed phase reaction rates of large molecules in viscous milieu persist. Experimental studies of Kramers theory rely on scaling reaction rates with inverse solvent viscosity, which is often equated with the bulk friction coefficient based on simple hydrodynamic relations. Apart from the difficulty of abstraction of the prefactor details from experimental data, it is not clear why the linearity of rate versus inverse viscosity, k ∝ η(-1), deviates widely for many reactions studied. In most cases, the deviation simulates a power law k ∝ η(-n), where the exponent n assumes fractional values. In rate-viscosity studies presented here, results for two reactions, unfolding of cytochrome c and cysteine protease activity of human ribosomal protein S4, show an exceedingly overdamped rate over a wide viscosity range, registering n values up to 2.4. Although the origin of this extraordinary reaction friction is not known at present, the results indicate that the viscosity exponent need not be bound by the 0-1 limit as generally suggested. For the third reaction studied here, thermal dissociation of CO from nativelike cytochrome c, the rate-viscosity behavior can be explained using Grote-Hynes theory of time-dependent friction in conjunction with correlated motions intrinsic to the protein. Analysis of the glycerol viscosity-dependent rate for the CO dissociation reaction in the presence of urea as the second variable shows that the protein stabilizing effect of subdenaturing amounts of urea is not affected by the bulk viscosity. It appears that a myriad of factors as diverse as parameter uncertainty due to the difficulty of knowing the exact reaction friction and both mode and consequences of protein-solvent interaction work in a complex manner to convey as though Kramers rate equation is not absolute. PMID:26135219

  8. Lead chloride affects sperm motility and acrosome reaction in mice: lead affects mice sperm motility and acrosome reaction.

    PubMed

    Oliveira, Helena; Spanò, Marcello; Santos, Conceição; Pereira, Maria de Lourdes

    2009-08-01

    Lead is highly toxic and persistent in the environment and, thus, a major concern for public health. In this study, the effects of lead chloride (PbCl2) on mouse epididymal sperm were evaluated. Male mice were subcutaneously injected with 74 and 100 mg PbCl2/kg body weight for four consecutive days. Sperm was collected from the epididymis and several parameters of sperm function, such as sperm density, motility, viability, mitochondrial function, acrosome integrity and morphology, were evaluated. Furthermore, DNA fragmentation was assessed by the terminal deoxylnucleotidyl transferase-mediated deoxyuridine triphosphate (dUTP) nick-end labelling (TUNEL) assay and chromatin integrity was evaluated by sperm chromatin structure assay (SCSA). In order to assess direct effects on existing sperm population, we sacrificed one group for each condition at day 5. The effects of lead upon one entire spermatogenic cycle were evaluated on day 35. Both lead concentrations used in this work affected sperm motility, although no significant differences were observed in sperm viability, mitochondrial function and DNA/chromatin integrity. However, a decrease in the percentage of intact acrosomes was also observed, mirroring a lead-induced premature acrosome reaction. Thus, the results obtained indicate that, together with impaired motility, the effect of lead toxicity on acrosome integrity, leading to premature reaction, may compromise the ability of sperm to fertilize the oocyte. PMID:18594995

  9. A transition in the spatially integrated reaction rate of bimolecular reaction-diffusion systems

    NASA Astrophysics Data System (ADS)

    Arshadi, Masoud; Rajaram, Harihar

    2015-09-01

    Numerical simulations of diffusion with bimolecular reaction demonstrate a transition in the spatially integrated reaction rate—increasing with time initially, and transitioning to a decrease with time. In previous work, this reaction-diffusion problem has been analyzed as a Stefan problem involving a distinct moving boundary (reaction front), leading to predictions that front motion scales as √t, and correspondingly the spatially integrated reaction rate decreases as the square root of time 1/√t. We present a general nondimensionalization of the problem and a perturbation analysis to show that there is an early time regime where the spatially integrated reaction rate scales as √t rather than 1/√t. The duration of this early time regime (where the spatially integrated reaction rate is kinetically rather than diffusion controlled) is shown to depend on the kinetic rate parameters, diffusion coefficients, and initial concentrations of the two species. Numerical simulation results confirm the theoretical estimates of the transition time. We present illustrative calculations in the context of in situ chemical oxidation for remediation of fractured rock systems where contaminants are largely dissolved in the rock matrix. We consider different contaminants of concern (COCs), including TCE, PCE, MTBE, and RDX. While the early time regime is very short lived for TCE, it can persist over months to years for MTBE and RDX, due to slow oxidation kinetics.

  10. Controlling the rates of biochemical reactions and signaling networks by shape and volume changes.

    PubMed

    Lizana, L; Bauer, B; Orwar, O

    2008-03-18

    In biological systems, chemical activity takes place in micrometer- and nanometer-sized compartments that constantly change in shape and volume. These ever-changing cellular compartments embed chemical reactions, and we demonstrate that the rates of such incorporated reactions are directly affected by the ongoing shape reconfigurations. First, we show that the rate of product formation in an enzymatic reaction can be regulated by simple volume contraction-dilation transitions. The results suggest that mitochondria may regulate the dynamics of interior reaction pathways (e.g., the Krebs cycle) by volume changes. We then show the effect of shape changes on reactions occurring in more complex and structured systems by using biomimetic networks composed of micrometer-sized compartments joined together by nanotubes. Chemical activity was measured by implementing an enzymatic reaction-diffusion system. During ongoing reactions, the network connectivity is changed suddenly (similar to the dynamic tube formations found inside Golgi stacks, for example), and the effect on the reaction is registered. We show that spatiotemporal properties of the reaction-diffusion system are extremely sensitive to sudden changes in network topology and that chemical reactions can be initiated, or boosted, in certain nodes as a function of connectivity. PMID:18337513

  11. Facial and affective reactions to tastes and their modulation by sadness and joy.

    PubMed

    Greimel, Ellen; Macht, Michael; Krumhuber, Eva; Ellgring, Heiner

    2006-09-30

    This study examined adults' affective and facial reactions to tastes which differ in quality and valence, and the impact of sadness and joy on these reactions. Thirty-six male and female subjects participated voluntarily. Subjects each tasted 6 ml of a sweet chocolate drink, a bitter quinine solution (0.0015 M) and a bitter-sweet soft drink. Following a baseline period, either joy or sadness was induced using film clips before the same taste stimuli were presented for a second time. Subjects rated the drinks' pleasantness and intensity of taste immediately after each stimulus presentation. Facial reactions were videotaped and analysed using the Facial Action Coding System (FACS [P. Ekman, W.V. Friesen, Facial Action Coding System: Manual. Palo Alto, CA: Consulting Psychologists Press; 1978., P. Ekman, W. Friesen, J. Hager, Facial Action Coding System. Salt Lake City, Utah: Research Nexus; 2002.]). The results strongly indicated that the tastes produced specific facial reactions that bear strong similarities to the facial reactivity patterns found in human newborns. The data also suggest that some adults' facial reactions serve additional communicative functions. Emotions modulated taste ratings, but not facial reactions to tastes. In particular, ratings of the sweet stimulus were modulated in congruence with emotion quality, such that joy increased and sadness decreased the pleasantness and sweetness of the sweet stimulus. No emotion-congruent modulation was found for the pleasantness and intensity ratings of the bitter or the bitter-sweet stimulus. This 'robustness' of bitter taste ratings may reflect a biologically meaningful mechanism. PMID:16857218

  12. Reaction rate uncertainties and the ν p-process

    NASA Astrophysics Data System (ADS)

    Fröhlich, C.; Rauscher, T.

    2012-11-01

    Current hydrodynamical simulations of core collapse supernovae find proton-rich early ejecta. At the same time, the models fail to eject neutron-rich matter, thus leaving the origin of the main r-process elements unsolved. However, the proton-rich neutrino-driven winds from supernovae have been identified as a possible production site for light n-capture elements beyond iron (such as Ge, Sr, Y, Zr) through the νp-process. The detailed nucleosynthesis patterns of the νp-process depend on the hydrodynamic conditions and the nuclear reaction rates of key reactions. We investigate the impact of reaction rate uncertainties on the νp-process nucleosynthesis.

  13. Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

    NASA Technical Reports Server (NTRS)

    Cardelino, Beatriz H.

    2002-01-01

    There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

  14. A transport equation for reaction rate in turbulent flows

    NASA Astrophysics Data System (ADS)

    Sabelnikov, V. A.; Lipatnikov, A. N.; Chakraborty, N.; Nishiki, S.; Hasegawa, T.

    2016-08-01

    New transport equations for chemical reaction rate and its mean value in turbulent flows have been derived and analyzed. Local perturbations of the reaction zone by turbulent eddies are shown to play a pivotal role even for weakly turbulent flows. The mean-reaction-rate transport equation is shown to involve two unclosed dominant terms and a joint closure relation for the sum of these two terms is developed. Obtained analytical results and, in particular, the closure relation are supported by processing two widely recognized sets of data obtained from earlier direct numerical simulations of statistically planar 1D premixed flames associated with both weak large-scale and intense small-scale turbulence.

  15. Reaction rate uncertainties and the {nu}p-process

    SciTech Connect

    Froehlich, C.; Rauscher, T.

    2012-11-12

    Current hydrodynamical simulations of core collapse supernovae find proton-rich early ejecta. At the same time, the models fail to eject neutron-rich matter, thus leaving the origin of the main r-process elements unsolved. However, the proton-rich neutrino-driven winds from supernovae have been identified as a possible production site for light n-capture elements beyond iron (such as Ge, Sr, Y, Zr) through the {nu}p-process. The detailed nucleosynthesis patterns of the {nu}p-process depend on the hydrodynamic conditions and the nuclear reaction rates of key reactions. We investigate the impact of reaction rate uncertainties on the {nu}p-process nucleosynthesis.

  16. Quantum and semiclassical theories of chemical reaction rates

    SciTech Connect

    Miller, W.H. |

    1995-09-01

    A rigorous quantum mechanical theory (and a semiclassical approximation thereto) is described for calculating chemical reaction rates ``directly``, i.e., without having to solve the complete state-to-state reactive scattering problem. The approach has many vestiges of transition state theory, for which it may be thought of as the rigorous generalization.

  17. Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy.

    PubMed

    Catlow, C Richard A

    2016-08-01

    Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources. PMID:27329206

  18. Assessment of reaction-rate predictions of a collision-energy approach for chemical reactions in atmospheric flows.

    SciTech Connect

    Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

    2010-06-01

    A recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates is assessed for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary non-equilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological nonequilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, significant differences can be found. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

  19. Assessing hydrodynamic effects on jarosite dissolution rates, reaction products, and preservation on Mars

    NASA Astrophysics Data System (ADS)

    Dixon, Emily M.; Elwood Madden, Andrew S.; Hausrath, Elisabeth M.; Elwood Madden, Megan E.

    2015-04-01

    Jarosite flow-through dissolution experiments were conducted in ultrapure water (UPW), pH 2 sulfuric acid, and saturated NaCl and CaCl2 brines at 295-298 K to investigate how hydrologic variables may affect jarosite preservation and reaction products on Mars. K+-based dissolution rates in flowing UPW did not vary significantly with flow rate, indicating that mineral surface reactions control dissolution rates over the range of flow rates investigated. In all of the solutions tested, hydrologic variables do not significantly affect extent of jarosite alteration; therefore, jarosite is equally likely to be preserved in flowing or stagnant waters on Mars. However, increasing flow rate did affect the mineralogy and accumulation of secondary reaction products. Iron release rates in dilute solutions increased as the flow rate increased, likely due to nanoscale iron (hydr)oxide transport in flowing water. Anhydrite formed in CaCl2 brine flow-through experiments despite low temperatures, while metastable gypsum and bassanite were observed in batch experiments. Therefore, observations of the hydration state of calcium sulfate minerals on Mars may provide clues to unravel past salinity and hydrologic conditions as well as temperatures and vapor pressures.

  20. Code System to Calculate Integral Parameters with Reaction Rates from WIMS Output.

    1994-10-25

    Version 00 REACTION calculates different integral parameters related to neutron reactions on reactor lattices, from reaction rates calculated with WIMSD4 code, and comparisons with experimental values.

  1. Multidimensional normative ratings for the International Affective Picture System.

    PubMed

    Libkuman, Terry M; Otani, Hajime; Kern, Rosalie; Viger, Steen G; Novak, Nicole

    2007-05-01

    The purpose of the present investigation was to replicate and extend the International Affective Picture System norms (Ito, Cacioppo, & Lang, 1998; Lang, Bradley, & Cuthbert, 1999). These norms were developed to provide researchers with photographic slides that varied in emotional evocation, especially arousal and valence. In addition to collecting rating data on the dimensions of arousal and valence, we collected data on the dimensions of consequentiality, meaningfulness, familiarity, distinctiveness, and memorability. Furthermore, we collected ratings on the primary emotions of happiness, surprise, sadness, anger, disgust, and fear. A total of 1,302 participants were tested in small groups. The participants in each group rated a subset of 18 slides on 14 dimensions. Ratings were obtained on 703 slides. The means and standard deviations for all of the ratings are provided. We found our valence ratings to be similar to the previous norms. In contrast, our participants were more likely to rate the slides as less arousing than in the previous norms. The mean ratings on the remaining 12 dimensions were all below the midpoint of the 9-point Likert scale. However, sufficient variability in ratings across the slides indicates that selecting slides on the basis of these variables is feasible. Overall, the present ratings should allow investigators to use these norms for research purposes, especially in research dealing with the interrelationships among emotion and cognition. The means and standard deviations for emotions may be downloaded as an Excel spreadsheet from www.psychonomic.org/archive. PMID:17695361

  2. Rate of reaction of OH with HNO3

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Ravishankara, A. R.; Kreutter, N. M.; Shah, R. C.; Nicovich, J. M.; Thompson, R. L.; Wuebbles, D. J.

    1981-01-01

    Measurements of the kinetics of the reaction of OH with HNO3, and mechanisms of HNO3 removal from the stratosphere, are reported. Bimolecular rate constants were determined at temperatures between 224 and 366 K by monitoring the concentrations of OH radicals produced by HNO3 photolysis and HNO3 according to their resonance fluorescence and 184.9-nm absorption, respectively. The rate constant measured at 298 K is found to be somewhat faster than previously accepted values, with a negative temperature dependence. Calculations of a one-dimensional transport-kinetic atmospheric model on the basis of the new rate constant indicate reductions in O3 depletion due to chlorofluoromethane release and NOx injection, of magnitudes dependent on the nature of the reaction products.

  3. Reaction rate and products for the reaction O/3P/ + H2CO

    NASA Technical Reports Server (NTRS)

    Chang, J. S.; Barker, J. R.

    1979-01-01

    A study of reaction kinetics of O + H2CO in a discharge-flow system using mass spectrometric detection of reactants and products is presented. It was performed under both oxygen-atom-rich and formaldehyde-rich conditions over the 296 to 437 K range, showing that the global bimolecular rate constant is in agreement with other studies. This study differs from others in that the reaction products can be observed, and a substantial yield of a primary reaction product was measured with a mass spectral peak at m/e=44. This suggests that the global reaction rate probably consists of combination, as well as of simple abstraction. For the combination, one hypothesis is that triplet dioxymethylene is formed which polymerizes to triplet formic acid; the vibrationally excited triplet formic acid may decompose to form several sets of products, including HCO + OH and HCO2 + H.

  4. Scaling of geochemical reaction rates via advective solute transport.

    PubMed

    Hunt, A G; Ghanbarian, B; Skinner, T E; Ewing, R P

    2015-07-01

    Transport in porous media is quite complex, and still yields occasional surprises. In geological porous media, the rate at which chemical reactions (e.g., weathering and dissolution) occur is found to diminish by orders of magnitude with increasing time or distance. The temporal rates of laboratory experiments and field observations differ, and extrapolating from laboratory experiments (in months) to field rates (in millions of years) can lead to order-of-magnitude errors. The reactions are transport-limited, but characterizing them using standard solute transport expressions can yield results in agreement with experiment only if spurious assumptions and parameters are introduced. We previously developed a theory of non-reactive solute transport based on applying critical path analysis to the cluster statistics of percolation. The fractal structure of the clusters can be used to generate solute distributions in both time and space. Solute velocities calculated from the temporal evolution of that distribution have the same time dependence as reaction-rate scaling in a wide range of field studies and laboratory experiments, covering some 10 decades in time. The present theory thus both explains a wide range of experiments, and also predicts changes in the scaling behavior in individual systems with increasing time and/or length scales. No other theory captures these variations in scaling by invoking a single physical mechanism. Because the successfully predicted chemical reactions include known results for silicate weathering rates, our theory provides a framework for understanding changes in the global carbon cycle, including its effects on extinctions, climate change, soil production, and denudation rates. It further provides a basis for understanding the fundamental time scales of hydrology and shallow geochemistry, as well as the basis of industrial agriculture. PMID:26232976

  5. Scaling of geochemical reaction rates via advective solute transport

    NASA Astrophysics Data System (ADS)

    Hunt, A. G.; Ghanbarian, B.; Skinner, T. E.; Ewing, R. P.

    2015-07-01

    Transport in porous media is quite complex, and still yields occasional surprises. In geological porous media, the rate at which chemical reactions (e.g., weathering and dissolution) occur is found to diminish by orders of magnitude with increasing time or distance. The temporal rates of laboratory experiments and field observations differ, and extrapolating from laboratory experiments (in months) to field rates (in millions of years) can lead to order-of-magnitude errors. The reactions are transport-limited, but characterizing them using standard solute transport expressions can yield results in agreement with experiment only if spurious assumptions and parameters are introduced. We previously developed a theory of non-reactive solute transport based on applying critical path analysis to the cluster statistics of percolation. The fractal structure of the clusters can be used to generate solute distributions in both time and space. Solute velocities calculated from the temporal evolution of that distribution have the same time dependence as reaction-rate scaling in a wide range of field studies and laboratory experiments, covering some 10 decades in time. The present theory thus both explains a wide range of experiments, and also predicts changes in the scaling behavior in individual systems with increasing time and/or length scales. No other theory captures these variations in scaling by invoking a single physical mechanism. Because the successfully predicted chemical reactions include known results for silicate weathering rates, our theory provides a framework for understanding changes in the global carbon cycle, including its effects on extinctions, climate change, soil production, and denudation rates. It further provides a basis for understanding the fundamental time scales of hydrology and shallow geochemistry, as well as the basis of industrial agriculture.

  6. Stellar Evolution Constraints on the Triple-α Reaction Rate

    NASA Astrophysics Data System (ADS)

    Suda, Takuma; Hirschi, Raphael; Fujimoto, Masayuki Y.

    2011-11-01

    We investigate the quantitative constraint on the triple-α reaction rate based on stellar evolution theory, motivated by the recent significant revision of the rate proposed by nuclear physics calculations. Targeted stellar models were computed in order to investigate the impact of that rate in the mass range of 0.8 <= M/M sun <= 25 and in the metallicity range between Z = 0 and Z = 0.02. The revised rate has a significant impact on the evolution of low- and intermediate-mass stars, while its influence on the evolution of massive stars (M >~ 10 M sun) is minimal. We find that employing the revised rate suppresses helium shell flashes on asymptotic giant branch phase for stars in the initial mass range 0.8 <= M/M sun <= 6, which is contradictory to what is observed. The absence of helium shell flashes is due to the weak temperature dependence of the revised triple-α reaction cross section at the temperature involved. In our models, it is suggested that the temperature dependence of the cross section should have at least ν > 10 at T = (1-1.2) × 108 K where the cross section is proportional to T ν. We also derive the helium ignition curve to estimate the maximum cross section to retain the low-mass first red giants. The semi-analytically derived ignition curves suggest that the reaction rate should be less than ~10-29 cm6 s-1 mole-2 at ≈107.8 K, which corresponds to about three orders of magnitude larger than that of the NACRE compilation. In an effort to compromise with the revised rates, we calculate and analyze models with enhanced CNO cycle reaction rates to increase the maximum luminosity of the first giant branch. However, it is impossible to reach the typical red giant branch tip luminosity even if all the reaction rates related to CNO cycles are enhanced by more than 10 orders of magnitude.

  7. STELLAR EVOLUTION CONSTRAINTS ON THE TRIPLE-{alpha} REACTION RATE

    SciTech Connect

    Suda, Takuma; Fujimoto, Masayuki Y.; Hirschi, Raphael

    2011-11-01

    We investigate the quantitative constraint on the triple-{alpha} reaction rate based on stellar evolution theory, motivated by the recent significant revision of the rate proposed by nuclear physics calculations. Targeted stellar models were computed in order to investigate the impact of that rate in the mass range of 0.8 {<=} M/M{sub sun} {<=} 25 and in the metallicity range between Z = 0 and Z = 0.02. The revised rate has a significant impact on the evolution of low- and intermediate-mass stars, while its influence on the evolution of massive stars (M {approx}> 10 M{sub sun}) is minimal. We find that employing the revised rate suppresses helium shell flashes on asymptotic giant branch phase for stars in the initial mass range 0.8 {<=} M/M{sub sun} {<=} 6, which is contradictory to what is observed. The absence of helium shell flashes is due to the weak temperature dependence of the revised triple-{alpha} reaction cross section at the temperature involved. In our models, it is suggested that the temperature dependence of the cross section should have at least {nu} > 10 at T = (1-1.2) Multiplication-Sign 10{sup 8} K where the cross section is proportional to T {sup {nu}}. We also derive the helium ignition curve to estimate the maximum cross section to retain the low-mass first red giants. The semi-analytically derived ignition curves suggest that the reaction rate should be less than {approx}10{sup -29} cm{sup 6} s{sup -1} mole{sup -2} at Almost-Equal-To 10{sup 7.8} K, which corresponds to about three orders of magnitude larger than that of the NACRE compilation. In an effort to compromise with the revised rates, we calculate and analyze models with enhanced CNO cycle reaction rates to increase the maximum luminosity of the first giant branch. However, it is impossible to reach the typical red giant branch tip luminosity even if all the reaction rates related to CNO cycles are enhanced by more than 10 orders of magnitude.

  8. The astrophysical reaction rate for the {sup 18}F(p,{alpha}){sup 15}O reaction

    SciTech Connect

    Rehm, K.E.; Paul, M.; Roberts, A.D.

    1996-03-01

    Proton and alpha widths for a 3/2{sup +} ({ell}{sub p} = 0) state in {sup 19}Ne at E{sub x} = 7.1 MeV have been extracted using the results of recent measurements of the {sup 18}F(p,{alpha}){sup 15}O reaction. This {ell}{sub p} = 0 resonance dominates the astrophysical reaction rates at temperatures T{sub 9} > 0.5.

  9. Sensitivity study of explosive nucleosynthesis in type Ia supernovae: Modification of individual thermonuclear reaction rates

    NASA Astrophysics Data System (ADS)

    Bravo, Eduardo; Martínez-Pinedo, Gabriel

    2012-05-01

    Background: Type Ia supernovae contribute significantly to the nucleosynthesis of many Fe-group and intermediate-mass elements. However, the robustness of nucleosynthesis obtained via models of this class of explosions has not been studied in depth until now.Purpose: We explore the sensitivity of the nucleosynthesis resulting from thermonuclear explosions of massive white dwarfs with respect to uncertainties in nuclear reaction rates. We put particular emphasis on indentifying the individual reactions rates that most strongly affect the isotopic products of these supernovae.Method: We have adopted a standard one-dimensional delayed detonation model of the explosion of a Chandrasekhar-mass white dwarf and have postprocessed the thermodynamic trajectories of every mass shell with a nucleosynthetic code to obtain the chemical composition of the ejected matter. We have considered increases (decreases) by a factor of 10 on the rates of 1196 nuclear reactions (simultaneously with their inverse reactions), repeating the nucleosynthesis calculations after modification of each reaction rate pair. We have computed as well hydrodynamic models for different rates of the fusion reactions of 12C and of 16O. From the calculations we have selected the reactions that have the largest impact on the supernova yields, and we have computed again the nucleosynthesis using two or three alternative prescriptions for their rates, taken from the JINA REACLIB database. For the three reactions with the largest sensitivity we have analyzed as well the temperature ranges where a modification of their rates has the strongest effect on nucleosynthesis.Results: The nucleosynthesis resulting from the type Ia supernova models is quite robust with respect to variations of nuclear reaction rates, with the exception of the reaction of fusion of two 12C nuclei. The energy of the explosion changes by less than ˜4% when the rates of the reactions 12C+12C or 16O+16O are multiplied by a factor of ×10 or

  10. Pore-Scale Process Coupling and Effective Surface Reaction Rates in Heterogeneous Subsurface Materials

    SciTech Connect

    Liu, Chongxuan; Liu, Yuanyuan; Kerisit, Sebastien N.; Zachara, John M.

    2015-09-01

    This manuscript provides a review of pore-scale researches in literature including experimental and numerical approaches, and scale-dependent behavior of geochemical and biogeochemical reaction rates in heterogeneous porous media. A mathematical equation that can be used to predict the scale-dependent behavior of geochemical reaction rates in heterogeneous porous media has been derived. The derived effective rate expression explicitly links the effective reaction rate constant to the intrinsic rate constant, and to the pore-scale variations in reactant concentrations in porous media. Molecular simulations to calculate the intrinsic rate constants were provided. A few examples of pore-scale simulations were used to demonstrate the application of the equation to calculate effective rate constants in heterogeneous materials. The results indicate that the deviation of effective rate constant from the intrinsic rate in heterogeneous porous media is caused by the pore-scale distributions of reactants and their correlation, which are affected by the pore-scale coupling of reactions and transport.

  11. Development and validation of the Affective Self Rating Scale for manic, depressive, and mixed affective states.

    PubMed

    Adler, Mats; Liberg, Benny; Andersson, Stig; Isacsson, Göran; Hetta, Jerker

    2008-01-01

    Most rating scales for affective disorders measure either depressive or hypomanic/manic symptoms and there are few scales for hypomania/mania in a self-rating format. We wanted to develop and validate a self-rating scale for comprehensive assessment of depressive, manic/hypomanic and mixed affective states. We developed an 18-item self-rating scale starting with the DSM-IV criteria for depression and mania, with subscales for depression and mania. The scale was evaluated on 61 patients with a diagnosis of affective disorder, predominantly bipolar disorder type I, using Montgomery-Asberg Depression Rating Scale (MADRS), Hypomania Interview Guide-Clinical version (HIGH-C) and Clinical Global Impression scale, modified for bipolar patients (CGI-BP) as reference scales. Internal consistency of the scale measured by Cronbach's alpha was 0.89 for the depression subscale and 0.91 for the mania subscale. Spearman's correlation coefficients (two-tailed) between the depression subscale and MADRS was 0.74 (P<0.01) and between mania subscale and HIGH-C 0.80 (P<0.01). A rotated factor analysis of the scale supported the separation of symptoms in the mania and depression subscale. We established that the self-rating scales sensitivity to identify mixed states, with combined cut-offs on the MADRS and HIGH-C as reference, was 0.90 with a specificity of 0.71. The study shows that the Affective Self Rating Scale is highly correlated with ratings of established interview scales for depression and mania and that it may aid the detection of mixed affective states. PMID:18569776

  12. Pore size and the lab-field reaction rate riddle

    NASA Astrophysics Data System (ADS)

    Emmanuel, S.; Ague, J. J.; Walderhaug, O.

    2009-12-01

    Pore size is usually thought to influence the rate of crystal growth during diagenesis and metamorphism by controlling the ratio of surface area to fluid volume. However, theory suggests that in micron-scale to nanometer-scale pores, interfacial energy effects can also become important. We used mercury porosimetry to investigate the pore-size distributions in naturally cemented sandstone adjacent to stylolites and found that quartz precipitation was inhibited in pores smaller than 10 microns in diameter. We demonstrate that standard kinetic models cannot reproduce the observed pore-size patterns in mineralized samples; by contrast, excellent fits with the data are obtained when interfacial energy effects are taken into account. Moreover, as such micron-scale pores comprise the overwhelming majority of surface area in the sandstone, average reaction rates for the rock are significantly reduced. Reaction rates in geological media determined in field studies can be orders of magnitude lower than those measured in laboratory experiments, and we propose that reduced reaction rates in rocks with micron-scale porosity could account for the apparent paradox.

  13. Recovery rate affects the effective epidemic threshold with synchronous updating.

    PubMed

    Shu, Panpan; Wang, Wei; Tang, Ming; Zhao, Pengcheng; Zhang, Yi-Cheng

    2016-06-01

    Accurate identification of effective epidemic threshold is essential for understanding epidemic dynamics on complex networks. In this paper, we systematically study how the recovery rate affects the susceptible-infected-removed spreading dynamics on complex networks, where synchronous and asynchronous updating processes are taken into account. We derive the theoretical effective epidemic threshold and final outbreak size based on the edge-based compartmental theory. To validate the proposed theoretical predictions, extensive numerical experiments are implemented by using asynchronous and synchronous updating methods. When asynchronous updating method is used in simulations, recovery rate does not affect the final state of spreading dynamics. But with synchronous updating, we find that the effective epidemic threshold decreases with recovery rate, and final outbreak size increases with recovery rate. A good agreement between the theoretical predictions and the numerical results are observed on both synthetic and real-world networks. Our results extend the existing theoretical studies and help us to understand the phase transition with arbitrary recovery rate. PMID:27368773

  14. A model for reaction rates in turbulent reacting flows

    NASA Technical Reports Server (NTRS)

    Chinitz, W.; Evans, J. S.

    1984-01-01

    To account for the turbulent temperature and species-concentration fluctuations, a model is presented on the effects of chemical reaction rates in computer analyses of turbulent reacting flows. The model results in two parameters which multiply the terms in the reaction-rate equations. For these two parameters, graphs are presented as functions of the mean values and intensity of the turbulent fluctuations of the temperature and species concentrations. These graphs will facilitate incorporation of the model into existing computer programs which describe turbulent reacting flows. When the model was used in a two-dimensional parabolic-flow computer code to predict the behavior of an experimental, supersonic hydrogen jet burning in air, some improvement in agreement with the experimental data was obtained in the far field in the region near the jet centerline. Recommendations are included for further improvement of the model and for additional comparisons with experimental data.

  15. Suppression of excited-state contributions to stellar reaction rates

    NASA Astrophysics Data System (ADS)

    Rauscher, T.

    2013-09-01

    It has been shown in previous work [Kiss , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.101.191101 101, 191101 (2008); Rauscher , Phys. Rev. C10.1103/PhysRevC.80.035801 80, 035801 (2009)] that a suppression of the stellar enhancement factor (SEF) occurs in some endothermic reactions at and far from stability. This effect is re-evaluated using the ground-state contributions to the stellar reaction rates, which were shown to be better suited to judging the importance of excited-state contributions than the previously applied SEFs. An update of the tables shown in the latter work is given. The new evaluation finds 2350 cases (out of a full set of 57 513 reactions) for which the ground-state contribution is larger in the reaction direction with a negative reaction Q value than in the exothermic direction, thus providing exceptions to the commonly applied Q value rule. The results confirm the Coulomb suppression effect but lead to a larger number of exceptions than previously found. This is due to the fact that often a large variation in the g.s. contribution does not lead to a sizable change in the SEF. On the other hand, several previously identified cases do not appear anymore because it is found that their g.s. contribution is smaller than inferred from the SEF.

  16. Triple-α reaction rate constrained by stellar evolution models

    NASA Astrophysics Data System (ADS)

    Suda, Takuma; Hirschi, Raphael; Fujimoto, Masayuki Y.

    2012-11-01

    We investigate the quantitative constraint on the triple-α reaction rate based on stellar evolution theory, motivated by the recent significant revision of the rate proposed by nuclear physics calculations. Targeted stellar models were computed in order to investigate the impact of that rate in the mass range of 0.8<=M/Msolar<=25 and in the metallicity range between Z = 0 and Z = 0.02. The revised rate has a significant impact on the evolution of low-and intermediate-mass stars, while its influence on the evolution of massive stars (M > 10Msolar) is minimal. We find that employing the revised rate suppresses helium shell flashes on AGB phase for stars in the initial mass range 0.8<=M/Msolar<=6, which is contradictory to what is observed. The absence of helium shell flashes is due to the weak temperature dependence of the revised triple-α reaction cross section at the temperature involved. In our models, it is suggested that the temperature dependence of the cross section should have at least ν > 10 at T = 1-1.2×108K where the cross section is proportional to Tν. We also derive the helium ignition curve to estimate the maximum cross section to retain the low-mass first red giants. The semi-analytically derived ignition curves suggest that the reaction rate should be less than ~ 10-29 cm6 s-1 mole-2 at ~ 107.8 K, which corresponds to about three orders of magnitude larger than that of the NACRE compilation.

  17. Triple-{alpha} reaction rate constrained by stellar evolution models

    SciTech Connect

    Suda, Takuma; Hirschi, Raphael; Fujimoto, Masayuki Y.

    2012-11-12

    We investigate the quantitative constraint on the triple-{alpha} reaction rate based on stellar evolution theory, motivated by the recent significant revision of the rate proposed by nuclear physics calculations. Targeted stellar models were computed in order to investigate the impact of that rate in the mass range of 0.8{<=}M/M{sub Circled-Dot-Operator }{<=}25 and in the metallicity range between Z= 0 and Z= 0.02. The revised rate has a significant impact on the evolution of low-and intermediate-mass stars, while its influence on the evolution of massive stars (M > 10M{sub Circled-Dot-Operator }) is minimal. We find that employing the revised rate suppresses helium shell flashes on AGB phase for stars in the initial mass range 0.8{<=}M/M{sub Circled-Dot-Operator }{<=}6, which is contradictory to what is observed. The absence of helium shell flashes is due to the weak temperature dependence of the revised triple-{alpha} reaction cross section at the temperature involved. In our models, it is suggested that the temperature dependence of the cross section should have at least {nu} > 10 at T = 1-1.2 Multiplication-Sign 10{sup 8}K where the cross section is proportional to T{sup {nu}}. We also derive the helium ignition curve to estimate the maximum cross section to retain the low-mass first red giants. The semi-analytically derived ignition curves suggest that the reaction rate should be less than {approx} 10{sup -29} cm{sup 6} s{sup -1} mole{sup -2} at Almost-Equal-To 10{sup 7.8} K, which corresponds to about three orders of magnitude larger than that of the NACRE compilation.

  18. Rate of language evolution is affected by population size.

    PubMed

    Bromham, Lindell; Hua, Xia; Fitzpatrick, Thomas G; Greenhill, Simon J

    2015-02-17

    The effect of population size on patterns and rates of language evolution is controversial. Do languages with larger speaker populations change faster due to a greater capacity for innovation, or do smaller populations change faster due to more efficient diffusion of innovations? Do smaller populations suffer greater loss of language elements through founder effects or drift, or do languages with more speakers lose features due to a process of simplification? Revealing the influence of population size on the tempo and mode of language evolution not only will clarify underlying mechanisms of language change but also has practical implications for the way that language data are used to reconstruct the history of human cultures. Here, we provide, to our knowledge, the first empirical, statistically robust test of the influence of population size on rates of language evolution, controlling for the evolutionary history of the populations and formally comparing the fit of different models of language evolution. We compare rates of gain and loss of cognate words for basic vocabulary in Polynesian languages, an ideal test case with a well-defined history. We demonstrate that larger populations have higher rates of gain of new words whereas smaller populations have higher rates of word loss. These results show that demographic factors can influence rates of language evolution and that rates of gain and loss are affected differently. These findings are strikingly consistent with general predictions of evolutionary models. PMID:25646448

  19. Rate of language evolution is affected by population size

    PubMed Central

    Bromham, Lindell; Hua, Xia; Fitzpatrick, Thomas G.; Greenhill, Simon J.

    2015-01-01

    The effect of population size on patterns and rates of language evolution is controversial. Do languages with larger speaker populations change faster due to a greater capacity for innovation, or do smaller populations change faster due to more efficient diffusion of innovations? Do smaller populations suffer greater loss of language elements through founder effects or drift, or do languages with more speakers lose features due to a process of simplification? Revealing the influence of population size on the tempo and mode of language evolution not only will clarify underlying mechanisms of language change but also has practical implications for the way that language data are used to reconstruct the history of human cultures. Here, we provide, to our knowledge, the first empirical, statistically robust test of the influence of population size on rates of language evolution, controlling for the evolutionary history of the populations and formally comparing the fit of different models of language evolution. We compare rates of gain and loss of cognate words for basic vocabulary in Polynesian languages, an ideal test case with a well-defined history. We demonstrate that larger populations have higher rates of gain of new words whereas smaller populations have higher rates of word loss. These results show that demographic factors can influence rates of language evolution and that rates of gain and loss are affected differently. These findings are strikingly consistent with general predictions of evolutionary models. PMID:25646448

  20. Application of semiclassical methods to reaction rate theory

    SciTech Connect

    Hernandez, R.

    1993-11-01

    This work is concerned with the development of approximate methods to describe relatively large chemical systems. This effort has been divided into two primary directions: First, we have extended and applied a semiclassical transition state theory (SCTST) originally proposed by Miller to obtain microcanonical and canonical (thermal) rates for chemical reactions described by a nonseparable Hamiltonian, i.e. most reactions. Second, we have developed a method to describe the fluctuations of decay rates of individual energy states from the average RRKM rate in systems where the direct calculation of individual rates would be impossible. Combined with the semiclassical theory this latter effort has provided a direct comparison to the experimental results of Moore and coworkers. In SCTST, the Hamiltonian is expanded about the barrier and the ``good`` action-angle variables are obtained perturbatively; a WKB analysis of the effectively one-dimensional reactive direction then provides the transmission probabilities. The advantages of this local approximate treatment are that it includes tunneling effects and anharmonicity, and it systematically provides a multi-dimensional dividing surface in phase space. The SCTST thermal rate expression has been reformulated providing increased numerical efficiency (as compared to a naive Boltzmann average), an appealing link to conventional transition state theory (involving a ``prereactive`` partition function depending on the action of the reactive mode), and the ability to go beyond the perturbative approximation.

  1. Determination of the rate constant of hydroperoxyl radical reaction with phenol

    NASA Astrophysics Data System (ADS)

    Kozmér, Zsuzsanna; Arany, Eszter; Alapi, Tünde; Takács, Erzsébet; Wojnárovits, László; Dombi, András

    2014-09-01

    The rate constant of HO2rad reaction with phenol (kHO2rad +phenol) was investigated. The primary radical set produced in water γ radiolysis (rad OH, eaq- and Hrad ) was transformed to HO2rad /O2rad - by using dissolved oxygen and formate anion (in the form of either formic acid or sodium formate). The concentration ratio of HO2rad /O2rad - was affected by the pH value of the solution: under acidic conditions (using HCOOH) almost all radicals were converted to HO2rad , while under alkaline conditions (using HCOONa) to O2rad -. The degradation rate of phenol was significantly higher using HCOOH. From the ratio of reaction rates under the two reaction conditions kHO2rad +phenol was estimated to be (2.7±1.2)×103 L mol-1 s-1.

  2. Are physicians' ratings of pain affected by patients' physical attractiveness?

    PubMed

    Hadjistavropoulos, H D; Ross, M A; von Baeyer, C L

    1990-01-01

    The degree to which physical attractiveness and nonverbal expressions of pain influence physicians' perceptions of pain was investigated. Photographs of eight female university students were represented in four experimental conditions created by the manipulation of cosmetics, hairstyles, and facial expressions: (a) attractive-no pain, (b) attractive-pain, (c) unattractive-no pain, and (d) unattractive-pain. Each photograph was accompanied by a brief description of the patient's pain problem that was standard across conditions. Medical residents (N = 60) viewed the photographs and rated each patient's pain, distress, negative affective experience, health, personality, blame for the situation, and the physician's own solicitude for the patient. The results showed that physicians' ratings of pain were influenced both by attractiveness of patients and by nonverbal expressions of pain. Unattractive patients, and patients who were expressing pain, were perceived as experiencing more pain, distress, and negative affective experiences than attractive patients and patients who were not expressing pain. Unattractive patients also received higher ratings of solicitude on the doctor's part and lower ratings of health than attractive patients. Physician's assessments of pain appear to be influenced by the physical attractiveness of the patient. PMID:2367884

  3. Facial affective reactions to bitter-tasting foods and body mass index in adults.

    PubMed

    Garcia-Burgos, D; Zamora, M C

    2013-12-01

    Differences in food consumption among body-weight statuses (e.g., higher fruit intake linked with lower body mass index (BMI) and energy-dense products with higher BMI) has raised the question of why people who are overweight or are at risk of becoming overweight eat differently from thinner people. One explanation, in terms of sensitivity to affective properties of food, suggests that palatability-driven consumption is likely to be an important contributor to food intake, and therefore body weight. Extending this approach to unpalatable tastes, we examined the relationship between aversive reactions to foods and BMI. We hypothesized that people who have a high BMI will show more negative affective reactions to bitter-tasting stimuli, even after controlling for sensory perception differences. Given that hedonic reactions may influence consumption even without conscious feelings of pleasure/displeasure, the facial expressions were included in order to provide more direct access to affective systems than subjective reports. Forty adults (28 females, 12 males) participated voluntarily. Their ages ranged from 18 to 46 years (M=24.2, SD=5.8). On the basis of BMI, participants were classified as low BMI (BMI<20; n=20) and high BMI (BMI>23; n=20). The mean BMI was 19.1 for low BMI (SD=0.7) and 25.2 for high BMI participants (SD=1.8). Each subject tasted 5 mL of a grapefruit juice drink and a bitter chocolate drink. Subjects rated the drinks' hedonic and incentive value, familiarity and bitter intensity immediately after each stimulus presentation. The results indicated that high BMI participants reacted to bitter stimuli showing more profound changes from baseline in neutral and disgust facial expressions compared with low BMI. No differences between groups were detected for the subjective pleasantness and familiarity. The research here is the first to examine how affective facial reactions to bitter food, apart from taste responsiveness, can predict differences in BMI

  4. Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

    NASA Technical Reports Server (NTRS)

    Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J.

    1986-01-01

    The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

  5. Omphacite breakdown reactions and relation to eclogite exhumation rates

    NASA Astrophysics Data System (ADS)

    Anderson, Eric D.; Moecher, David P.

    2007-09-01

    Clinopyroxene + plagioclase (±Hbl ± Qtz) symplectites after omphacite are widely cited as evidence for prior eclogite-facies or high-pressure (HP) metamorphism. Precursor omphacite compositions of retrograde eclogites, used for reconstructing retrograde P- T paths, are commonly estimated by reintegrating symplectite phases with the assumption that the symplectite-forming reactions were isochemical. Comparisons of broadbeam symplectite compositions to adjacent unreacted pyroxene from various symplectites after clinopyroxene from the Appalachian Blue Ridge (ABR) and Western Gneiss Region (WGR) suggest that the symplectite forming reactions are largely isochemical. Endmember calculations based on reintegrated symplectite compositions from the ABR and WGR suggest that a minor Ca-Eskola (CaEs) component (XCaEs = 0.04-0.15) was present in precursor HP clinopyroxene. WGR symplectites consist of fine-grained (˜1 μm-scale), vermicular intergrowths of Pl + Cpx II ± Hbl that occur at grain boundaries or internally. ABR symplectites contain coarser (˜10 μm-scale) planar lamellae and rods of Pl + Cpx II + Qtz + Hbl within clinopyroxene cores. The contrasting textures correlate with decompression and cooling rate, and degree of overstepping of the retrograde reaction (lamellar: slow, erosionally controlled exhumation with slow/low overstepping; fine-grained, grainboundary symplectite: rapid, tectonic exhumation with rapid/high overstepping). Variations in XCaEs, Xjd, and XCaTs of precursor HP omphacite are related to the symplectic mineral assemblages that result from decompression. Quartz-normative symplectities indicate quartz-producing retrograde reactions (e.g., breakdown of precursor CaEs); quartz-free symplectities (e.g., diopside + plagioclase after omphacite) indicate quartz-consuming reactions (jd, CaTs breakdown) outpaced quartz-producing reactions.

  6. Rate constant for the reaction of atomic chlorine with methane

    NASA Technical Reports Server (NTRS)

    Lin, C. L.; Leu, M. T.; Demore, W. B.

    1978-01-01

    The rate constant and temperature dependence of the Cl + CH4 reaction have been investigated by the techniques of competitive chlorination of CH4/C2H6 mixtures and by discharge-flow/mass spectroscopy. The objectives were to determine an accurate value for the rate constant for use in stratospheric modeling, and to clarify discrepancies in results previously obtained by different techniques. The results deduced from the competitive chlorination study are in good agreement with the absolute values measured by the mass spectrometric method, and at temperatures above 300 K are in good agreement with measurements by other techniques based on resonance fluorescence detection of atomic chlorine. However, in the 220-300 K region, the competitive experiments indicate lower rate constants than those obtained by resonance fluorescence methods, and do not reproduce the curved Arrhenius plots seen in some of those studies.

  7. r-PROCESS Reaction Rates for the Actinides and Beyond

    NASA Astrophysics Data System (ADS)

    Panov, I. V.; Korneev, I. Yu.; Rauscher, T.; Thielemann, F.-K.

    2011-10-01

    We discuss the importance of different fission rates for the formation of heavy and superheavy nuclei in the astrophysical r-process. Neutron-induced reaction rates, including fission and neutron capture, are calculated in the temperature range 108 ≤ T(K) ≤ 1010 within the framework of the statistical model for targets with the atomic number 84 ≤ Z ≤ 118 (from Po to Uuo) from the neutron to the proton drip-line for different mass and fission barrier predictions based on Thomas-Fermi (TF), Extended Thomas-Fermi plus Strutinsky Integral (ETFSI), Finite-Range Droplet Model (FRDM) and Hartree-Fock-Bogolyubov (HFB) approaches. The contribution of spontaneous fission as well as beta-delayed fission to the recycling r-process is discussed. We also discuss the possibility of rate tests, based on mini r-processed yields in nuclear explosions.

  8. What Is Beautiful Feels Good: Affective Reactions to Physical Attractiveness.

    ERIC Educational Resources Information Center

    Carducci, Bernardo J.; Ogan, Tamra A.

    Previous research has consistently demonstrated that variations in physical attractiveness elicit different evaluative and behavioral responses. To assess differences in affective responses to variations in physical attractiveness and the affect of sex on those responses, 76 college students (31 male and 45 female) viewed colored slides of an…

  9. Acid–base chemical reaction model for nucleation rates in the polluted atmospheric boundary layer

    PubMed Central

    Chen, Modi; Titcombe, Mari; Jiang, Jingkun; Jen, Coty; Kuang, Chongai; Fischer, Marc L.; Eisele, Fred L.; Siepmann, J. Ilja; Hanson, David R.; Zhao, Jun; McMurry, Peter H.

    2012-01-01

    Climate models show that particles formed by nucleation can affect cloud cover and, therefore, the earth's radiation budget. Measurements worldwide show that nucleation rates in the atmospheric boundary layer are positively correlated with concentrations of sulfuric acid vapor. However, current nucleation theories do not correctly predict either the observed nucleation rates or their functional dependence on sulfuric acid concentrations. This paper develops an alternative approach for modeling nucleation rates, based on a sequence of acid–base reactions. The model uses empirical estimates of sulfuric acid evaporation rates obtained from new measurements of neutral molecular clusters. The model predicts that nucleation rates equal the sulfuric acid vapor collision rate times a prefactor that is less than unity and that depends on the concentrations of basic gaseous compounds and preexisting particles. Predicted nucleation rates and their dependence on sulfuric acid vapor concentrations are in reasonable agreement with measurements from Mexico City and Atlanta. PMID:23091030

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

    USGS Publications Warehouse

    Bahr, J.M.

    1990-01-01

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

  11. RPMDRATE: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    NASA Astrophysics Data System (ADS)

    Suleimanov, Yu. V.; Allen, J. W.; Green, W. H.

    2013-03-01

    We present RPMDRATE, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH4, OH+CH4 and H+C2H6 reactions. Catalogue identifier: AENW_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AENW_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: MIT license No. of lines in distributed program, including test data, etc.: 94512 No. of bytes in distributed program, including test data, etc.: 1395674 Distribution format: tar.gz Programming language: Fortran 90/95, Python (version 2.6.x or later, including any version of Python 3, is recommended). Computer: Not computer specific. Operating system: Any for which Python, Fortran 90/95 compiler and the required external routines are available. Has the code been vectorized or parallelized?: The program can efficiently utilize 4096+ processors, depending on problem and available computer. At low temperatures, 110 processors are reasonable for a typical umbrella integration run with an analytic potential energy function and gradients on the latest x86-64 machines.

  12. Rate-Controlled Constrained-Equilibrium Theory of Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Keck, James C.

    2008-08-01

    The Rate-Controlled Constrained-Equilibrium (RCCE) method for simplifying the treatment of reactions in complex systems is summarized and the selection of constraints for both close-to and far-from equilibrium systems is discussed. Illustrative examples of RCCE calculations of carbon monoxide concentrations in the exhaust products of an internal combustion engine and ignition delays for methane-oxygen mixtures in a constant volume adiabatic chamber are given and compared with "detailed" calculations. The advantages of RCCE calculations over "detailed" calculations are discussed.

  13. Kinetics of Imidazole Catalyzed Ester Hydrolysis: Use of Buffer Dilutions to Determine Spontaneous Rate, Catalyzed Rate, and Reaction Order.

    ERIC Educational Resources Information Center

    Lombardo, Anthony

    1982-01-01

    Described is an advanced undergraduate kinetics experiment using buffer dilutions to determine spontaneous rate, catalyzed rate, and reaction order. The reaction utilized is hydrolysis of p-nitro-phenyl acetate in presence of imidazole, which has been shown to enhance rate of the reaction. (Author/JN)

  14. Affective and cognitive reactions to subliminal flicker from fluorescent lighting.

    PubMed

    Knez, Igor

    2014-05-01

    This study renews the classical concept of subliminal perception (Peirce & Jastrow, 1884) by investigating the impact of subliminal flicker from fluorescent lighting on affect and cognitive performance. It was predicted that low compared to high frequency lighting (latter compared to former emits non-flickering light) would evoke larger changes in affective states and also impair cognitive performance. Subjects reported high rather than low frequency lighting to be more pleasant, which, in turn, enhanced their problem solving performance. This suggests that sensory processing can take place outside of conscious awareness resulting in conscious emotional consequences; indicating a role of affect in subliminal/implicit perception, and that positive affect may facilitate cognitive task performance. PMID:24685568

  15. Courting disaster: How diversification rate affects fitness under risk.

    PubMed

    Ratcliff, William C; Hawthorne, Peter; Libby, Eric

    2015-01-01

    Life is full of risk. To deal with this uncertainty, many organisms have evolved bet-hedging strategies that spread risk through phenotypic diversification. These rates of diversification can vary by orders of magnitude in different species. Here we examine how key characteristics of risk and organismal ecology affect the fitness consequences of variation in diversification rate. We find that rapid diversification is strongly favored when the risk faced has a wide spatial extent, with a single disaster affecting a large fraction of the population. This advantage is especially great in small populations subject to frequent disaster. In contrast, when risk is correlated through time, slow diversification is favored because it allows adaptive tracking of disasters that tend to occur in series. Naturally evolved diversification mechanisms in diverse organisms facing a broad array of environmental risks largely support these results. The theory presented in this article provides a testable ecological hypothesis to explain the prevalence of slow stochastic switching among microbes and rapid, within-clutch diversification strategies among plants and animals. PMID:25410817

  16. Courting disaster: How diversification rate affects fitness under risk

    PubMed Central

    Ratcliff, William C; Hawthorne, Peter; Libby, Eric

    2015-01-01

    Life is full of risk. To deal with this uncertainty, many organisms have evolved bet-hedging strategies that spread risk through phenotypic diversification. These rates of diversification can vary by orders of magnitude in different species. Here we examine how key characteristics of risk and organismal ecology affect the fitness consequences of variation in diversification rate. We find that rapid diversification is strongly favored when the risk faced has a wide spatial extent, with a single disaster affecting a large fraction of the population. This advantage is especially great in small populations subject to frequent disaster. In contrast, when risk is correlated through time, slow diversification is favored because it allows adaptive tracking of disasters that tend to occur in series. Naturally evolved diversification mechanisms in diverse organisms facing a broad array of environmental risks largely support these results. The theory presented in this article provides a testable ecological hypothesis to explain the prevalence of slow stochastic switching among microbes and rapid, within-clutch diversification strategies among plants and animals. PMID:25410817

  17. Primordial lithium - New reaction rates, new abundances, new constraints

    NASA Technical Reports Server (NTRS)

    Kawano, Lawrence; Schramm, David; Steigman, Gary

    1988-01-01

    Newly measured nuclear reaction rates for H-3(alpha, gamma)Li-7 (higher than previous values) and Li-7(p, alpha)He-4 (lower than previous values) are shown to increase the Li-7 yield from big band nucleosynthesis for lower baryon-to-photon ratio (less than about 4 x 10 to the 10th). Recent revisions in the He-3(alpha, gamma)Be-7 and the D(p, gamma)He-3 rates enhance the high (greater than 4 x 10 to the 10th) Li-7(Be) production. New, independent determinations of Li abundances in extreme population II stars are in excellent agreement with the work of Spites and give continued confidence in the use of Li-7 in big bang baryon density determinations.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  19. Pore and Continuum Scale Study of the Effect of Subgrid Transport Heterogeneity on Redox Reaction Rates

    SciTech Connect

    Liu, Yuanyuan; Liu, Chongxuan; Zhang, Changyong; Yang, Xiaofan; Zachara, John M.

    2015-08-01

    A micromodel system with a pore structure for heterogeneous flow and transport was used to investigate the effect of subgrid transport heterogeneity on redox reaction rates. Hematite reductive dissolution by injecting a reduced form of flavin mononucleotide (FMNH2) at variable flow rates was used as an example to probe the variations of redox reaction rates in different subgrid transport domains. Experiments, pore-scale simulations, and macroscopic modeling were performed to measure and simulate in-situ hematite reduction and to evaluate the scaling behavior of the redox reaction rates from the pore to macroscopic scales. The results indicated that the measured pore-scale rates of hematite reduction were consistent with the predictions from a pore scale reactive transport model. A general trend is that hematite reduction followed reductant transport pathways, starting from the advection-dominated pores toward the interior of diffusion-dominated domains. Two types of diffusion domains were considered in the micromodel: a micropore diffusion domain, which locates inside solid grains or aggregates where reactant transport is limited by diffusion; and a macropore diffusion domain, which locates at wedged, dead-end pore spaces created by the grain-grain contacts. The rate of hematite reduction in the advection-dominated domain was faster than those in the diffusion-controlled domains, and the rate in the macropore diffusion domain was faster than that in the micropore domain. The reduction rates in the advection and macropore diffusion domains increased with increasing flow rate, but were affected by different mechanisms. The rate increase in the advection domain was controlled by the mass action effect as a faster flow supplied more reactants, and the rate increase in the macropore domain was more affected by the rate of mass exchange with the advection domain, which increased with increasing flow rate. The hematite reduction rate in the micropore domain was, however

  20. Nucleation and reaction rates controlled by local reaction volume and reaction-induced stress - spinel layer growth as an example

    NASA Astrophysics Data System (ADS)

    Götze, Lutz C.; Milke, Ralf; Dohmen, Ralf; Wirth, Richard

    2014-05-01

    We observed the growth of spinel sensu stricto (MgAl2O4) between periclase (MgO) and corundum (Al2O3) in thin films deposited by the pulsed laser deposition method on crystallographically oriented single crystal substrates. The starting samples consisted of cut and ultra polished single crystals of either corundum (parallel (0001)) or periclase (parallel (111)) and an amorphous source layer of the respective reactant that in the very first stages of the experiments became polycrystalline. The cutting direction in the substrate minerals ensures that the substrate phases start to react along their close-packed hexagonal oxygen layers which allows topotactical growth of the newly formed spinel. The entire layer setup on the substrate crystals was only a few 100 nm thick. The growth of these spinel product layers was monitored in-situ using a heating attachment and synchrotron X-ray diffraction. From the reacted samples we took electron transparent foils by the focused ion beam method and analysed them ex-situ by TEM. At 1000°C we found a difference in spinel growth rate between one and two orders of magnitude between the two substrates, all other parameters held constant. At 900 and 1000 °C spinel had formed after one hour by 0.004 nm/s (900°C) and 0.034 nm/s (1000°C) on corundum substrate, while on periclase substrate the reaction had gone completely through the Al2O3 source layer transforming it to spinel by at least 15-30 times higher reaction rates (boundary values) and probably even faster. At 800°C no reaction occurred between periclase layers and corundum single crystals, whereas spinel crystallized at a (linearized) rate of 46 nm/h on periclase single crystals. We explain our findings by the local reaction volume at the periclase-corundum interface. Many studies (including this one) have established that spinel grows by cation exchange in a rather immobile oxygen sublattice. This mechanism implies a negative volume change at the Sp-Per interface (by -13

  1. Identification of factors affecting birth rate in Czech Republic

    NASA Astrophysics Data System (ADS)

    Zámková, Martina; Blašková, Veronika

    2013-10-01

    This article is concerned with identifying economic factors primarily that affect birth rates in Czech Republic. To find the relationship between the magnitudes, we used the multivariate regression analysis and for modeling, we used a time series of annual values (1994-2011) both economic indicators and indicators related to demographics. Due to potential problems with apparent dependence we first cleansed all series obtained from the Czech Statistical Office using first differences. It is clear from the final model that meets all assumptions that there is a positive correlation between birth rates and the financial situation of households. We described the financial situation of households by GDP per capita, gross wages and consumer price index. As expected a positive correlation was proved for GDP per capita and gross wages and negative dependence was proved for the consumer price index. In addition to these economic variables in the model there were used also demographic characteristics of the workforce and the number of employed people. It can be stated that if the Czech Republic wants to support an increase in the birth rate, it is necessary to consider the financial support for households with small children.

  2. Affective Understanding in Young Preschoolers and Reactions to Peers' Emotions.

    ERIC Educational Resources Information Center

    Denham, Susanne A.

    Age, specific emotion, and linguistic modality (verbal vs. non-verbal) were predicted to affect knowledge of emotion in young preschoolers (N = 45, mean age = 40.7 mos). Prosocial response to emotion and knowledge of emotion were also predicted to be related, given naturalistic observation and the use of contextually valid emotion knowledge…

  3. Somatic, Affective and Behavioral Distress Reactions across Cultures

    ERIC Educational Resources Information Center

    Canel-Cinarbas, Deniz; Aegisdottir, Stefania

    2010-01-01

    The purpose of the present study was to compare the expression and frequency of somatic, affective and cognitive symptoms of distress across Turkish and U.S. university students. An open-ended free-list question was used to elicit distress responses from 827 Turkish and U.S. participants. The coding was done using classical content analysis. It…

  4. Dietary restriction of rodents decreases aging rate without affecting initial mortality rate -- a meta-analysis.

    PubMed

    Simons, Mirre J P; Koch, Wouter; Verhulst, Simon

    2013-06-01

    Dietary restriction (DR) extends lifespan in multiple species from various taxa. This effect can arise via two distinct but not mutually exclusive ways: a change in aging rate and/or vulnerability to the aging process (i.e. initial mortality rate). When DR affects vulnerability, this lowers mortality instantly, whereas a change in aging rate will gradually lower mortality risk over time. Unraveling how DR extends lifespan is of interest because it may guide toward understanding the mechanism(s) mediating lifespan extension and also has practical implications for the application of DR. We reanalyzed published survival data from 82 pairs of survival curves from DR experiments in rats and mice by fitting Gompertz and also Gompertz-Makeham models. The addition of the Makeham parameter has been reported to improve the estimation of Gompertz parameters. Both models separate initial mortality rate (vulnerability) from an age-dependent increase in mortality (aging rate). We subjected the obtained Gompertz parameters to a meta-analysis. We find that DR reduced aging rate without affecting vulnerability. The latter contrasts with the conclusion of a recent analysis of a largely overlapping data set, and we show how the earlier finding is due to a statistical artifact. Our analysis indicates that the biology underlying the life-extending effect of DR in rodents likely involves attenuated accumulation of damage, which contrasts with the acute effect of DR on mortality reported for Drosophila. Moreover, our findings show that the often-reported correlation between aging rate and vulnerability does not constrain changing aging rate without affecting vulnerability simultaneously. PMID:23438200

  5. Rate Constant for the OH + CO Reaction at Low Temperatures.

    PubMed

    Liu, Yingdi; Sander, Stanley P

    2015-10-01

    Rate constants for the reaction of OH + CO → products (1) have been measured using laser photolysis/laser-induced fluorescence (LP/LIF) over the temperature range 193–296 K and at pressures of 50–700 Torr of Ar and N2. The reaction was studied under pseudo-first-order conditions, monitoring the decay of OH in the presence of a large excess of CO. The rate constants can be expressed as a combination of bimolecular and termolecular components. The bimolecular component was found to be temperature-independent with an expression given by kbi(T) = (1.54 ± 0.14) × 10(–13)[e(–(13±17)/T)] cm(3) molecule(–1) s(–1), with an error of one standard deviation. The termolecular component was fitted to the expression, kter = k0(T)[M]/[1 + (k0(T)[M]/k∞(T)] × 0.6({1+[log10(k0(T)[M]/k∞(T))]2}−1) where k0(T) = k0(300)(T/300)(−n) and k∞(T) = k∞(300)(T/300)(−m). The parameters for k0(T) were determined to be k0(300) = (6.0±0.5) × 10(−33) cm(6) molecule(–2) s(–1) in N2 and k0(300) = (3.4 ± 0.3) × 10(–33) cm(6) molecule(–2) s(–1) in Ar, with n = 1.9±0.5 and 2.0±0.4 in N2 and Ar, respectively. These parameters were determined using k0(T) and m from the NASA kinetics data evaluation (JPL Publication No. 10-6) since the experimental pressure range was far from the high-pressure limit. Addition of low concentrations of O2 had no discernible effect on the mechanism of the OH + CO reaction but resulted in secondary reactions which regenerated OH. PMID:26305192

  6. Factors affecting the heart rate during self-paced walking.

    PubMed

    Bassey, E J; Macdonald, I A; Patrick, J M

    1982-01-01

    The results of 277 self-paced walking tests have been analysed for the effects of body composition, sex and age using step-up multiple regression analysis. Equations are given for the influence of the significant factors on chosen walking speeds and on heart rate (fc) (standardised at 4.8 km . h-1 by interpolation from points recorded at three walking speeds). The basic equations are: Normal speed (km . h-1) = 1.72 + 2.13 stature (m) - 0.008 age (years) Fast speed (km . h-1) = 0.54 + 3.69 stature (m) - 0.016 age (years) For men: fc4.8 (beat . min-1) = 161 - 50.7 stature (m) + 0.223 body weight (kg) For women: fc4.8 (beat . min-1) = 161 - 50.7 stature (m) + 0.223 body weight (kg) + 4.43 The significant factors affecting freely chosen walking speeds are stature and age. When estimates of body composition are available, percentage fat is found to be the most influential single factor affecting fc, while sex no longer has a significant effect, and age now has a negative influence. When allowance is made for these factors the effects of customary physical activity can be seen more clearly. PMID:7199445

  7. In Search of Reaction Rate Scaling Law for Supersonic Combustion

    NASA Astrophysics Data System (ADS)

    Ladeinde, Foluso; Lou, Zhipeng; Li, Wenhai

    2015-11-01

    As a way of employing the flamelet approach, which was developed essentially for incompressible flows, to model supersonic combustion, the role ascribed to pressure has not been very convincing. That is, the reaction rate is often scaled on the square of the pressure in the finite Mach number flow field relative to the usually atmospheric static pressure field used in the generation of the flamelet library. This scaling assumption is quite simple and will therefore be very attractive if it has a sound theoretical basis and it works for a large selection of high-speed combustion flows. We try to find some justifications for different scaling laws, with the hope of coming up with a more universally-acceptable flamelet procedure for supersonic combustion.

  8. The effects of vacuum polarization on thermonuclear reaction rates

    NASA Technical Reports Server (NTRS)

    Gould, Robert J.

    1990-01-01

    Added to the pure Coulomb potential, the contribution from vacuum polarization increases the barrier, reducing the wave function (u) for reacting nuclei within the range of nuclear forces. The cross section and reaction rate are then reduced accordingly by a factor proportional to u squared. The effect is treated by evaluating the vacuum polarization potential as a small correction to the Coulomb term, then computing u in a WKB formulation. The calculation is done analytically employing the small r power-series expansion for the Uehling potential to express the final result in terms of convenient parameters. At a temperature of 1.4 x 10 to the 7th K the (negative) correction is 1.3 percent for the fundamental fusion process p + p yields d + e(+) + nu.

  9. High Heating Rates Affect Greatly the Inactivation Rate of Escherichia coli

    PubMed Central

    Huertas, Juan-Pablo; Aznar, Arantxa; Esnoz, Arturo; Fernández, Pablo S.; Iguaz, Asunción; Periago, Paula M.; Palop, Alfredo

    2016-01-01

    Heat resistance of microorganisms can be affected by different influencing factors. Although, the effect of heating rates has been scarcely explored by the scientific community, recent researches have unraveled its important effect on the thermal resistance of different species of vegetative bacteria. Typically heating rates described in the literature ranged from 1 to 20°C/min but the impact of much higher heating rates is unclear. The aim of this research was to explore the effect of different heating rates, such as those currently achieved in the heat exchangers used in the food industry, on the heat resistance of Escherichia coli. A pilot plant tubular heat exchanger and a thermoresistometer Mastia were used for this purpose. Results showed that fast heating rates had a deep impact on the thermal resistance of E. coli. Heating rates between 20 and 50°C/min were achieved in the heat exchanger, which were much slower than those around 20°C/s achieved in the thermoresistometer. In all cases, these high heating rates led to higher inactivation than expected: in the heat exchanger, for all the experiments performed, when the observed inactivation had reached about seven log cycles, the predictions estimated about 1 log cycle of inactivation; in the thermoresistometer these differences between observed and predicted values were even more than 10 times higher, from 4.07 log cycles observed to 0.34 predicted at a flow rate of 70 mL/min and a maximum heating rate of 14.7°C/s. A quantification of the impact of the heating rates on the level of inactivation achieved was established. These results point out the important effect that the heating rate has on the thermal resistance of E. coli, with high heating rates resulting in an additional sensitization to heat and therefore an effective food safety strategy in terms of food processing. PMID:27563300

  10. High Heating Rates Affect Greatly the Inactivation Rate of Escherichia coli.

    PubMed

    Huertas, Juan-Pablo; Aznar, Arantxa; Esnoz, Arturo; Fernández, Pablo S; Iguaz, Asunción; Periago, Paula M; Palop, Alfredo

    2016-01-01

    Heat resistance of microorganisms can be affected by different influencing factors. Although, the effect of heating rates has been scarcely explored by the scientific community, recent researches have unraveled its important effect on the thermal resistance of different species of vegetative bacteria. Typically heating rates described in the literature ranged from 1 to 20°C/min but the impact of much higher heating rates is unclear. The aim of this research was to explore the effect of different heating rates, such as those currently achieved in the heat exchangers used in the food industry, on the heat resistance of Escherichia coli. A pilot plant tubular heat exchanger and a thermoresistometer Mastia were used for this purpose. Results showed that fast heating rates had a deep impact on the thermal resistance of E. coli. Heating rates between 20 and 50°C/min were achieved in the heat exchanger, which were much slower than those around 20°C/s achieved in the thermoresistometer. In all cases, these high heating rates led to higher inactivation than expected: in the heat exchanger, for all the experiments performed, when the observed inactivation had reached about seven log cycles, the predictions estimated about 1 log cycle of inactivation; in the thermoresistometer these differences between observed and predicted values were even more than 10 times higher, from 4.07 log cycles observed to 0.34 predicted at a flow rate of 70 mL/min and a maximum heating rate of 14.7°C/s. A quantification of the impact of the heating rates on the level of inactivation achieved was established. These results point out the important effect that the heating rate has on the thermal resistance of E. coli, with high heating rates resulting in an additional sensitization to heat and therefore an effective food safety strategy in terms of food processing. PMID:27563300

  11. Correcting reaction rates measured by saturation-transfer magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Gabr, Refaat E.; Weiss, Robert G.; Bottomley, Paul A.

    2008-04-01

    Off-resonance or spillover irradiation and incomplete saturation can introduce significant errors in the estimates of chemical rate constants measured by saturation-transfer magnetic resonance spectroscopy (MRS). Existing methods of correction are effective only over a limited parameter range. Here, a general approach of numerically solving the Bloch-McConnell equations to calculate exchange rates, relaxation times and concentrations for the saturation-transfer experiment is investigated, but found to require more measurements and higher signal-to-noise ratios than in vivo studies can practically afford. As an alternative, correction formulae for the reaction rate are provided which account for the expected parameter ranges and limited measurements available in vivo. The correction term is a quadratic function of experimental measurements. In computer simulations, the new formulae showed negligible bias and reduced the maximum error in the rate constants by about 3-fold compared to traditional formulae, and the error scatter by about 4-fold, over a wide range of parameters for conventional saturation transfer employing progressive saturation, and for the four-angle saturation-transfer method applied to the creatine kinase (CK) reaction in the human heart at 1.5 T. In normal in vivo spectra affected by spillover, the correction increases the mean calculated forward CK reaction rate by 6-16% over traditional and prior correction formulae.

  12. Measurement of sulfur dioxide reaction rates in wintertime orographic clouds

    SciTech Connect

    Snider, J.R.

    1989-01-01

    Releases of SO2 into the wintertime orographic clouds at Elk Mountain in southeastern Wyoming were utilized to accelerate the rate of SO2 oxidation to cloud-water dissolved sulfate (SO4(-2)). Background SO2 mixing ratios were 0.6 parts-per-billion by volume (ppbv) and were consistent with the remote location of the experimental site and with supplemental cloud water, snow, and aerosol composition measurements. Background mixing ratios of hydrogen peroxide (H2O2) and the organohydroperoxides, expressed as methyl hydroperoxide (MHP), were 0.15 and 0.17 ppbv, respectively. The concentration of H2O2 in cloud water, obtained as rime, was also monitored. Analysis of these findings suggests that both reactive loss of H2O2 and volatilization during riming are mechanisms for H2O2 loss. The pseudo first-order SO2 depletion rates varied between 2 and 72 percent /hr (x=32 plus or minus 22 percent/hr, n=10). Observed depletions of H2O2 (x=0.030 ppbv) were consistent with observed yields of SO4(-2) (x=0.027 ppbv) and with model predictions. Observed depletions of MHP were not significantly different from 0.0 ppbv. This observation is both consistent with the much smaller solubility of MHP, compared with H2O2, and with the results of 16 model simulations. Reactions between dissolved SO2 and O3, between SO2 and O2, and between SO2 and HCHO were calculated to contribute less than 40 percent to the total amount of SO4(-2). These reactions were inferred to be inhibited by the low pH (less than 5) of the Elk Mountain cloud water. It is concluded that H2O2 is the dominant SO2 oxidant in these clouds, and that the laboratory measurements form an adequate basis for predicting the rate of in-cloud oxidation of SO2 by H2O2.

  13. Pressure Dependence of Gas-Phase Reaction Rates

    ERIC Educational Resources Information Center

    De Persis, Stephanie; Dollet, Alain; Teyssandier, Francis

    2004-01-01

    It is presented that only simple concepts, mainly taken from activated-complex or transition-state theory, are required to explain and analytically describe the influence of pressure on gas-phase reaction kinetics. The simplest kind of elementary gas-phase reaction is a unimolecular decomposition reaction.

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

    USGS Publications Warehouse

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

    1984-01-01

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

  15. Metabolic rate, latitude and thermal stability of roosts, but not phylogeny, affect rewarming rates of bats.

    PubMed

    Menzies, Allyson K; Webber, Quinn M R; Baloun, Dylan E; McGuire, Liam P; Muise, Kristina A; Coté, Damien; Tinkler, Samantha; Willis, Craig K R

    2016-10-01

    Torpor is an adaptation that allows many endotherms to save energy by abandoning the energetic cost of maintaining elevated body temperatures. Although torpor reduces energy consumption, the metabolic heat production required to arouse from torpor is energetically expensive and can impact the overall cost of torpor. The rate at which rewarming occurs can impact the cost of arousal, therefore, factors influencing rewarming rates of heterothermic endotherms could have influenced the evolution of rewarming rates and overall energetic costs of arousal from torpor. Bats are a useful taxon for studies of ecological and behavioral correlates of rewarming rate because of the widespread expression of heterothermy and ecological diversity across the >1200 known species. We used a comparative analysis of 45 bat species to test the hypothesis that ecological, behavioral, and physiological factors affect rewarming rates. We used basal metabolic rate (BMR) as an index of thermogenic capacity, and local climate (i.e., latitude of geographic range), roost stability and maximum colony size as ecological and behavioral predictors of rewarming rate. After controlling for phylogeny, high BMR was associated with rapid rewarming while species that live at higher absolute latitudes and in less thermally stable roosts also rewarmed most rapidly. These patterns suggests that some bat species rely on passive rewarming and social thermoregulation to reduce costs of rewarming, while others might rely on thermogenic capacity to maintain rapid rewarming rates in order to reduce energetic costs of arousal. Our results highlight species-specific traits associated with maintaining positive energy balance in a wide range of climates, while also providing insight into possible mechanisms underlying the evolution of heterothermy in endotherms. PMID:27317837

  16. The role of negative affectivity in pay-at-risk reactions: a longitudinal study.

    PubMed

    Begley, Thomas; Lee, Cynthia

    2005-03-01

    In this article, the authors examine the moderating role of negative and positive affectivity on the relationship of bonus size with bonus satisfaction and distributive justice in a company that had installed an unpopular pay-at-risk (PAR) compensation system. Extending the met expectations hypothesis, the authors predict that those low in negative affectivity will show a more pronounced positive relationship between size of PAR bonus and bonus reactions than those high in negative affectivity. Conversely, the authors expect positive affectivity to be unrelated to pay reactions. The results support their hypotheses. Implications are discussed. PMID:15769246

  17. Photonuclear and radiative capture reaction rates for Nuclear Astrophysics

    NASA Astrophysics Data System (ADS)

    Beard, Mary; Frauendorf, S.; Kaempfer, B.; Scwengner, R.; Wiescher, M.

    2011-10-01

    The vast majority of nuclei heavier than iron are synthesisized via the capture of neutrons. There are however 35 naturally occurring nuclei, including isotopes of Mo and La, located on the neutron-deficient size of the valley of stability. It has been proposed that these nuclei, referred to as p-nuclei, are produced via sequential photo-dissociation reactions in the oxygen-neon shell burning regions of a pre-supernova star. As such, cross sections for p-nuclei production are particularly sensitive to the gamma-ray strength function, which, though dominated by the giant dipole resonance, may contain extra strength contributions near to the neutron threshold. Recently new (γ, γ') cross section measurements have been performed at the ELBE facility at Helmholtz-Zentrum Dresden-Rossendorf for the nuclei ^92-100Mo, ^88Sr, ^90Zr and ^139La probing the photo-absorption cross section over an energy range 4.5 - 6 MeV, up to the neutron separation threshold. The use of these measurements as a test of existing gamma-ray strength function models, and the consequent impact on p-nuclei production rates, will be discussed.

  18. Enhanced reaction rates in NDP analysis with neutron scattering

    SciTech Connect

    Downing, R. Gregory

    2014-04-15

    Neutron depth profiling (NDP) makes accessible quantitative information on a few isotopic concentration profiles ranging from the surface into the sample a few micrometers. Because the candidate analytes for NDP are few, there is little interference encountered. Furthermore, neutrons have no charge so mixed chemical states in the sample are of no direct concern. There are a few nuclides that exhibit large probabilities for neutron scattering. The effect of neutron scattering on NDP measurements has not previously been evaluated as a basis for either enhancing the reaction rates or as a source of measurement error. Hydrogen is a common element exhibiting large neutron scattering probability found in or around sample volumes being analyzed by NDP. A systematic study was conducted to determine the degree of signal change when neutron scattering occurs during analysis. The relative signal perturbation was evaluated for materials of varied neutron scattering probability, concentration, total mass, and geometry. Signal enhancements up to 50% are observed when the hydrogen density is high and in close proximity to the region of analysis with neutron beams of sub thermal energies. Greater signal enhancements for the same neutron number density are reported for thermal neutron beams. Even adhesive tape used to position the sample produces a measureable signal enhancement. Because of the shallow volume, negligible distortion of the NDP measured profile shape is encountered from neutron scattering.

  19. Reaction mechanism and rate constants of the CH+CH4 reaction: a theoretical study

    NASA Astrophysics Data System (ADS)

    Ribeiro, Joao Marcelo; Mebel, Alexander M.

    2015-07-01

    Ab initio and density functional calculations have been performed to elucidate the mechanism of CH radical insertion into methane. The results show that the reaction can be viewed to occur via two stages. On the first stage, the CH radical approaches methane without large structural changes to acquire proper positioning for the subsequent stage, where H-migration occurs from CH4 to CH, along with a C-C bond formation. Where the first stage ends and the second begins, a tight transition state was located using the B3LYP/6-311G(d,p) and MP4(SDQ)/6-311++G(d,p) methods. Using a rigid rotor - harmonic oscillator approach within transition state theory, we show that at the MP5/6-311++G(d,p)//MP4(SDQ)/6-311++G(d,p) level the calculated rate constants are in a reasonably good agreement with experiment in a broad temperature range of 145-581 K. Even at low temperatures, the insertion reaction bottleneck is found about the location of the tight transition state, rather than at long separations between the CH and CH4 reactants. In addition, high level CCSD(T)-F12/CBS calculations of the remainder of the C2H5 potential energy surface predict the CH+CH4 reaction to proceed via the initial insertion step to the ethyl radical which then can emit a hydrogen atom to form highly exothermic C2H4+H products.

  20. Molecule-based approach for computing chemical-reaction rates in upper atmosphere hypersonic flows.

    SciTech Connect

    Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

    2009-08-01

    This report summarizes the work completed during FY2009 for the LDRD project 09-1332 'Molecule-Based Approach for Computing Chemical-Reaction Rates in Upper-Atmosphere Hypersonic Flows'. The goal of this project was to apply a recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary nonequilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological non-equilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, the difference between the two models can exceed 10 orders of magnitude. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates. Extensions of the model to reactions typically found in combustion flows and ionizing reactions are also found to be in very good agreement with available measurements, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

  1. On the ambiguity of the reaction rate constants in multivariate curve resolution for reversible first-order reaction systems.

    PubMed

    Schröder, Henning; Sawall, Mathias; Kubis, Christoph; Selent, Detlef; Hess, Dieter; Franke, Robert; Börner, Armin; Neymeyr, Klaus

    2016-07-13

    If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data. PMID:27237834

  2. The effects of physical and geochemical heterogeneities on hydro-geochemical transport and effective reaction rates

    NASA Astrophysics Data System (ADS)

    Atchley, Adam L.; Navarre-Sitchler, Alexis K.; Maxwell, Reed M.

    2014-09-01

    The role of coupled physical and geochemical heterogeneities in hydro-geochemical transport is investigated by simulating three-dimensional transport in a heterogeneous system with kinetic mineral reactions. Ensembles of 100 physically heterogeneous realizations were simulated for three geochemical conditions: 1) spatially homogeneous reactive mineral surface area, 2) reactive surface area positively correlated to hydraulic heterogeneity, and 3) reactive surface area negatively correlated to hydraulic heterogeneity. Groundwater chemistry and the corresponding effective reaction rates were calculated at three transverse planes to quantify differences in plume evolution due to heterogeneity in mineral reaction rates and solute residence time (τ). The model is based on a hypothetical CO2 intrusion into groundwater from a carbon capture utilization and storage (CCUS) operation where CO2 dissolution and formation of carbonic acid created geochemical dis-equilibrium between fluids and the mineral galena that resulted in increased aqueous lead (Pb2 +) concentrations. Calcite dissolution buffered the pH change and created conditions of galena oversaturation, which then reduced lead concentrations along the flow path. Near the leak kinetic geochemical reactions control the release of solutes into the fluid, but further along the flow path mineral solubility controls solute concentrations. Simulation results demonstrate the impact of heterogeneous distribution of geochemical reactive surface area in coordination with physical heterogeneity on the effective reaction rate (Krxn,eff) and Pb2 + concentrations within the plume. Dissimilarities between ensemble Pb2 + concentration and Krxn,eff are attributed to how geochemical heterogeneity affects the time (τeq) and therefore advection distance (Leq) required for the system to re-establish geochemical equilibrium. Only after geochemical equilibrium is re-established, Krxn,eff and Pb2 + concentrations are the same for all three

  3. The effects of physical and geochemical heterogeneities on hydro-geochemical transport and effective reaction rates.

    PubMed

    Atchley, Adam L; Navarre-Sitchler, Alexis K; Maxwell, Reed M

    2014-09-01

    The role of coupled physical and geochemical heterogeneities in hydro-geochemical transport is investigated by simulating three-dimensional transport in a heterogeneous system with kinetic mineral reactions. Ensembles of 100 physically heterogeneous realizations were simulated for three geochemical conditions: 1) spatially homogeneous reactive mineral surface area, 2) reactive surface area positively correlated to hydraulic heterogeneity, and 3) reactive surface area negatively correlated to hydraulic heterogeneity. Groundwater chemistry and the corresponding effective reaction rates were calculated at three transverse planes to quantify differences in plume evolution due to heterogeneity in mineral reaction rates and solute residence time (τ). The model is based on a hypothetical CO2 intrusion into groundwater from a carbon capture utilization and storage (CCUS) operation where CO2 dissolution and formation of carbonic acid created geochemical dis-equilibrium between fluids and the mineral galena that resulted in increased aqueous lead (Pb(2+)) concentrations. Calcite dissolution buffered the pH change and created conditions of galena oversaturation, which then reduced lead concentrations along the flow path. Near the leak kinetic geochemical reactions control the release of solutes into the fluid, but further along the flow path mineral solubility controls solute concentrations. Simulation results demonstrate the impact of heterogeneous distribution of geochemical reactive surface area in coordination with physical heterogeneity on the effective reaction rate (Krxn,eff) and Pb(2+) concentrations within the plume. Dissimilarities between ensemble Pb(2+) concentration and Krxn,eff are attributed to how geochemical heterogeneity affects the time (τeq) and therefore advection distance (Leq) required for the system to re-establish geochemical equilibrium. Only after geochemical equilibrium is re-established, Krxn,eff and Pb(2+) concentrations are the same for all

  4. Optimal reconstruction of reaction rates from particle distributions

    NASA Astrophysics Data System (ADS)

    Fernandez-Garcia, Daniel; Sanchez-Vila, Xavier

    2010-05-01

    Random walk particle tracking methodologies to simulate solute transport of conservative species constitute an attractive alternative for their computational efficiency and absence of numerical dispersion. Yet, problems stemming from the reconstruction of concentrations from particle distributions have typically prevented its use in reactive transport problems. The numerical problem mainly arises from the need to first reconstruct the concentrations of species/components from a discrete number of particles, which is an error prone process, and then computing a spatial functional of the concentrations and/or its derivatives (either spatial or temporal). Errors are then propagated, so that common strategies to reconstruct this functional require an unfeasible amount of particles when dealing with nonlinear reactive transport problems. In this context, this article presents a methodology to directly reconstruct this functional based on kernel density estimators. The methodology mitigates the error propagation in the evaluation of the functional by avoiding the prior estimation of the actual concentrations of species. The multivariate kernel associated with the corresponding functional depends on the size of the support volume, which defines the area over which a given particle can influence the functional. The shape of the kernel functions and the size of the support volume determines the degree of smoothing, which is optimized to obtain the best unbiased predictor of the functional using an iterative plug-in support volume selector. We applied the methodology to directly reconstruct the reaction rates of a precipitation/dissolution problem involving the mixing of two different waters carrying two aqueous species in chemical equilibrium and moving through a randomly heterogeneous porous medium.

  5. Even low alcohol concentrations affect obstacle avoidance reactions in healthy senior individuals

    PubMed Central

    2010-01-01

    Background Alcohol is a commonly used social drug and driving under influence is a well-established risk factor for traffic accidents[1]. To improve road safety, legal limits are set for blood alcohol concentration (BAC) and driving, usually at 0.05% (most European countries) or 0.08% (most US states, Canada and UK). In contrast, for walking there are no legal limits, yet there are numerous accounts of people stumbling and falling after drinking. Alcohol, even at these low concentrations, affects brain function and increases fall risk. An increased fall risk has been associated with impaired obstacle avoidance skills. Low level BACs are likely to affect obstacle avoidance reactions during gait, since the brain areas that are presumably involved in these reactions have been shown to be influenced by alcohol. Therefore we investigated the effect of low to moderate alcohol consumption on such reactions. Thirteen healthy senior individuals (mean(SD) age: 61.5(4.4) years, 9 male) were subjected to an obstacle avoidance task on a treadmill after low alcohol consumption. Fast stepping adjustments were required to successfully avoid suddenly appearing obstacles. Response times and amplitudes of the m. biceps femoris, a prime mover, as well as avoidance failure rates were assessed. Findings After the first alcoholic drink, 12 of the 13 participants already had slower responses. Without exception, all participants' biceps femoris response times were delayed after the final alcoholic drink (avg ± sd:180 ± 20 ms; p < 0.001) compared to when participants were sober (156 ± 16 ms). Biceps femoris response times were significantly delayed from BACs of 0.035% onwards and were strongly associated with increasing levels of BAC (r = 0.6; p < 0.001). These delays had important behavioural consequences. Chances of hitting the obstacle were doubled with increased BACs. Conclusions The present results clearly show that even with BACs considered to be safe for driving, obstacle

  6. Reaction time in gait initiation depends on the time available for affective processing.

    PubMed

    Gélat, Thierry; Chapus, Carole Ferrel

    2015-11-16

    Previous studies have reported that reaction time in gait initiation was affected by emotion eliciting pictures. This study examined the effect of a change in the delay between image onset and the imperative "go" on reaction time. From a standing posture, 19 young adults had to walk (several steps) toward pleasant or unpleasant images in two conditions. In the short condition, the word "go" appeared 500ms after image onset and participants were instructed to initiate gait as soon as possible after the word go appeared. In the long condition, the same procedure was used but the word "go" appeared 3000ms after image onset. Results demonstrated that motor responses were faster for pleasant pictures than unpleasant ones in the short condition. In contrast, no significant difference was found between both categories of pictures in the long condition. Moreover, we found that self ratings of valence of unpleasant pictures were less unpleasant in the long condition than in the short one whereas there was no difference for pleasant pictures between both conditions. This result reflected a change in the affective significance of unpleasant pictures in the long condition. We also found in the long condition, that the body was inclined forward and to the stance limb during the standing posture and importantly with a similar extent for pleasant and unpleasant pictures. This change clearly reflected a facilitation of the gait initiation process. Overall, results suggested that this gait facilitation when confronted to unpleasant pictures resulted from emotional regulation processes enabling to reappraise these pictures and to override the initial avoidance tendency that they caused. PMID:26455865

  7. Cross sections and reaction rates of relevance to aeronomy

    SciTech Connect

    Fox, J.L. )

    1991-01-01

    Experimental and theoretical data relevant to models and measurements of the chemical and thermal structures and luminosity of the thermospheres of the earth and planets published during the last four years are surveyed. Among chemical processes, attention is given to ion-molecule reactions, dissociative recombination of molecular ions, and reactions between neutral species. Both reactions between ground state species and species in excited states are considered, including energy transfer and quenching. Measured and calculated cross sections for interactions of solar radiation with atmospheric species, such as photoabsorption, photoionization, and photodissociation and related processes are surveyed.

  8. External Load Affects Ground Reaction Force Parameters Non-uniformly during Running in Weightlessness

    NASA Technical Reports Server (NTRS)

    DeWitt, John; Schaffner, Grant; Laughlin, Mitzi; Loehr, James; Hagan, R. Donald

    2004-01-01

    Long-term exposure to microgravity induces detrimefits to the musculcskdetal system (Schneider et al., 1995; LeBlanc et al., 2000). Treadmill exercise is used onboard the International Space Station as an exercise countermeasure to musculoskeletal deconditioning due to spaceflight. During locomotive exercise in weightlessness (0G), crewmembers wear a harness attached to an external loading mechanism (EL). The EL pulls the crewmember toward the treadmill, and provides resistive load during the impact and propulsive phases of gait. The resulting forces may be important in stimulating bone maintenance (Turner, 1998). The EL can be applied via a bungee and carabineer clip configuration attached to the harness and can be manipulated to create varying amounts of load levels during exercise. Ground-based research performed using a vertically mounted treadmill found that peak ground reaction forces (GRF) during running at an EL of less than one body weight (BW) are less than those that occur during running in normal gravity (1G) (Davis et al., 1996). However, it is not known how the GRF are affected by the EL in a true OG environment. Locomotion while suspended may result in biomechanics that differ from free running. The purpose of this investigation was to determine how EL affects peak impact force, peak propulsive force, loading rate, and impulse of the GRF during running in 0G. It was hypothesized that increasing EL would result in increases in each GRF parameter.

  9. Nutrient transport as affected by rate of overland flow

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Little information is currently available concerning the effects of varying flow rate on nutrient transport by overland flow. The objective of this study was to measure the effects of overland flow rate on nutrient transport following the application of beef cattle or swine manure to plots containin...

  10. Leptin expression affects metabolic rate in zebrafish embryos (D. rerio)

    PubMed Central

    Dalman, Mark R.; Liu, Qin; King, Mason D.; Bagatto, Brian; Londraville, Richard L.

    2013-01-01

    We used antisense morpholino oligonucleotide technology to knockdown leptin-(A) gene expression in developing zebrafish embryos and measured its effects on metabolic rate and cardiovascular function. Using two indicators of metabolic rate, oxygen consumption was significantly lower in leptin morphants early in development [<48 hours post-fertilization (hpf)], while acid production was significantly lower in morphants later in development (>48 hpf). Oxygen utilization rates in <48 hpf embryos and acid production in 72 hpf embryos could be rescued to that of wildtype embryos by recombinant leptin coinjected with antisense morpholino. Leptin is established to influence metabolic rate in mammals, and these data suggest leptin signaling also influences metabolic rate in fishes. PMID:23847542

  11. Upscaling of reaction rates in reactive transport using pore-scale reactive transport model

    NASA Astrophysics Data System (ADS)

    Yoon, H.; Dewers, T. A.; Arnold, B. W.; Major, J. R.; Eichhubl, P.; Srinivasan, S.

    2013-12-01

    Dissolved CO2 during geological CO2 storage may react with minerals in fractured rocks, confined aquifers, or faults, resulting in mineral precipitation and dissolution. The overall rate of reaction can be affected by coupled processes among hydrodynamics, transport, and reactions at the (sub) pore-scale. In this research pore-scale modeling of coupled fluid flow, reactive transport, and heterogeneous reaction at the mineral surface is applied to account for permeability alterations caused by precipitation-induced pore-blocking. This work is motivated by the observed CO2 seeps from a natural analog to geologic CO2 sequestration at Crystal Geyser, Utah. A key observation is the lateral migration of CO2 seep sites at a scale of ~ 100 meters over time. A pore-scale model provides fundamental mechanistic explanations of how calcite precipitation alters flow paths by pore plugging under different geochemical compositions and pore configurations. In addition, response function of reaction rates will be constructed from pore-scale simulations which account for a range of reaction regimes characterized by the Damkohler and Peclet numbers. Newly developed response functions will be used in a continuum scale model that may account for large-scale phenomena mimicking lateral migration of surface CO2 seeps. Comparison of field observations and simulations results will provide mechanistic explanations of the lateral migration and enhance our understanding of subsurface processes associated with the CO2 injection. This work is supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security

  12. Rates of primary electron transfer reactions in the photosystem I reaction center reconstituted with different quinones as the secondary acceptor

    SciTech Connect

    Kumazaki, Shigeichi; Kandori, Hideki; Yoshihara, Keitaro ); Iwaki, Masayo; Itoh, Shigeru ); Ikegamu, Isamu )

    1994-10-27

    Rates of sequential electron transfer reactions from the primary electron donor chlorophyll dimer (P700) to the electron acceptor chlorophyll a-686 (A[sub 0]) and to the secondary acceptor quinone (Q[sub [phi

  13. Interactive Program System for Integration of Reaction Rate Equations.

    ERIC Educational Resources Information Center

    Chesick, John P.

    1988-01-01

    Describes a Pascal-language based kinetics rate package for the microcomputer. Considers possible ecological uses for the program and illustrates results for several rate laws. Discusses hardware and software needs for adequate operation. (ML)

  14. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    NASA Technical Reports Server (NTRS)

    Tsotsis, T. T.; Sane, R. C.

    1987-01-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  15. Quick and Easy Rate Equations for Multistep Reactions

    ERIC Educational Resources Information Center

    Savage, Phillip E.

    2008-01-01

    Students rarely see closed-form analytical rate equations derived from underlying chemical mechanisms that contain more than a few steps unless restrictive simplifying assumptions (e.g., existence of a rate-determining step) are made. Yet, work published decades ago allows closed-form analytical rate equations to be written quickly and easily for…

  16. Women's Self-Disclosure of HIV Infection: Rates, Reasons, Reactions.

    ERIC Educational Resources Information Center

    Simoni, Jane M.; And Others

    1995-01-01

    A survey of 65 ethnically diverse women revealed relatively low rates of disclosure of HIV-positive serostatus to extended family members, somewhat higher rates for immediate family members, and highest rates for lovers or friends. Spanish-speaking Latinas were less likely to disclose their serostatus than English-speaking Latinas, African…

  17. Development of the new approach to the diffusion-limited reaction rate theory

    SciTech Connect

    Veshchunov, M. S.

    2012-04-15

    The new approach to the diffusion-limited reaction rate theory, recently proposed by the author, is further developed on the base of a similar approach to Brownian coagulation. The traditional diffusion approach to calculation of the reaction rate is critically analyzed. In particular, it is shown that the traditional approach is applicable only in the special case of reactions with a large reaction radius and the mean inter-particle distances, and become inappropriate in calculating the reaction rate in the case of a relatively small reaction radius. In the latter case, most important for chemical reactions, particle collisions occur not in the diffusion regime but mainly in the kinetic regime characterized by homogeneous (random) spatial distribution of particles on the length scale of the mean inter-particle distance. The calculated reaction rate for a small reaction radius in three dimensions formally (and fortuitously) coincides with the expression derived in the traditional approach for reactions with a large reaction radius, but notably deviates at large times from the traditional result in the planar two-dimensional geometry. In application to reactions on discrete lattice sites, new relations for the reaction rate constants are derived for both three-dimensional and two-dimensional lattices.

  18. Does Vessel Noise Affect Oyster Toadfish Calling Rates?

    PubMed

    Luczkovich, Joseph J; Krahforst, Cecilia S; Hoppe, Harry; Sprague, Mark W

    2016-01-01

    The question we addressed in this study is whether oyster toadfish respond to vessel disturbances by calling less when vessels with lower frequency spectra are present in a sound recording and afterward. Long-term data recorders were deployed at the Neuse (high vessel-noise site) and Pamlico (low vessel-noise site) Rivers. There were many fewer toadfish detections at the high vessel-noise site than the low-noise station. Calling rates were lower in the high-boat traffic area, suggesting that toadfish cannot call over loud vessel noise, reducing the overall calling rate, and may have to call more often when vessels are not present. PMID:26611015

  19. Do Graduate Student Teacher Training Courses Affect Placement Rates?

    ERIC Educational Resources Information Center

    Ishiyama, John; Balarezo, Christine; Miles, Tom

    2014-01-01

    We investigate whether the existence of a required graduate course on "Teaching in Political Science" is related to overall job placement rates reported by graduate political science programs. We examine this in light of evidence from 73 public PhD-granting political science departments across the country. We find that the existence of…

  20. Camelina production affected by seeding rate and depth

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Camelina (Camelina sativa L.) is an oilseed that has shown potential as an alternative crop to diversify wheat-fallow systems in the northern Great Plains. However, agronomic information is lacking for management of this relatively new crop. The impact of seeding depth and rate were determined in s...

  1. Fluctuation enhanced electrochemical reaction rates at the nanoscale.

    PubMed

    García-Morales, Vladimir; Krischer, Katharina

    2010-03-01

    The electrode potential constitutes a dynamical variable whenever an electrode is resistively coupled to the electric circuit. We show that at the nanoscale, the discreteness and stochasticity of an electron transfer event causes fluctuations of the electrode potential that render all elementary electrochemical reactions to be faster on a nanoelectrode than predicted by the macroscopic (Butler-Volmer) electrochemical kinetics. This phenomenon is substantiated by means of a generalized (electro)chemical master equation. PMID:20176966

  2. Error Rate Comparison during Polymerase Chain Reaction by DNA Polymerase.

    PubMed

    McInerney, Peter; Adams, Paul; Hadi, Masood Z

    2014-01-01

    As larger-scale cloning projects become more prevalent, there is an increasing need for comparisons among high fidelity DNA polymerases used for PCR amplification. All polymerases marketed for PCR applications are tested for fidelity properties (i.e., error rate determination) by vendors, and numerous literature reports have addressed PCR enzyme fidelity. Nonetheless, it is often difficult to make direct comparisons among different enzymes due to numerous methodological and analytical differences from study to study. We have measured the error rates for 6 DNA polymerases commonly used in PCR applications, including 3 polymerases typically used for cloning applications requiring high fidelity. Error rate measurement values reported here were obtained by direct sequencing of cloned PCR products. The strategy employed here allows interrogation of error rate across a very large DNA sequence space, since 94 unique DNA targets were used as templates for PCR cloning. The six enzymes included in the study, Taq polymerase, AccuPrime-Taq High Fidelity, KOD Hot Start, cloned Pfu polymerase, Phusion Hot Start, and Pwo polymerase, we find the lowest error rates with Pfu, Phusion, and Pwo polymerases. Error rates are comparable for these 3 enzymes and are >10x lower than the error rate observed with Taq polymerase. Mutation spectra are reported, with the 3 high fidelity enzymes displaying broadly similar types of mutations. For these enzymes, transition mutations predominate, with little bias observed for type of transition. PMID:25197572

  3. Error Rate Comparison during Polymerase Chain Reaction by DNA Polymerase

    DOE PAGESBeta

    McInerney, Peter; Adams, Paul; Hadi, Masood Z.

    2014-01-01

    As larger-scale cloning projects become more prevalent, there is an increasing need for comparisons among high fidelity DNA polymerases used for PCR amplification. All polymerases marketed for PCR applications are tested for fidelity properties (i.e., error rate determination) by vendors, and numerous literature reports have addressed PCR enzyme fidelity. Nonetheless, it is often difficult to make direct comparisons among different enzymes due to numerous methodological and analytical differences from study to study. We have measured the error rates for 6 DNA polymerases commonly used in PCR applications, including 3 polymerases typically used for cloning applications requiring high fidelity. Errormore » rate measurement values reported here were obtained by direct sequencing of cloned PCR products. The strategy employed here allows interrogation of error rate across a very large DNA sequence space, since 94 unique DNA targets were used as templates for PCR cloning. The six enzymes included in the study, Taq polymerase, AccuPrime-Taq High Fidelity, KOD Hot Start, cloned Pfu polymerase, Phusion Hot Start, and Pwo polymerase, we find the lowest error rates with Pfu , Phusion, and Pwo polymerases. Error rates are comparable for these 3 enzymes and are >10x lower than the error rate observed with Taq polymerase. Mutation spectra are reported, with the 3 high fidelity enzymes displaying broadly similar types of mutations. For these enzymes, transition mutations predominate, with little bias observed for type of transition.« less

  4. Error Rate Comparison during Polymerase Chain Reaction by DNA Polymerase

    PubMed Central

    McInerney, Peter; Adams, Paul; Hadi, Masood Z.

    2014-01-01

    As larger-scale cloning projects become more prevalent, there is an increasing need for comparisons among high fidelity DNA polymerases used for PCR amplification. All polymerases marketed for PCR applications are tested for fidelity properties (i.e., error rate determination) by vendors, and numerous literature reports have addressed PCR enzyme fidelity. Nonetheless, it is often difficult to make direct comparisons among different enzymes due to numerous methodological and analytical differences from study to study. We have measured the error rates for 6 DNA polymerases commonly used in PCR applications, including 3 polymerases typically used for cloning applications requiring high fidelity. Error rate measurement values reported here were obtained by direct sequencing of cloned PCR products. The strategy employed here allows interrogation of error rate across a very large DNA sequence space, since 94 unique DNA targets were used as templates for PCR cloning. The six enzymes included in the study, Taq polymerase, AccuPrime-Taq High Fidelity, KOD Hot Start, cloned Pfu polymerase, Phusion Hot Start, and Pwo polymerase, we find the lowest error rates with Pfu, Phusion, and Pwo polymerases. Error rates are comparable for these 3 enzymes and are >10x lower than the error rate observed with Taq polymerase. Mutation spectra are reported, with the 3 high fidelity enzymes displaying broadly similar types of mutations. For these enzymes, transition mutations predominate, with little bias observed for type of transition. PMID:25197572

  5. Local divergence of thermal reaction norms among amphibian populations is affected by pond temperature variation.

    PubMed

    Richter-Boix, Alex; Katzenberger, Marco; Duarte, Helder; Quintela, María; Tejedo, Miguel; Laurila, Anssi

    2015-08-01

    Although temperature variation is known to cause large-scale adaptive divergence, its potential role as a selective factor over microgeographic scales is less well-understood. Here, we investigated how variation in breeding pond temperature affects divergence in multiple physiological (thermal performance curve and critical thermal maximum [CTmax]) and life-history (thermal developmental reaction norms) traits in a network of Rana arvalis populations. The results supported adaptive responses to face two main constraints limiting the evolution of thermal adaptation. First, we found support for the faster-slower model, indicating an adaptive response to compensate for the thermodynamic constraint of low temperatures in colder environments. Second, we found evidence for the generalist-specialist trade-off with populations from colder and less thermally variable environments exhibiting a specialist phenotype performing at higher rates but over a narrower range of temperatures. By contrast, the local optimal temperature for locomotor performance and CTmax did not match either mean or maximum pond temperatures. These results highlight the complexity of the adaptive multiple-trait thermal responses in natural populations, and the role of local thermal variation as a selective force driving diversity in life-history and physiological traits in the presence of gene flow. PMID:26118477

  6. The Implicit Association Test as a Class Assignment: Student Affective and Attitudinal Reactions

    ERIC Educational Resources Information Center

    Morris, Kathryn A.; Ashburn-Nardo, Leslie

    2010-01-01

    The Implicit Association Test (IAT) is a popular means of examining "hidden" biases. However, some express concerns about classroom use of the IAT, citing students' potentially negative affective reactions to taking the IAT and discovering their implicit biases. To investigate the validity of this criticism, 35 social psychology students completed…

  7. Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Bayes, K.

    1998-01-01

    Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

  8. Effect of temperature oscillation on chemical reaction rates in the atmosphere

    NASA Technical Reports Server (NTRS)

    Eberstein, I. J.

    1974-01-01

    The effect of temperature fluctuations on atmospheric ozone chemistry is examined by considering the Chapman photochemical theory of ozone transport to calculate globally averaged ozone production rates from mean reaction rates, activation energies, and recombination processes.

  9. Upper atmosphere research: Reaction rate and optical measurements

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Allen, J. E., Jr.; Nava, D. F.; Payne, W. A., Jr.

    1990-01-01

    The objective is to provide photochemical, kinetic, and spectroscopic information necessary for photochemical models of the Earth's upper atmosphere and to examine reactions or reactants not presently in the models to either confirm the correctness of their exclusion or provide evidence to justify future inclusion in the models. New initiatives are being taken in technique development (many of them laser based) and in the application of established techniques to address gaps in the photochemical/kinetic data base, as well as to provide increasingly reliable information.

  10. Interlaboratory reaction rate program. 12th progress report, November 1976-October 1979

    SciTech Connect

    Lippincott, E.P.; McElroy, W.N.; Preston, C.C.

    1980-09-01

    The Interlaboratory Reaction Rate UILRR) program is establishing the capability to accurately measure neutron-induced reactions and reaction rates for reactor fuels and materials development programs. The goal for the principal fission reactions, /sup 235/U, /sup 238/U and /sup 239/Pu, is an accuracy to within +- 5% at the 95% confidence level. Accurate measurement of other fission and nonfission reactions is also required, but to a lesser accuracy, between +- 5% and 10% at the 95% confidence level. A secondary program objective is improvement in knowledge of the nuclear parameters involved in the standarization of fuels and materials dosimetry measurements of neutron flux, spectra, fluence and burnup.

  11. Family Poverty Affects the Rate of Human Infant Brain Growth

    PubMed Central

    Hanson, Jamie L.; Hair, Nicole; Shen, Dinggang G.; Shi, Feng; Gilmore, John H.; Wolfe, Barbara L.; Pollak, Seth D.

    2013-01-01

    Living in poverty places children at very high risk for problems across a variety of domains, including schooling, behavioral regulation, and health. Aspects of cognitive functioning, such as information processing, may underlie these kinds of problems. How might poverty affect the brain functions underlying these cognitive processes? Here, we address this question by observing and analyzing repeated measures of brain development of young children between five months and four years of age from economically diverse backgrounds (n = 77). In doing so, we have the opportunity to observe changes in brain growth as children begin to experience the effects of poverty. These children underwent MRI scanning, with subjects completing between 1 and 7 scans longitudinally. Two hundred and three MRI scans were divided into different tissue types using a novel image processing algorithm specifically designed to analyze brain data from young infants. Total gray, white, and cerebral (summation of total gray and white matter) volumes were examined along with volumes of the frontal, parietal, temporal, and occipital lobes. Infants from low-income families had lower volumes of gray matter, tissue critical for processing of information and execution of actions. These differences were found for both the frontal and parietal lobes. No differences were detected in white matter, temporal lobe volumes, or occipital lobe volumes. In addition, differences in brain growth were found to vary with socioeconomic status (SES), with children from lower-income households having slower trajectories of growth during infancy and early childhood. Volumetric differences were associated with the emergence of disruptive behavioral problems. PMID:24349025

  12. Family poverty affects the rate of human infant brain growth.

    PubMed

    Hanson, Jamie L; Hair, Nicole; Shen, Dinggang G; Shi, Feng; Gilmore, John H; Wolfe, Barbara L; Pollak, Seth D

    2013-01-01

    Living in poverty places children at very high risk for problems across a variety of domains, including schooling, behavioral regulation, and health. Aspects of cognitive functioning, such as information processing, may underlie these kinds of problems. How might poverty affect the brain functions underlying these cognitive processes? Here, we address this question by observing and analyzing repeated measures of brain development of young children between five months and four years of age from economically diverse backgrounds (n = 77). In doing so, we have the opportunity to observe changes in brain growth as children begin to experience the effects of poverty. These children underwent MRI scanning, with subjects completing between 1 and 7 scans longitudinally. Two hundred and three MRI scans were divided into different tissue types using a novel image processing algorithm specifically designed to analyze brain data from young infants. Total gray, white, and cerebral (summation of total gray and white matter) volumes were examined along with volumes of the frontal, parietal, temporal, and occipital lobes. Infants from low-income families had lower volumes of gray matter, tissue critical for processing of information and execution of actions. These differences were found for both the frontal and parietal lobes. No differences were detected in white matter, temporal lobe volumes, or occipital lobe volumes. In addition, differences in brain growth were found to vary with socioeconomic status (SES), with children from lower-income households having slower trajectories of growth during infancy and early childhood. Volumetric differences were associated with the emergence of disruptive behavioral problems. PMID:24349025

  13. Design Factors Affecting the Reaction Time for Identifying Toilet Signs: A Preliminary Study.

    PubMed

    Chen, Yi-Lang; Sie, Cai-Cin

    2016-04-01

    This study focused on the manner in which design factors affect the reaction time for identifying toilet signs. Taiwanese university students and staff members (50 men, 50 women; M age = 23.5 year, SD = 5.7) participated in the study. The 36 toilet signs were modified on three factors (six presenting styles, two figure-ground exchanges, and three colors), and the reaction time data of all participants were collected when the signs were presented in a simulation onscreen. Participants were quickest when reading Chinese text, followed by graphics and English texts. The findings also showed that men and women had different reaction times across various design combinations. These findings can serve as a reference for practically designing toilet signs, since design factors can lead to difficulties with comprehension based on reaction time measurements. PMID:27166339

  14. Controlling the emotional heart: heart rate biofeedback improves cardiac control during emotional reactions.

    PubMed

    Peira, Nathalie; Fredrikson, Mats; Pourtois, Gilles

    2014-03-01

    When regulating negative emotional reactions, one goal is to reduce physiological reactions. However, not all regulation strategies succeed in doing that. We tested whether heart rate biofeedback helped participants reduce physiological reactions in response to negative and neutral pictures. When viewing neutral pictures, participants could regulate their heart rate whether the heart rate feedback was real or not. In contrast, when viewing negative pictures, participants could regulate heart rate only when feedback was real. Ratings of task success paralleled heart rate. Participants' general level of anxiety, emotion awareness, or cognitive emotion regulation strategies did not influence the results. Our findings show that accurate online heart rate biofeedback provides an efficient way to down-regulate autonomic physiological reactions when encountering negative stimuli. PMID:24373886

  15. PEPA-1* genotype affects return rate for hatchery steelhead

    USGS Publications Warehouse

    Reisenbichler, R.R.; Hayes, M.C.; Rubin, S.P.; Wetzel, L.A.; Baker, B.M.

    2006-01-01

    Allozymes continue to be useful as genetic markers in a variety of studies; however, their utility often hinges on the selective neutrality of the allelic variation. Our study tested for neutrality between the two most common alleles (*100 and *110) at the cytosol nonspecific dipeptidase locus (PEPA-1*) in steelhead Oncorhynchus mykiss from Dworshak National Fish Hatchery in Idaho. We tested for differential growth and survival among fish with the * 100/100, *100/ 110, and *110/110 genotypes rearing in a hatchery or a natural stream. We repeated the study for two year-classes, using heterozygous (*100/110) adults to make the experimental crosses. This design avoided differences in family contribution among genotypes because each cross produced all three genotypes. We divided the progeny from each family into two groups. One group was reared in a hatchery for 1 year and then released for migration to the sea and subsequent return to the hatchery as adults. The other group was released into a natural stream and monitored for 3 years. We found no significant differences in size or survival among PEPA-1* genotypes for either the naturally reared fish or the hatchery-reared fish immediately prior to release as smolts. For females, survival to returning adult also was similar among genotypes; however, hatchery-reared males with the *110/110 genotype returned at a higher rate than did males with the *100/ 100 genotype; heterozygous males were intermediate. These results indicate that selection occurs at the PEPA-1* locus or at one or more loci tightly linked to it. The finding of nearly equal frequencies for these two alleles in the source population suggests that selection differentials among genotypes reverse or vary from year to year; otherwise, steady directional selection would drive the *100 allele to low frequencies or extinction. Locus PEPA-1* seems inappropriate for genetic marks in studies of steelhead that span the full life cycle and probably should be avoided

  16. The Gaseous Explosive Reaction : the Effect of Pressure on the Rate of Propagation of the Reaction Zone and upon the Rate of Molecular Transformation

    NASA Technical Reports Server (NTRS)

    Stevens, F W

    1932-01-01

    This study of gaseous explosive reaction has brought out a number of important fundamental characteristics of the explosive reaction indicating that the basal processes of the transformation are much simpler and corresponds more closely to the general laws and principles of ordinary transformations than is usually supposed. The report calls attention to the point that the rate of molecular transformation within the zone was found in all cases to be proportional to pressure, that the transformation within the zone is the result of binary impacts. This result is of unusual interest in the case of the reaction of heavy hydrocarbon fuels and the reaction mechanism proposed by the recent kinetic theory of chain reactions.

  17. Rate of Conditioned Reinforcement Affects Observing Rate but Not Resistance to Change

    ERIC Educational Resources Information Center

    Shahan, Timothy A.; Podlesnik, Christopher A.

    2005-01-01

    The effects of rate of conditioned reinforcement on the resistance to change of operant behavior have not been examined. In addition, the effects of rate of conditioned reinforcement on the rate of observing have not been adequately examined. In two experiments, a multiple schedule of observing-response procedures was used to examine the effects…

  18. Simulation of Transport and Reaction Using Random Walks: Reactions Without Concentrations and the Automatic Simulation of Drastically Different Thermodynamic--- Versus Diffusion---Limited Reaction Rates

    NASA Astrophysics Data System (ADS)

    Benson, D. A.; Meerschaert, M. M.

    2008-12-01

    We extend the advantages of Lagrangian random walk particle tracking (RWPT) methods that have long been used to simulate advection and dispersion in highly heterogeneous media. By formulating dissolution as a random, independent decay process, the classical continuum rate law is recovered. A novel formulation of the random precipitation process requires a consideration of the probability that two nearby particles will occupy the same differential volume in a given time period. This depends on local mixing (as by diffusion) and the total domain particle number density, which are fixed and therefore easy to calculate. The result is that the effective reaction rate follows two regimes. First, for high thermodynamic reaction probability and/or fast mixing, the classical continuum rate laws are reproduced. These are coded in the Gillespie method. This implies an exponentially fast approach to equilibrium. Second, for diffusion (mixing) limited reaction rates, equilibrium is approached much more slowly, following a power law that differs for 1-, 2-, or 3-d. At long enough times, the classical law of mass action for equilibrium reactions is reproduced, in an ensemble sense, for either rate regime. The same number of parameters for A+B ⇌ C are needed in a probabilistic versus continuum reaction simulation---one each for forward and backward probabilities that correspond to continuum thermodynamic rates. The random nature of the simulations allows for significant disequilibrium in any given region at any time that is independent of the numerical details such as time stepping or particle density. This is exemplified by nearby or intermingled groups of reactants and little or no product---a result that is often noted in the field that is difficult to reconcile with continuum methods or coarse-grained Eulerian models. Our results support both the recent experiments that show mixing-limited reactions and the results of perturbed advection-dispersion-reaction continuum models

  19. Simulation of biochemical reactions with time-dependent rates by the rejection-based algorithm

    SciTech Connect

    Thanh, Vo Hong; Priami, Corrado

    2015-08-07

    We address the problem of simulating biochemical reaction networks with time-dependent rates and propose a new algorithm based on our rejection-based stochastic simulation algorithm (RSSA) [Thanh et al., J. Chem. Phys. 141(13), 134116 (2014)]. The computation for selecting next reaction firings by our time-dependent RSSA (tRSSA) is computationally efficient. Furthermore, the generated trajectory is exact by exploiting the rejection-based mechanism. We benchmark tRSSA on different biological systems with varying forms of reaction rates to demonstrate its applicability and efficiency. We reveal that for nontrivial cases, the selection of reaction firings in existing algorithms introduces approximations because the integration of reaction rates is very computationally demanding and simplifying assumptions are introduced. The selection of the next reaction firing by our approach is easier while preserving the exactness.

  20. The effect of temperature fluctuations of reaction rate constants in turbulent reacting flows

    NASA Technical Reports Server (NTRS)

    Chinitz, W.; Antaki, P. J.; Kassar, G. M.

    1981-01-01

    Current models of turbulent reacting flows frequently use Arrhenius reaction rate constants obtained from static or laminar flow theory and/or experiments, or from best fits of static, laminar, and turbulent data. By treating the reaction rate constant as a continuous random variable which is temperature-dependent, the present study assesses the effect of turbulent temperature fluctuations on the reaction rate constant. This model requires that a probability density function (PDF) describing the nature of the fluctuations be specified. Three PDFs are examined: the clipped Gaussian, the beta PDF, and the ramp model. All the models indicate that the reaction rate constant is greater in a turbulent flow field than in an equivalent laminar flow. In addition, an amplification ratio, which is the ratio of the turbulent rate constant to the laminar rate constant, is defined and its behavior as a function of the mean temperature fluctuations is described

  1. VizieR Online Data Catalog: Brussels nuclear reaction rate library (Aikawa+, 2005)

    NASA Astrophysics Data System (ADS)

    Aikawa, M.; Arnould, M.; Goriely, S.; Jorissen, A.; Takahashi, K.

    2005-07-01

    The present data is part of the Brussels nuclear reaction rate library (BRUSLIB) for astrophysics applications and concerns nuclear reaction rate predictions calculated within the statistical Hauser-Feshbach approximation and making use of global and coherent microscopic nuclear models for the quantities (nuclear masses, nuclear structure properties, nuclear level densities, gamma-ray strength functions, optical potentials) entering the rate calculations. (4 data files).

  2. Chiral polymerization in open systems from chiral-selective reaction rates.

    PubMed

    Gleiser, Marcelo; Nelson, Bradley J; Walker, Sara Imari

    2012-08-01

    We investigate the possibility that prebiotic homochirality can be achieved exclusively through chiral-selective reaction rate parameters without any other explicit mechanism for chiral bias. Specifically, we examine an open network of polymerization reactions, where the reaction rates can have chiral-selective values. The reactions are neither autocatalytic nor do they contain explicit enantiomeric cross-inhibition terms. We are thus investigating how rare a set of chiral-selective reaction rates needs to be in order to generate a reasonable amount of chiral bias. We quantify our results adopting a statistical approach: varying both the mean value and the rms dispersion of the relevant reaction rates, we show that moderate to high levels of chiral excess can be achieved with fairly small chiral bias, below 10%. Considering the various unknowns related to prebiotic chemical networks in early Earth and the dependence of reaction rates to environmental properties such as temperature and pressure variations, we argue that homochirality could have been achieved from moderate amounts of chiral selectivity in the reaction rates. PMID:22610131

  3. A simple expression for the apparent reaction rate of large wood char gasification with steam.

    PubMed

    Umeki, Kentaro; Roh, Seon-Ah; Min, Tai-Jin; Namioka, Tomoaki; Yoshikawa, Kunio

    2010-06-01

    A simple expression for the apparent reaction rate of large wood char gasification with steam is proposed. Large char samples were gasified under steam atmosphere using a thermo-balance reactor. The apparent reaction rate was expressed as the product of the intrinsic rate and the effective factor. The effective factor was modified to include the effect of change in char diameter and intrinsic reaction rate during the reaction. Assuming uniform conversion ratio throughout a particle, the simplified reaction scheme was divided into three stages. In the initial stage, the local conversion ratio increases without particle shrinkage. In the middle stage, the particle shrinks following the shrinking core model without change in the local conversion ratio. In the final stage, the local conversion ratio increases without particle shrinkage. The validity of the modified effective value was confirmed by comparison with experimental results. PMID:20144863

  4. Determination of the Temperature Dependence of the Rate Constants for HO2/Acetonylperoxy Reaction and Acetonylperoxy Self-Reaction

    NASA Astrophysics Data System (ADS)

    Darby, E. C.; Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

    2014-12-01

    Reactions of hydroperoxy radical, HO2, with carbonyl containing RO2 can play an important role in the oxidation chemistry of the troposphere. Discovered radical product channels in addition to radical termination channels have resulted in increased study of these important reactions. In our continued study of HO2 reactions with acetonylperoxy and acetylperoxy radicals, we report here our first results on the kinetics of the acetonylperoxy system. Previous studies have resulted in conflicting results and no temperature dependence of the rate constants. Using the Infrared Kinetic Spectroscopy (IRKS) method in which a temperature-controlled slow-flow tube apparatus and laser flash photolysis of Cl2 are used to produce HO2 and CH3C(O)CH2O2 from methanol and acetone, respectively, we studied the chemical kinetics involved over the temperature range of 295 to 240 K. Rates of chemical reaction were determined by monitoring the HO2 concentration as a function of time by sensitive near-IR diode laser wavelength modulation spectroscopy while simultaneously measuring the disappearance of [CH3C(O)CH2O2] in the ultraviolet at 300 nm. The simultaneous fits resulted in the determination of the temperature dependence of the rate constants for the HO2/acetonylperoxy reaction and the acetonylperoxy self-reaction. At the lower temperatures, the reactions of HO2 and CH3C(O)CH2O2 with the adducts HO2•CH3OH and HO2•CH3C(O)CH3 formed in significant concentrations needed to be included in the fitting models.

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

    USGS Publications Warehouse

    Bahr, Jean M.; Rubin, Jacob

    1987-01-01

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

  6. Parameters affecting the microwave-specific acceleration of a chemical reaction.

    PubMed

    Chen, Po-Kai; Rosana, Michael R; Dudley, Gregory B; Stiegman, A E

    2014-08-15

    Under appropriate conditions, significant microwave-specific enhancement of the reaction rate of an organic chemical reaction can be observed. Specifically, the unimolecular Claisen rearrangement of allyl p-nitrophenyl ether (ApNE) dissolved in naphthalene was studied under microwave heating and conventional convective (thermal) heating. Under constant microwave power, reaching a temperature of 185 °C, a 4-fold rate enhancement was observed in the microwave over that using convective heating; this means that the microwave reaction was proceeding at an effective temperature of 202 °C. Conversely, under constant temperature microwave conditions (200 °C), a negligible (∼1.5-fold) microwave-specific rate enhancement was observed. The largest microwave-specific rate enhancement was observed when a series of 300 W pulses, programmed for 145-175 °C and 85-155 °C cycles, where 2- and 9-fold rate enhancements, over what would be predicted by conventional thermal heating, was observed, respectively. The postulated origins of the microwave-specific effect are purely thermal and arise from selective heating of ApNE, a microwave-absorbing reactant in a nonabsorbing solvent. Under these conditions, excess heat is accumulated in the domains around the ApNE solute so that it experiences a higher effective temperature than the measured temperature of the bulk medium, resulting in an accelerated unimolecular rearrangement. PMID:25050921

  7. Words That Fascinate the Listener: Predicting Affective Ratings of On-Line Lectures

    ERIC Educational Resources Information Center

    Weninger, Felix; Staudt, Pascal; Schuller, Björn

    2013-01-01

    In a large scale study on 843 transcripts of Technology, Entertainment and Design (TED) talks, the authors address the relation between word usage and categorical affective ratings of lectures by a large group of internet users. Users rated the lectures by assigning one or more predefined tags which relate to the affective state evoked in the…

  8. Rate Of Conditioned Reinforcement Affects Observing Rate But Not Resistance To Change

    PubMed Central

    Shahan, Timothy A; Podlesnik, Christopher A

    2005-01-01

    The effects of rate of conditioned reinforcement on the resistance to change of operant behavior have not been examined. In addition, the effects of rate of conditioned reinforcement on the rate of observing have not been adequately examined. In two experiments, a multiple schedule of observing-response procedures was used to examine the effects of rate of conditioned reinforcement on observing rates and resistance to change. In a rich component, observing responses produced a higher frequency of stimuli correlated with alternating periods of random-interval schedule primary reinforcement or extinction. In a lean component, observing responses produced similar schedule-correlated stimuli but at a lower frequency. The rate of primary reinforcement in both components was the same. In Experiment 1, a 4:1 ratio of stimulus production was arranged by the rich and lean components. In Experiment 2, the ratio of stimulus production rates was increased to 6:1. In both experiments, observing rates were higher in the rich component than in the lean component. Disruptions in observing produced by presession feeding, extinction of observing responses, and response-independent food deliveries during intercomponent intervals usually were similar in the rich and lean components. When differences in resistance to change did occur, observing tended to be more resistant to change in the lean component. If resistance to change is accepted as a more appropriate measure of response strength than absolute response rates, then the present results provide no evidence that higher rates of stimuli generally considered to function as conditioned reinforcers engender greater response strength. PMID:16156134

  9. Temperature trends for reaction rates, hydrogen generation, and partitioning of iron during experimental serpentinization of olivine

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.; Klein, Frieder; Robbins, Mark; Moskowitz, Bruce; Berquó, Thelma S.; Jöns, Niels; Bach, Wolfgang; Templeton, Alexis

    2016-05-01

    A series of laboratory experiments were conducted to examine how partitioning of Fe among solid reaction products and rates of H2 generation vary as a function of temperature during serpentinization of olivine. Individual experiments were conducted at temperatures ranging from 200 to 320 °C, with reaction times spanning a few days to over a year. The extent of reaction ranged from <1% to ∼23%. Inferred rates for serpentinization of olivine during the experiments were 50-80 times slower than older studies had reported but are consistent with more recent results, indicating that serpentinization may proceed more slowly than previously thought. Reaction products were dominated by chrysotile, brucite, and magnetite, with minor amounts of magnesite, dolomite, and iowaite. The chrysotile contained only small amounts of Fe (XFe = 0.03-0.05, with ∼25% present as ferric Fe in octahedral sites), and displayed little variation in composition with reaction temperature. Conversely, the Fe contents of brucite (XFe = 0.01-0.09) increased steadily with decreasing reaction temperature. Analysis of the reaction products indicated that the stoichiometry of the serpentinization reactions varied with temperature, but remained constant with increasing reaction progress at a given temperature. The observed distribution of Fe among the reaction products does not appear to be entirely consistent with existing equilibrium models of Fe partitioning during serpentinization, suggesting improved models that include kinetic factors or multiple reaction steps need to be developed. Rates of H2 generation increased steeply from 200 to 300 °C, but dropped off at higher temperatures. This trend in H2 generation rates is attributable to a combination of the overall rate of serpentinization reactions and increased partitioning of Fe into brucite rather than magnetite at lower temperatures. The results suggest that millimolal concentration of H2 could be attained in moderately hot hydrothermal

  10. Estimation of the prevalence and rate of acute transfusion reactions occurring in Windhoek, Namibia

    PubMed Central

    Meza, Benjamin P.L.; Lohrke, Britta; Wilkinson, Robert; Pitman, John P.; Shiraishi, Ray W.; Bock, Naomi; Lowrance, David W.; Kuehnert, Matthew J.; Mataranyika, Mary; Basavaraju, Sridhar V.

    2014-01-01

    Background Acute transfusion reactions are probably common in sub-Saharan Africa, but transfusion reaction surveillance systems have not been widely established. In 2008, the Blood Transfusion Service of Namibia implemented a national acute transfusion reaction surveillance system, but substantial under-reporting was suspected. We estimated the actual prevalence and rate of acute transfusion reactions occurring in Windhoek, Namibia. Methods The percentage of transfusion events resulting in a reported acute transfusion reaction was calculated. Actual percentage and rates of acute transfusion reactions per 1,000 transfused units were estimated by reviewing patients’ records from six hospitals, which transfuse >99% of all blood in Windhoek. Patients’ records for 1,162 transfusion events occurring between 1st January – 31st December 2011 were randomly selected. Clinical and demographic information were abstracted and Centers for Disease Control and Prevention National Healthcare Safety Network criteria were applied to categorize acute transfusion reactions1. Results From January 1 – December 31, 2011, there were 3,697 transfusion events (involving 10,338 blood units) in the selected hospitals. Eight (0.2%) acute transfusion reactions were reported to the surveillance system. Of the 1,162 transfusion events selected, medical records for 785 transfusion events were analysed, and 28 acute transfusion reactions were detected, of which only one had also been reported to the surveillance system. An estimated 3.4% (95% confidence interval [CI]: 2.3–4.4) of transfusion events in Windhoek resulted in an acute transfusion reaction, with an estimated rate of 11.5 (95% CI: 7.6–14.5) acute transfusion reactions per 1,000 transfused units. Conclusion The estimated actual rate of acute transfusion reactions is higher than the rate reported to the national haemovigilance system. Improved surveillance and interventions to reduce transfusion-related morbidity and mortality

  11. A mesoscopic reaction rate model for shock initiation of multi-component PBX explosives.

    PubMed

    Liu, Y R; Duan, Z P; Zhang, Z Y; Ou, Z C; Huang, F L

    2016-11-01

    The primary goal of this research is to develop a three-term mesoscopic reaction rate model that consists of a hot-spot ignition, a low-pressure slow burning and a high-pressure fast reaction terms for shock initiation of multi-component Plastic Bonded Explosives (PBX). Thereinto, based on the DZK hot-spot model for a single-component PBX explosive, the hot-spot ignition term as well as its reaction rate is obtained through a "mixing rule" of the explosive components; new expressions for both the low-pressure slow burning term and the high-pressure fast reaction term are also obtained by establishing the relationships between the reaction rate of the multi-component PBX explosive and that of its explosive components, based on the low-pressure slow burning term and the high-pressure fast reaction term of a mesoscopic reaction rate model. Furthermore, for verification, the new reaction rate model is incorporated into the DYNA2D code to simulate numerically the shock initiation process of the PBXC03 and the PBXC10 multi-component PBX explosives, and the numerical results of the pressure histories at different Lagrange locations in explosive are found to be in good agreements with previous experimental data. PMID:27258213

  12. The sonochemical degradation of azobenzene and related azo dyes: Rate enhancements via Fenton's reactions

    SciTech Connect

    Joseph, J.M.; Destaillats, H.; Hung, H.M.; Hoffmann, M.R.

    2000-01-20

    The sonochemical degradation of aqueous solutions of azobenzene and related azo dyes (methyl orange, o-methyl red, and p-methyl red) was performed at 500 kHz and 50 W, under air, O{sub 2}, or Ar saturation at 288 K. Reaction products and intermediates were identified by HPLC-ES-MS. Total organic carbon (TOC) was also determined as a function of reaction time. The authors propose a reaction mechanism based on the observed species and the extent and rate of TOC depletion. The effects of the dye structures and of the background gas on the sonochemical bleaching rates were also investigated. The reaction rates for o-methyl red were approximately 30--40% faster than those for the other compounds. Saturating with Ar instead of air or O{sub 2} increased the pseudo first-order rate constants for the degradation by 10%. The acceleration of the sonochemical bleaching and the mineralization process upon addition of Fe(II) was also investigated in Ar-saturated methyl orange solutions. A 3-fold increase in the reaction rate was observed at optimal Fe(II) concentrations. This kinetic effect is quantitatively accounted for by a simple kinetic model based on the reaction of Fe(II) with sonochemically produced H{sub 2}O{sub 2} (Fenton's reaction). This latter effect illustrates a simple way of achieving a substantial improvement in the efficiency of sonochemical degradation reactions.

  13. Does exposure to an artificial ULF magnetic field affect blood pressure, heart rate variability and mood?

    PubMed

    Mitsutake, Gen; Otsuka, Kuniaki; Oinuma, Sachiko; Ferguson, Ian; Cornélissen, Germaine; Wanliss, James; Halberg, Franz

    2004-10-01

    The aim of this study was to determine whether an artificial magnetic field with an amplitude and frequency equivalent to those of geomagnetic pulsations during geomagnetic storms could affect physiology and psychology. Three healthy volunteers wore anambulatory BP monitor and an ECG recorder around the clock for 12 consecutive weekends in Winnipeg, Manitoba, Canada. In a room shielded against ELF and VLF waves, they were exposed for 8 hours per week to either a 50 nT 0.0016 Hz or a sham magnetic field at one of six circadian stages. Real exposure randomly alternated with sham exposure. They provided saliva and recorded mood and reaction time every 4 hours while awake. Systolic (S) and diastolic (D) blood pressure (BP), and heart rate (HR) were recorded every 30 minutes. Spectral analysis of HR variability (HRV) was performed using the maximum entropy method and a complex demodulation method. For these variables, daily means were compared between real and sham exposure, using paired t-tests. Their circadian MESOR, amplitude, and acrophase were analyzed and summarized using single cosinor and population-mean cosinor. Circadian rhythms were demonstrated for HR, SBP, DBP for sham exposure, salivary flow rate, positive affect, vigor, and subjective alertness (p < 0.001, -0.02). One participant showed higher HR, lower LF, HF, and VLF powers, and a steeper power-law slope (p < 0.005, -0.0001) in an early night exposure to the real magnetic field, but not in other circadian stages. There was no significant difference between circadian responses to real and sham exposure in any variable at any circadian stage. PMID:15754834

  14. Evidence of reaction rate influencing cubic and hexagonal phase formation process in CdS nanocrystals

    NASA Astrophysics Data System (ADS)

    Deka, Kuldeep; Kalita, M. P. C.

    2016-05-01

    CdS nanocrystals are synthesized by co-precipitation method using 2-mercaptoethanol (ME) as capping agent. Cubic, hexagonal and their mixture are obtained by varying the ME concentration. Lower (higher) ME concentration results in cubic (hexagonal) phase. The crystallite sizes are in the range 3-7 nm. Increase in ME concentration lead to lower reaction rate between Cd2+ and S2- of the precursors, and slower reaction rate is found to favor hexagonal phase formation over the cubic one in CdS nanocrystals. Role of reaction rate in the phase formation process provides a way to synthesize CdS nanocrystals in desired crystal phase.

  15. Thermonuclear reaction rate of 18Ne(α ,p ) 21Na from Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Mohr, P.; Longland, R.; Iliadis, C.

    2014-12-01

    The 18Ne(α ,p ) 21Na reaction impacts the break-out from the hot CNO cycles to the r p process in type-I x-ray bursts. We present a revised thermonuclear reaction rate, which is based on the latest experimental data. The new rate is derived from Monte Carlo calculations, taking into account the uncertainties of all nuclear physics input quantities. In addition, we present the reaction rate uncertainty and probability density versus temperature. Our results are also consistent with estimates obtained using different indirect approaches.

  16. SISGR - In situ characterization and modeling of formation reactions under extreme heating rates in nanostructured multilayer foils

    SciTech Connect

    Hufnagel, Todd C.

    2014-06-09

    Materials subjected to extreme conditions, such as very rapid heating, behave differently than materials under more ordinary conditions. In this program we examined the effect of rapid heating on solid-state chemical reactions in metallic materials. One primary goal was to develop experimental techniques capable of observing these reactions, which can occur at heating rates in excess of one million degrees Celsius per second. One approach that we used is x-ray diffraction performed using microfocused x-ray beams and very fast x-ray detectors. A second approach is the use of a pulsed electron source for dynamic transmission electron microscopy. With these techniques we were able to observe how the heating rate affects the chemical reaction, from which we were able to discern general principles about how these reactions proceed. A second thrust of this program was to develop computational tools to help us understand and predict the reactions. From atomic-scale simulations were learned about the interdiffusion between different metals at high heating rates, and about how new crystalline phases form. A second class of computational models allow us to predict the shape of the reaction front that occurs in these materials, and to connect our understanding of interdiffusion from the atomistic simulations to measurements made in the laboratory. Both the experimental and computational techniques developed in this program are expected to be broadly applicable to a wider range of scientific problems than the intermetallic solid-state reactions studied here. For example, we have already begun using the x-ray techniques to study how materials respond to mechanical deformation at very high rates.

  17. ACTIVE: a program to calculate and plot reaction rates from ANISN calculated fluxes

    SciTech Connect

    Judd, J.L.

    1981-12-01

    The ACTIVE code calculates spatial heating rates, tritium production rates, neutron reaction rates, and energy spectra from particle fluxes calculated by ANISN. ACTIVE has a variety of input options including the capability to plot all calculated spatial distributions. The code was primarily designed for use with fusion first wall/blanket systems, but could be applied to any one-dimensional problem.

  18. Rate constants measured for hydrated electron reactions with peptides and proteins

    NASA Technical Reports Server (NTRS)

    Braams, R.

    1968-01-01

    Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

  19. Out of the frying pan, into the fire: mixed affective reactions to social proximity in borderline and avoidant personality disorders in daily life.

    PubMed

    Gadassi, Reuma; Snir, Avigal; Berenson, Kathy; Downey, Geraldine; Rafaeli, Eshkol

    2014-08-01

    Social proximity typically helps individuals meet their belongingness needs, but several forms of psychopathology, including borderline and avoidant personality disorders (BPD and APD, respectively) are characterized by social difficulties. This experience-sampling study is one of the first to directly investigate the affective reactions of individuals with BPD and APD (compared with healthy controls [HC]) to social proximity in daily life. We examined both person-level and day-level reactions. At the person level, the rate of social proximity across the diary period was associated with diminished feelings of rejection, isolation, shame, and dissociation in the HC group. In contrast, it was not associated with any affective reaction in the BPD group, and was associated with decreased rejection and isolation on the one hand, but also with increased anxiety in the APD group. At the day level, we used multilevel regression to examine affective reactions when in social proximity. The HC group showed a consistent benefit when in social proximity. In contrast, both PD groups exhibited mixed affective reactions to social proximity; specifically, benefits (increased positive affect, decreased rejection, isolation, and dissociation) were interspersed with costs (increased shame for both PD groups; increased anger for BPD; increased anxiety for APD). The mixed reactions found in both PDs may contribute to the disturbed relationships of individuals with these disorders. PMID:24933280

  20. The Impact of the Uncertainties in the 12C(α,γ)16O Reaction Rate on the Asteroseismology of ZZ Ceti Stars: First Results

    NASA Astrophysics Data System (ADS)

    De Gerónimo, Francisco C.; Córsico, Alejandro H.; Althaus, Leandro G.; Romero, Alejandra D.

    2015-06-01

    We assess for the first time the impact that the uncertainties affecting the 12C(α,γ)16O reaction rate have on the asteroseismological inferences of ZZ Ceti stars. For our adopted test-case, the well studied DAV star G117-B15A, we found that the incomplete knowledge of the 12C(α,γ)16O nuclear reaction rate results in a moderate dispersion of the structural parameters of the asteroseismological model.

  1. Narrative Centrality and Negative Affectivity: Independent and Interactive Contributors to Stress Reactions

    PubMed Central

    Rubin, David C.; Boals, Adriel; Hoyle, Rick H.

    2014-01-01

    Reactions to stressful negative events have long been studied using approaches based on either the narrative interpretation of the event or the traits of the individual. Here, we integrate these two approaches by using individual differences measures of both the narrative interpretation of the stressful event as central to one’s life and the personality characteristic of negative affectivity. We show that they each have independent contributions to stress reactions, and that high levels on both produce greater than additive effects. The effects on posttraumatic stress symptoms are substantial for both undergraduates (Study 1, n = 2,296; Study 3, n = 488) and veterans (Study 2, n = 104), with mean levels for participants low on both measures near floor on posttraumatic stress symptoms and those high on both measures scoring at or above diagnostic thresholds. Study 3 included three measures of narrative centrality and three of negative affectivity to demonstrate that the effects were not limited to a single measure. In Study 4 (n = 987), measures associated with symptoms of posttraumatic stress correlated substantially with either with measures of narrative centrality or measures of negative affectivity. The concepts of narrative centrality and negative affectivity and the results are consistent with findings from clinical populations using similar measures and with current approaches to therapy. In broad non-clinical populations, such as those used here, the results suggest that we might be able to substantially increase our ability to account for the severity of stress response by including both concepts. PMID:24294867

  2. A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reaction flows

    NASA Technical Reports Server (NTRS)

    Magnotti, F.; Diskin, G.; Matulaitis, J.; Chinitz, W.

    1984-01-01

    The use of silane (SiH4) as an effective ignitor and flame stabilizing pilot fuel is well documented. A reliable chemical kinetic mechanism for prediction of its behavior at the conditions encountered in the combustor of a SCRAMJET engine was calculated. The effects of hydrogen addition on hydrocarbon ignition and flame stabilization as a means for reduction of lengthy ignition delays and reaction times were studied. The ranges of applicability of chemical kinetic models of hydrogen-air combustors were also investigated. The CHARNAL computer code was applied to the turbulent reaction rate modeling.

  3. Comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reaction flows

    SciTech Connect

    Magnotti, F.; Diskin, G.; Matulaitis, J.; Chinitz, W.

    1984-01-01

    The use of silane (SiH4) as an effective ignitor and flame stabilizing pilot fuel is well documented. A reliable chemical kinetic mechanism for prediction of its behavior at the conditions encountered in the combustor of a SCRAMJET engine was calculated. The effects of hydrogen addition on hydrocarbon ignition and flame stabilization as a means for reduction of lengthy ignition delays and reaction times were studied. The ranges of applicability of chemical kinetic models of hydrogen-air combustors were also investigated. The CHARNAL computer code was applied to the turbulent reaction rate modeling.

  4. Astrophysical S-Factors and Reaction Rates of Threshold (p, n)-Reactions on {sup 99-102}Ru

    SciTech Connect

    Skakun, Ye.; Rauscher, T.

    2010-08-12

    Astrophysical S-factors of (p, n) reactions on {sup 99}Ru, {sup 100}Ru, {sup 101}Ru, and {sup 102}Ru were derived from the sum of experimental isomeric and ground states cross sections measured in the incident proton energy range of 5-9 MeV. They were compared with Hauser-Feshbach statistical model predictions of the NON-SMOKER code. Good agreement was found in the majority of cases. Reaction rates were derived up to 8.7 GK stellar temperature by combining experiment and theory.

  5. Nonequilibrium Contribution to the Rate of Reaction. III. Isothermal Multicomponent Systems

    DOE R&D Accomplishments Database

    Shizgal, B.; Karplus, M.

    1970-10-01

    The nonequilibrium contribution to the reaction rate of an isothermal multicomponent system is obtained by solution of the appropriate Chapman-Enskog equation; the system is composed of reactive species in contact with a heat bath of inert atoms M.

  6. Determining astrophysical three-body radiative capture reaction rates from inclusive Coulomb break-up measurements

    NASA Astrophysics Data System (ADS)

    Casal, J.; Rodríguez-Gallardo, M.; Arias, J. M.; Gómez-Camacho, J.

    2016-04-01

    A relationship between the Coulomb inclusive break-up probability and the radiative capture reaction rate for weakly bound three-body systems is established. This direct link provides a robust procedure to estimate the reaction rate for nuclei of astrophysical interest by measuring inclusive break-up processes at different energies and angles. This might be an advantageous alternative to the determination of reaction rates from the measurement of B (E 1 ) distributions through exclusive Coulomb break-up experiments. In addition, it provides a reference to assess the validity of different theoretical approaches that have been used to calculate reaction rates. The procedure is applied to 11Li (9Li+n +n ) and 6He (4He+n +n ) three-body systems for which some data exist.

  7. Anticipatory Heart Rate Deceleration and Reaction Time in Children with and without Referral for Learning Disability

    ERIC Educational Resources Information Center

    Sroufe, L. Alan; And Others

    1973-01-01

    The finding of major significance in this study concerns the effect of stimulant drug medication on the relationship between heart rate deceleration and reaction time with the clinic children. (Authors)

  8. Reaction mechanisms and rate constants of waste degradation in landfill bioreactor systems with enzymatic-enhancement.

    PubMed

    Jayasinghe, P A; Hettiaratchi, J P A; Mehrotra, A K; Kumar, S

    2014-06-01

    Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day. PMID:24759644

  9. Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

    DOEpatents

    Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Wegeng, Robert S [Richland, WA; Gao, Yufei [Kennewick, WA

    2003-04-01

    The present invention is a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber substantially matching a local heat transfer rate of a catalytic thermal chemical reaction. The key to the invention is a thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from the reaction chamber to the heat transfer chamber substantially matches the local heat transfer rate.

  10. Let's not be indifferent about neutrality: Neutral ratings in the International Affective Picture System (IAPS) mask mixed affective responses.

    PubMed

    Schneider, Iris K; Veenstra, Lotte; van Harreveld, Frenk; Schwarz, Norbert; Koole, Sander L

    2016-06-01

    The International Affective Picture System (IAPS) is a picture set used by researchers to select pictures that have been prerated on valence. Researchers rely on the ratings in the IAPS to accurately reflect the degree to which the pictures elicit affective responses. Here we show that this may not always be a safe assumption. More specifically, the scale used to measure valence in the IAPS ranges from positive to negative, implying that positive and negative feelings are end-points of the same construct. This makes interpretation of midpoint, or neutral ratings, especially problematic because it is impossible to tell whether these ratings are the result of neutral, or of mixed feelings. In other words, neutral ratings may not be as neutral as researchers assume them to be. Investigating this, in this work we show that pictures that seem neutral according to the valence ratings in the IAPS indeed vary in levels of ambivalence they elicit. Furthermore, the experience of ambivalence in response to these pictures is predictive of the arousal that people report feeling when viewing these pictures. These findings are of particular importance because neutrality differs from ambivalence in its specific psychological consequences, and by relying on seemingly neutral valance ratings, researchers may unwillingly introduce these consequences into their research design, undermining their level of experimental control. (PsycINFO Database Record PMID:26950363

  11. The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

    SciTech Connect

    Maher, K.; Steefel, C. I.; White, A.F.; Stonestrom, D.A.

    2009-02-25

    In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisser and [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO{sub 2}(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total

  12. A Unified Equation for the Reaction Rate in Dense Matter Stars

    SciTech Connect

    Gasques, L. R.; Wiescher, M.; Yakovlev, D. G.

    2007-10-26

    We analyze thermonuclear and pycnonuclear reaction rates in multi-component dense stellar plasma. First we describe calculations of the astrophysical S-factor at low energies using the Sao Paulo potential on the basis of the barrier penetration model. Then we present a simple phenomenological expression for a reaction rate. The expression contains several fit parameters which we adjust to reproduce the best microscopic calculations available in the literature.

  13. Shell and explosive hydrogen burning. Nuclear reaction rates for hydrogen burning in RGB, AGB and Novae

    NASA Astrophysics Data System (ADS)

    Boeltzig, A.; Bruno, C. G.; Cavanna, F.; Cristallo, S.; Davinson, T.; Depalo, R.; deBoer, R. J.; Di Leva, A.; Ferraro, F.; Imbriani, G.; Marigo, P.; Terrasi, F.; Wiescher, M.

    2016-04-01

    The nucleosynthesis of light elements, from helium up to silicon, mainly occurs in Red Giant and Asymptotic Giant Branch stars and Novae. The relative abundances of the synthesized nuclides critically depend on the rates of the nuclear processes involved, often through non-trivial reaction chains, combined with complex mixing mechanisms. In this paper, we summarize the contributions made by LUNA experiments in furthering our understanding of nuclear reaction rates necessary for modeling nucleosynthesis in AGB stars and Novae explosions.

  14. Analysis of turbulent free-jet hydrogen-air diffusion flames with finite chemical reaction rates

    NASA Technical Reports Server (NTRS)

    Sislian, J. P.; Glass, I. I.; Evans, J. S.

    1979-01-01

    A numerical analysis is presented of the nonequilibrium flow field resulting from the turbulent mixing and combustion of an axisymmetric hydrogen jet in a supersonic parallel ambient air stream. The effective turbulent transport properties are determined by means of a two-equation model of turbulence. The finite-rate chemistry model considers eight elementary reactions among six chemical species: H, O, H2O, OH, O2 and H2. The governing set of nonlinear partial differential equations was solved by using an implicit finite-difference procedure. Radial distributions were obtained at two downstream locations for some important variables affecting the flow development, such as the turbulent kinetic energy and its dissipation rate. The results show that these variables attain their peak values on the axis of symmetry. The computed distribution of velocity, temperature, and mass fractions of the chemical species gives a complete description of the flow field. The numerical predictions were compared with two sets of experimental data. Good qualitative agreement was obtained.

  15. Emotions over time: synchronicity and development of subjective, physiological, and facial affective reactions to music.

    PubMed

    Grewe, Oliver; Nagel, Frederik; Kopiez, Reinhard; Altenmüller, Eckart

    2007-11-01

    Most people are able to identify basic emotions expressed in music and experience affective reactions to music. But does music generally induce emotion? Does it elicit subjective feelings, physiological arousal, and motor reactions reliably in different individuals? In this interdisciplinary study, measurement of skin conductance, facial muscle activity, and self-monitoring were synchronized with musical stimuli. A group of 38 participants listened to classical, rock, and pop music and reported their feelings in a two-dimensional emotion space during listening. The first entrance of a solo voice or choir and the beginning of new sections were found to elicit interindividual changes in subjective feelings and physiological arousal. Quincy Jones' "Bossa Nova" motivated movement and laughing in more than half of the participants. Bodily reactions such as "goose bumps" and "shivers" could be stimulated by the "Tuba Mirum" from Mozart's Requiem in 7 of 38 participants. In addition, the authors repeated the experiment seven times with one participant to examine intraindividual stability of effects. This exploratory combination of approaches throws a new light on the astonishing complexity of affective music listening. PMID:18039047

  16. Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

    SciTech Connect

    Lindquist, W Brent

    2009-03-03

    The overall goal of the project was to bridge the gap between our knowledge of small-scale geochemical reaction rates and reaction rates meaningful for modeling transport at core scales. The working hypothesis was that reaction rates, determined from laboratory measurements based upon reactions typically conducted in well mixed batch reactors using pulverized reactive media may be significantly changed in in situ porous media flow due to rock microstructure heterogeneity. Specifically we hypothesized that, generally, reactive mineral surfaces are not uniformly accessible to reactive fluids due to the random deposition of mineral grains and to the variation in flow rates within a pore network. Expected bulk reaction rates would therefore have to be correctly up-scaled to reflect such heterogeneity. The specific objective was to develop a computational tool that integrates existing measurement capabilities with pore-scale network models of fluid flow and reactive transport. The existing measurement capabilities to be integrated consisted of (a) pore space morphology, (b) rock mineralogy, and (c) geochemical reaction rates. The objective was accomplished by: (1) characterizing sedimentary sandstone rock morphology using X-ray computed microtomography, (2) mapping rock mineralogy using back-scattered electron microscopy (BSE), X-ray dispersive spectroscopy (EDX) and CMT, (3) characterizing pore-accessible reactive mineral surface area, and (4) creating network models to model acidic CO{sub 2} saturated brine injection into the sandstone rock samples.

  17. Thick target measurement of the 40Ca(alpha,gamma)44Ti reaction rate

    SciTech Connect

    Sheets, S A; Burke, J T; Scielzo, N D; Phair, L; Bleuel, D; Norman, E B; Grant, P G; Hurst, A M; Tumey, S; Brown, T A; Stoyer, M

    2009-02-06

    The thick-target yield for the {sup 40}Ca({alpha},{gamma}){sup 44}Ti reaction has been measured for E{sub beam} = 4.13, 4.54, and 5.36 MeV using both an activation measurement and online {gamma}-ray spectroscopy. The results of the two measurements agree. From the measured yield a reaction rate is deduced that is smaller than statistical model calculations. This implies a smaller {sup 44}Ti production in supernova compared to recently measured {sup 40}Ca({alpha},{gamma}){sup 44}Ti reaction rates.

  18. Rate coefficients from quantum and quasi-classical cumulative reaction probabilities for the S(1D) + H2 reaction

    NASA Astrophysics Data System (ADS)

    Jambrina, P. G.; Lara, Manuel; Menéndez, M.; Launay, J.-M.; Aoiz, F. J.

    2012-10-01

    Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S(1D) + H2 → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories (SQCT). The calculations have been carried out on the widely used potential energy surface (PES) by Ho et al. [J. Chem. Phys. 116, 4124 (2002), 10.1063/1.1431280] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009), 10.1021/jp903790h]. The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S(1D).

  19. High-precision (p,t) reaction to determine {sup 25}Al(p,{gamma}){sup 26}Si reaction rates

    SciTech Connect

    Matic, A.; Berg, A. M. van den; Harakeh, M. N.; Woertche, H. J.; Berg, G. P. A.; Couder, M.; Goerres, J.; LeBlanc, P.; O'Brien, S.; Wiescher, M.; Fujita, K.; Hatanaka, K.; Sakemi, Y.; Shimizu, Y.; Tameshige, Y.; Tamii, A.; Yosoi, M.; Adachi, T.; Fujita, Y.; Shimbara, Y.

    2010-08-15

    Since the identification of ongoing {sup 26}Al production in the universe, the reaction sequence {sup 24}Mg(p,{gamma}){sup 25}Al({beta}{sup +{nu}}){sup 25}Mg(p,{gamma}){sup 26}Al has been studied intensively. At temperatures where the radiative capture on {sup 25}Al (t{sub 1/2}=7.2 s) becomes faster than the {beta}{sup +} decay, the production of {sup 26}Al can be reduced due to the depletion of {sup 25}Al. To determine the resonances relevant for the {sup 25}Al(p,{gamma}){sup 26}Si bypass reaction, we measured the {sup 28}Si(p,t){sup 26}Si reaction with high-energy precision using the Grand Raiden spectrometer at the Research Center for Nuclear Physics, Osaka. Several new energy levels were found above the p threshold and for known states excitation energies were determined with smaller uncertainties. The calculated stellar rates of the bypass reaction agree well with previous results, suggesting that these rates are well established.

  20. Rate constants of reactions of bromine with phenols in aqueous solution.

    PubMed

    Gallard, Hervé; Pellizzari, Fabien; Croué, Jean Philippe; Legube, B

    2003-07-01

    The kinetics of bromination of six ortho- and para-substituted phenols was investigated between pH 5 and pH 12 in aqueous solution. Kinetics was followed with a continuous-flow reactor previously validated by studying the fast reaction between chlorine and ammonia. The overall reaction rate between bromine and phenols is controlled by the reaction of HOBr with the phenoxide ion between pH 6 and pH 10. The reaction of HOBr with the undissociated phenols and the reaction of BrO(-) with the phenoxide ions become only significant for pH<6 and pH>10, respectively. The second-order rate constants for the reaction of HOBr with phenoxide ions vary between 1.4(+/-0.1)x10(3) and 2.1(+/-0.5)x10(8)M(-1)s(-1) for 2,4,6-trichlorophenol and 4-methylphenol, respectively. Hammett-type correlation was obtained for the reaction of HOBr with the phenoxide ions (log(k)=8.0-3.33 x Sigmasigma) and was compared with Hammett-type correlations of HOCl and HOI. The reaction rate of bromine with phenol-like organic compounds was estimated to be about 10(3)-fold higher than with chlorine and 10(3)-fold lower than with ozone in drinking water treatment conditions. PMID:12767291

  1. Recent Augmentations of the Functionality of the Thermonuclear Reaction Rate Calculator (TReRaC)

    NASA Astrophysics Data System (ADS)

    Thomsen, Kyle; Smith, Michael

    2011-10-01

    The chemical variety of our universe can be explained by stellar nucleosynthesis. Many thermonuclear reactions are studied by reproducing them in accelerator experiments and determining their rates. Using the codes available through the Computational Infrastructure for Nuclear Astrophysics (CINA), researchers can process the results of these experiments. One such program is the Thermonuclear Reaction Rate Calculator (TReRaC), which uses various experimental inputs including resonant energies, strengths, channel widths, and information on non-resonant contributions to calculate reaction rates. Presently, TReRaC is capable of quickly generating accurate rates which closely match those given in a number of publications. This adds to CINA capabilities by enabling a wider variety of nuclear information to generate rates. The next step in TReRaC's evolution is integration into the existing CINA complex so that it can be used by researchers worldwide.

  2. Genetic polymorphisms affect efficacy and adverse drug reactions of DMARDs in rheumatoid arthritis.

    PubMed

    Zhang, Ling Ling; Yang, Sen; Wei, Wei; Zhang, Xue Jun

    2014-11-01

    Disease-modifying antirheumatic drugs (DMARDs) and biological agents are critical in preventing the severe complications of rheumatoid arthritis (RA). However, the outcome of treatment with these drugs in RA patients is quite variable and unpredictable. Drug-metabolizing enzymes (dihydrofolate reductase, cytochrome P450 enzymes, N-acetyltransferases, etc.), drug transporters (ATP-binding cassette transporters), and drug targets (tumor necrosis factor-α receptors) are coded for by variant alleles. These gene polymorphisms may influence the pharmacokinetics, pharmacodynamics, and side effects of medicines. The cause for differences in efficacy and adverse drug reactions may be genetic variation in drug metabolism among individuals. Polymorphisms in drug transporter genes may change the distribution and excretion of medicines, and the sensitivity of the targets to drugs is strongly influenced by genetic variations. In this article, we review the genetic polymorphisms that affect the efficacy of DMARDs or the occurrence of adverse drug reactions associated with DMARDs in RA. PMID:25144752

  3. The Trauma of Peer Abuse: Effects of Relational Peer Victimization and Social Anxiety Disorder on Physiological and Affective Reactions to Social Exclusion

    PubMed Central

    Iffland, Benjamin; Sansen, Lisa Margareta; Catani, Claudia; Neuner, Frank

    2014-01-01

    Background: Social exclusion elicits emotional distress, negative mood, and physiological stress. Recent studies showed that these effects were more intense and persisting in socially anxious subjects. The present study examined whether the abnormal reactions of socially anxious subjects can be traced back to previous experiences of relational peer victimization during childhood and adolescence. Methods: Participants (N = 74) were patients with a diagnosis of social anxiety disorder as well as healthy controls. The patient and control groups were subdivided into two subgroups according to the subject’s reports about previous relational peer victimization. Immediate and delayed physiological (skin conductance level and heart rate) and affective reactions to a simulated social exclusion in a ball-toss game (Cyberball) were recorded. Results: Overall, subjects’ immediate reactions to social exclusion were an increase in skin conductance and a reduction of positive affect. Regardless of the diagnostic status, subjects with a history of relational peer victimization showed a more intense self-reported affective change that was accompanied by a blunted skin conductance response. However, the mood of the subjects with a history of peer victimization recovered during a 15 min waiting period. A diagnosis of social anxiety disorder did not affect the reactions to social exclusion on any measure. Conclusion: Findings indicate that stress reactions to social exclusion depend more on previous experiences of peer victimization than on a diagnosis of social anxiety disorder. The findings indicate that memories of negative social experiences can determine the initial stress reaction to social threats. PMID:24672491

  4. Reaction Rates of Semi-Volatile Organic Compounds with the Hydroxyl Radical.

    NASA Astrophysics Data System (ADS)

    Anderson, Philip Neal

    1995-01-01

    The atmosphere is the primary route of global dispersion of many semi-volatile organic compounds (SOCs), including polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans. While the long-distance atmospheric transport of these compounds has been well established, the importance of chemical reactions that may occur while SOCs are in the atmosphere is largely unknown. For most semi-volatile organic compounds in the vapor phase, the most significant atmospheric reaction is likely to be attack by the hydroxyl radical (OH). The importance of this removal pathway, relative to other loss mechanisms from the atmosphere, is dependent on the reaction rate of a given semi-volatile organic compound with OH. A system was constructed and validated to measure the reaction rate of OH with semi-volatile organic compounds in the laboratory. The system featured a small, heated, quartz chamber with on-line detection of reactants by mass spectrometry. OH radicals were generated by the 254 nm photolysis of O _3 in the presence of H_2 O. The temperature dependent reaction rates of OH with 15 polychlorinated biphenyl congeners (PCBs), containing 0-5 chlorines, were measured. Calculated atmospheric lifetimes of PCBs due to OH-initiated reactions ranged from 2 days for biphenyl to 34 days for a pentachlorobiphenyl. Using an average of reaction rates extrapolated to atmospheric temperatures, the lifetime in the atmosphere for total PCBs due to OH reaction was calculated. A model for the vertical concentration gradient of PCBs in the troposphere was developed and used to calculate the flux (16 mug m^{-2} yr^{-1}) and total global flow (8,300 tonnes yr^{-1}) of PCBs removed from the atmosphere by OH-PCB reaction. This pathway is very large in comparison to any other known permanent PCB loss processes from the environment, such as deep ocean sediment burial (240 tonnes yr^ {-1}). The reaction of PCBs with OH may be the dominant removal mechanism of PCBs from the natural environment.

  5. STARLIB: A Next-generation Reaction-rate Library for Nuclear Astrophysics

    NASA Astrophysics Data System (ADS)

    Sallaska, A. L.; Iliadis, C.; Champange, A. E.; Goriely, S.; Starrfield, S.; Timmes, F. X.

    2013-07-01

    STARLIB is a next-generation, all-purpose nuclear reaction-rate library. For the first time, this library provides the rate probability density at all temperature grid points for convenient implementation in models of stellar phenomena. The recommended rate and its associated uncertainties are also included. Currently, uncertainties are absent from all other rate libraries, and, although estimates have been attempted in previous evaluations and compilations, these are generally not based on rigorous statistical definitions. A common standard for deriving uncertainties is clearly warranted. STARLIB represents a first step in addressing this deficiency by providing a tabular, up-to-date database that supplies not only the rate and its uncertainty but also its distribution. Because a majority of rates are lognormally distributed, this allows the construction of rate probability densities from the columns of STARLIB. This structure is based on a recently suggested Monte Carlo method to calculate reaction rates, where uncertainties are rigorously defined. In STARLIB, experimental rates are supplemented with: (1) theoretical TALYS rates for reactions for which no experimental input is available, and (2) laboratory and theoretical weak rates. STARLIB includes all types of reactions of astrophysical interest to Z = 83, such as (p, γ), (p, α), (α, n), and corresponding reverse rates. Strong rates account for thermal target excitations. Here, we summarize our Monte Carlo formalism, introduce the library, compare methods of correcting rates for stellar environments, and discuss how to implement our library in Monte Carlo nucleosynthesis studies. We also present a method for accessing STARLIB on the Internet and outline updated Monte Carlo-based rates.

  6. Reaction rate and composition dependence of the stability of thermonuclear burning on accreting neutron stars

    SciTech Connect

    Keek, L.; Cyburt, R. H.; Heger, A.

    2014-06-01

    The stability of thermonuclear burning of hydrogen and helium accreted onto neutron stars is strongly dependent on the mass accretion rate. The burning behavior is observed to change from Type I X-ray bursts to stable burning, with oscillatory burning occurring at the transition. Simulations predict the transition at a 10 times higher mass accretion rate than observed. Using numerical models we investigate how the transition depends on the hydrogen, helium, and CNO mass fractions of the accreted material, as well as on the nuclear reaction rates of 3α and the hot-CNO breakout reactions {sup 15}O(α, γ){sup 19}Ne and {sup 18}Ne(α, p){sup 21}Na. For a lower hydrogen content the transition is at higher accretion rates. Furthermore, most experimentally allowed reaction rate variations change the transition accretion rate by at most 10%. A factor 10 decrease of the {sup 15}O(α, γ){sup 19}Ne rate, however, produces an increase of the transition accretion rate of 35%. None of our models reproduce the transition at the observed rate, and depending on the true {sup 15}O(α, γ){sup 19}Ne reaction rate, the actual discrepancy may be substantially larger. We find that the width of the interval of accretion rates with marginally stable burning depends strongly on both composition and reaction rates. Furthermore, close to the stability transition, our models predict that X-ray bursts have extended tails where freshly accreted fuel prolongs nuclear burning.

  7. Oxidation rate of iron sulfides as affected by surface area, morphology, oxygen concentration and autotrophic bacteria

    SciTech Connect

    Pugh, C.E.

    1984-05-01

    The relationship between surface area and rate of oxidation of Fe sulphides (pyrite and marcasite) separated from Texas lignite was studied. The reaction kinetics with respect to Fe sulphide morphology and particle size were evaluated. The oxygen concentration and the presence of autotrophic Fe and S-oxidizing bacteria (thiobacillus ferro-oxidans) on the rate of oxidation were also evaluated. The formation of sulphate from Fe sulphide was selected to measure the rate of oxidation. Relative reaction rates for different morphological forms of Fe sulphide were: marcasite > framboidal pyrite > massive pyrite. As the surface area of pyrite doubled, reaction rate increased by a factor of 1.5. Sulphate production for the 5 to 2 ..mu..m fraction was twice that of the 50 to 20 ..mu..m fraction. Reaction rate was approximately fivefold greater for non-inoculated treatments at 20% O/sub 2/ compared with 0% O/sub 2/ and was approximately ninefold greater for the same treatment inoculated with T. ferro-oxidans.

  8. Relationship between obesity, negative affect and basal heart rate in predicting heart rate reactivity to psychological stress among adolescents

    PubMed Central

    Park, Andres E.; Huynh, Pauline; Schell, Anne M.; Baker, Laura A.

    2015-01-01

    Reduced cardiovascular responses to psychological stressors have been found to be associated with both obesity and negative affect in adults, but have been less well studied in children and adolescent populations. These findings have most often been interpreted as reflecting reduced sympathetic nervous system response, perhaps associated with heightened baseline sympathetic activation among the obese and those manifesting negative affect. However, obesity and negative affect may themselves be correlated, raising the question of whether they both independently affect cardiovascular reactivity. The present study thus examined the separate effects of obesity and negative affect on both cardiovascular and skin conductance responses to stress (e.g., during a serial subtraction math task) in adolescents, while controlling for baseline levels of autonomic activity during rest. Both obesity and negative affect had independent and negative associations with cardiovascular reactivity, such that reduced stress responses were apparent for obese adolescents and those with high levels of negative affect. In contrast, neither obesity nor negative affect was related to skin conductance responses to stress, implicating specifically noradrenergic mechanisms rather than sympathetic mechanisms generally as being deficient. Moreover, baseline heart rate was unrelated to obesity in this sample, which suggests that heightened baseline of sympathetic activity is not necessary for the reduced cardiovascular reactivity to stress. PMID:26049136

  9. Temperature-dependent reaction-rate expression for oxygen recombination at Shuttle entry conditions

    NASA Technical Reports Server (NTRS)

    Zoby, E. V.; Simmonds, A. L.; Gupta, R. N.

    1984-01-01

    A temperature-dependent oxygen surface reaction-rate coefficient has been determined from experimental STS-2 heating and wall temperature data at altitudes of 77.91 km, 74.98 km, and 71.29 km. The coefficient is presented in an Arrhenius form and is shown to be less temperature dependent than previous results. Finite-rate viscous-shock-layer heating rates based on this present expression have been compared with predicted heating rates using the previous rate coefficients and with experimental heating data obtained over an extensive range of STS-2 and STS-3 entry conditions. A substantial improvement is obtained in comparison of experimental data and predicted heating rates using the present oxygen reaction-rate expression.

  10. Estimation of the reaction rate constant of HOCl by SMILES observation

    NASA Astrophysics Data System (ADS)

    Kuribayashi, Kouta; Kasai, Yasuko; Sato, Tomohiro; Sagawa, Hideo

    2012-07-01

    Hypochlorous acid, HOCl plays an important role to link the odd ClOx and the odd HOx in the atmospheric chemistry with the reaction: {ClO} + {HO_{2}} \\longrightarrow {HOCl} + {O_{2}} Quantitative understanding of the rate constant of the reaction (1.1) is essential for understanding the ozone loss in the mid-latitude region because of a view point of its rate controlling role in the ozone depletion chemistry. Reassessment of the reaction rate constant was pointed out from MIPAS/Envisat observations (von Clarmann et al., 2011) and balloon-borne observations (Kovalenko et al., 2007). Several laboratory studies had been reported, although the reaction rate constants have large uncertainties, as k{_{HOCl}} = (1.75 ± 0.52) × 10^{-12} exp[(368 ± 78)/T] (Hickson et al., 2007), and large discrepancies (Hickson et al., 2007;Stimpfle et al., 1979). Moreover, theoretical ab initio studies pointed out the pressure dependence of the reaction (1.1) (Xu et al., 2003). A new high-sensitive remote sensing technology named Superconducting SubMillimeter-wave Limb-Emission Sounder (SMILES) on the International Space Station (ISS) had observed diurnal variations of HOCl in the upper stratosphere/lower mesosphere (US/LM) region for the first time. ClO and HO_{2} were slso observed simultaneously with HOCl. SMILES performed the observations between 12^{{th}} October 2009 and 21^{{th}} April 2010. The latitude coverage of SMILES observation is normally 38°S-65°N. The altitude region of HOCl observation is about 28-70 km. We estimated the time period in which the reaction (1.1) becomes dominant in the ClO_{y} diurnal chemistry in US/LM. The reaction rate constant was directly estimated by decay of [ClO] and [HO_{2}] amounts in that period. The derived reaction rate constant represented well the increase of [HOCl] amount.

  11. [Incidence rate of adverse reaction/event by Qingkailing injection: a Meta-analysis of single rate].

    PubMed

    Ai, Chun-ling; Xie, Yan-ming; Li, Ming-quan; Wang, Lian-xin; Liao, Xing

    2015-12-01

    To systematically review the incidence rate of adverse drug reaction/event by Qingkailing injection. Such databases as the PubMed, EMbase, the Cochrane library, CNKI, VIP WanFang data and CBM were searched by computer from foundation to July 30, 2015. Two reviewers independently screened literature according to the inclusion and exclusion criteria, extracted data and cross check data. Then, Meta-analysis was performed by using the R 3.2.0 software, subgroup sensitivity analysis was performed based on age, mode of medicine, observation time and research quality. Sixty-three studies involving 9,793 patients with Qingkailing injection were included, 367 cases of adverse reactions/events were reported in total. The incidence rate of adverse reaction in skin and mucosa group was 2% [95% CI (0.02; 0.03)]; the digestive system adverse reaction was 6% [95% CI(0.05; 0.07); the injection site adverse reaction was 4% [95% CI (0.02; 0.07)]. In the digestive system as the main types of adverse reactions/events, incidence of children and adults were 4.6% [0.021 1; 0.097 7] and 6.9% [0.053 5; 0.089 8], respectively. Adverse reactions to skin and mucous membrane damage as the main performance/event type, the observation time > 7 days and ≤ 7 days incidence of 3% [0.012 9; 0.068 3] and 1.9% [0.007 8; 0.046 1], respectively. Subgroup analysis showed that different types of adverse reactions, combination in the incidence of adverse reactions/events were higher than that of single drug, the difference was statistically significant (P < 0.05). This study suggested the influence factors of adverse reactions occur, and clinical rational drug use, such as combination, age and other fators, and the influence factors vary in different populations. Therefore, clinical doctors for children and the elderly use special care was required for a clear and open spirit injection, the implementation of individualized medication. PMID:27245021

  12. REACLIB: A Reaction Rate Library for the Era of Collaborative Science

    NASA Astrophysics Data System (ADS)

    Meisel, Zachary

    2008-10-01

    Thermonuclear reaction rates and weak decay rates are of great importance to modern nuclear astrophysics. They are critical in the study of many topics such as Big Bang Nucleosynthesis, X-ray bursts, Supernovae, and S-process element formation, among others. The Joint Institute for Nuclear Astrophysics (JINA) has been created to increase connectivity amongst nuclear astrophysicists in our modern age of highly collaborative science. Within JINA there has been an effort to create a frequently updated and readily accessible database of thermonuclear reactions and weak decay rates. This database is the REACLIB library, which can be accessed at the web address: http://www.nscl.msu.edu/˜nero/db/. Here I will discuss the JINA REACLIB Project, including a new procedure to fit reaction rates as a function of temperature that takes full advantage of physicality. With these updated reaction rates, astrophysical modelers will no longer have to worry about the adverse effects of using obsolete reaction rate libraries lacking physical behavior.

  13. EFFECTS OF RING STRAIN ON GAS-PHASE RATE CONSTANTS. 2. OH RADICAL REACTIONS WITH CYCLOALKENES

    EPA Science Inventory

    Relative rate constants for the gas phase reactions of OH radicals with a series of cycloalkenes have been determined at 298 + or - 2 K, using methyl nitrite photolysis in air as a source of OH radicals. The data show that the rate constants for the nonconjugated cycloalkenes stu...

  14. Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

    DOEpatents

    Tonkovich, Anna Lee Y.; Wang, Yong; Wegeng, Robert S.; Gao, Yufei

    2003-09-09

    Reactors and processes are disclosed that can utilize high heat fluxes to obtain fast, steady-state reaction rates. Porous catalysts used in conjunction with microchannel reactors to obtain high rates of heat transfer are also disclosed. Reactors and processes that utilize short contact times, high heat flux and low pressure drop are described. Improved methods of steam reforming are also provided.

  15. Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

    DOEpatents

    Tonkovich, Anna Lee Y.; Wang, Yong; Wegeng, Robert S.; Gao, Yufei

    2006-05-16

    Reactors and processes are disclosed that can utilize high heat fluxes to obtain fast, steady-state reaction rates. Porous catalysts used in conjunction with microchannel reactors to obtain high rates of heat transfer are also disclosed. Reactors and processes that utilize short contact times, high heat flux and low pressure drop are described. Improved methods of steam reforming are also provided.

  16. Field measurement of slow metamorphic reaction rates at temperatures of 500 degrees to 600 degrees C

    PubMed

    Baxter; DePaolo

    2000-05-26

    High-temperature metamorphic reaction rates were measured using strontium isotopic ratios of garnet and whole rock from a field site near Simplon Pass, Switzerland. For metamorphic conditions of cooling from 612 degrees +/- 17 degrees C to 505 degrees +/- 15 degrees C at pressures up to 9.1 kilobars, the inferred bulk fluid-rock exchange rate is 1.3(-0.4)(+1.1) x 10(-7) grams of solid reacted per gram of solid per year, several orders of magnitude lower than laboratory-based estimates. The inferred reaction rate suggests that mineral chemistry may lag the evolving conditions in Earth's crust during mountain building. PMID:10827949

  17. Venus volcanism: Rate estimates from laboratory studies of sulfur gas-solid reactions

    NASA Technical Reports Server (NTRS)

    Ehlers, K.; Fegley, B., Jr.; Prinn, R. G.

    1989-01-01

    Thermochemical reactions between sulfur-bearing gases in the atmosphere of Venus and calcium-, iron-, magnesium-, and sulfur-bearing minerals on the surface of Venus are an integral part of a hypothesized cycle of thermochemical and photochemical reactions responsible for the maintenance of the global sulfuric acid cloud cover on Venus. SO2 is continually removed from the Venus atmosphere by reaction with calcium bearing minerals on the planet's surface. The rate of volcanism required to balance SO2 depletion by reactions with calcium bearing minerals on the Venus surface can therefore be deduced from a knowledge of the relevant gas-solid reaction rates combined with reasonable assumptions about the sulfur content of the erupted material (gas + magma). A laboratory program was carried out to measure the rates of reaction between SO2 and possible crustal minerals on Venus. The reaction of CaCO3(calcite) + SO2 yields CaSO4 (anhydrite) + CO was studied. Brief results are given.

  18. Rate Constant Change of Photo Reaction of Bacteriorhodopsin Observed in Trimeric Molecular System.

    PubMed

    Tsujiuchi, Yutaka; Masumoto, Hiroshi; Goto, Takashi

    2016-04-01

    To elucidate the time evolution of photo reaction of bacteriorhodopsin in glycerol mixed purple membrane at around 196 K under irradiation by red light, a kinetic model was constructed. The change of absorption with irradiation at times of 560 nm and 412 nm was analyzed for the purpose of determining reaction rates of photo reaction of bacteriorhodopsin and its product M intermediate. In this study it is shown that reaction rates of conversion from bacteriorhodopsin to the M intermediate can be explained by a set of linear differential equations. This model analysis concludes that bacteriorhodopsin in which constitutes a trimer unit with other two bacteriorhodopsin molecules changes into M intermediates in the 1.73 of reaction rate, in the initial step, and according to the number of M intermediate in a trimer unit, from three to one, the reaction rate of bacteriorhodopsin into M intermediates smaller as 1.73, 0.80, 0.19 which caused by influence of inter-molecular interaction between bacteriorhodopsin. PMID:27451646

  19. Effective reaction rates in diffusion-limited phosphorylation-dephosphorylation cycles

    NASA Astrophysics Data System (ADS)

    Szymańska, Paulina; Kochańczyk, Marek; Miekisz, Jacek; Lipniacki, Tomasz

    2015-02-01

    We investigate the kinetics of the ubiquitous phosphorylation-dephosphorylation cycle on biological membranes by means of kinetic Monte Carlo simulations on the triangular lattice. We establish the dependence of effective macroscopic reaction rate coefficients as well as the steady-state phosphorylated substrate fraction on the diffusion coefficient and concentrations of opposing enzymes: kinases and phosphatases. In the limits of zero and infinite diffusion, the numerical results agree with analytical predictions; these two limits give the lower and the upper bound for the macroscopic rate coefficients, respectively. In the zero-diffusion limit, which is important in the analysis of dense systems, phosphorylation and dephosphorylation reactions can convert only these substrates which remain in contact with opposing enzymes. In the most studied regime of nonzero but small diffusion, a contribution linearly proportional to the diffusion coefficient appears in the reaction rate. In this regime, the presence of opposing enzymes creates inhomogeneities in the (de)phosphorylated substrate distributions: The spatial correlation function shows that enzymes are surrounded by clouds of converted substrates. This effect becomes important at low enzyme concentrations, substantially lowering effective reaction rates. Effective reaction rates decrease with decreasing diffusion and this dependence is more pronounced for the less-abundant enzyme. Consequently, the steady-state fraction of phosphorylated substrates can increase or decrease with diffusion, depending on relative concentrations of both enzymes. Additionally, steady states are controlled by molecular crowders which, mostly by lowering the effective diffusion of reactants, favor the more abundant enzyme.

  20. Unbound states of (32)Cl andthe (31)S(p,gamma)(32)Cl reaction rate

    SciTech Connect

    Matos, M.; Blackmon, Jeff C; Linhardt, Laura; Bardayan, Daniel W; Nesaraja, Caroline D; Clark, Jason; Diebel, C.; O'Malley, Patrick; Parker, P.D.

    2011-01-01

    The {sup 31}S(p,{gamma}){sup 32}Cl reaction is expected to provide the dominant break-out path from the SiP cycle in novae and is important for understanding enrichments of sulfur observed in some nova ejecta. We studied the {sup 32}S(3He,t){sup 32}Cl charge-exchange reaction to determine properties of proton-unbound levels in {sup 32}Cl that have previously contributed significant uncertainties to the {sup 31}S(p,{gamma}){sup 32}Cl reaction rate. Measured triton magnetic rigidities were used to determine excitation energies in {sup 32}Cl. Proton-branching ratios were obtained by detecting decay protons from unbound {sup 32}Cl states in coincidence with tritons. An improved {sup 31}S(p,{gamma}){sup 32}Cl reaction rate was calculated including robust statistical and systematic uncertainties.

  1. Ab Initio Calculation of Rate Constants for Molecule-Surface Reactions with Chemical Accuracy.

    PubMed

    Piccini, GiovanniMaria; Alessio, Maristella; Sauer, Joachim

    2016-04-18

    The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide-and-conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction-type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre-exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude). PMID:27008460

  2. Ab Initio Calculation of Rate Constants for Molecule–Surface Reactions with Chemical Accuracy

    PubMed Central

    Piccini, GiovanniMaria; Alessio, Maristella

    2016-01-01

    Abstract The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide‐and‐conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction‐type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre‐exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude). PMID:27008460

  3. Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment

    DOE R&D Accomplishments Database

    Marcus, R. A.

    1964-01-01

    In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.

  4. Exploiting time-resolved magnetic field effects for determining radical ion reaction rates

    NASA Astrophysics Data System (ADS)

    Bessmertnykh, A. O.; Borovkov, V. I.; Bagryansky, V. A.; Molin, Yu N.

    2016-07-01

    The capabilities of the method of time-resolved magnetic field effect in determining the rates of charge transfer reactions between radical ions and molecules on a nanosecond time scale have been investigated. The approach relies on the electron spin coherence in radical pair's partners generated by ionizing radiation. The spin evolution of the pair is sensitive to the reaction since the latter results in changing magnetic interactions of the unpaired electron. This process can be monitored by magnetic-field-sensitive fluorescence from an irradiated sample that is illustrated using reactions involving alkane radical cations. The accuracy and limitations of the approach are discussed.

  5. Absolute rate parameters for the reaction of ground state atomic oxygen with dimethyl sulfide and episulfide

    NASA Technical Reports Server (NTRS)

    Lee, J. H.; Timmons, R. B.; Stief, L. J.

    1976-01-01

    It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.

  6. Considerations Based on Reaction Rate on Char Gasification Behavior in Two-stage Gasifier for Biomass

    NASA Astrophysics Data System (ADS)

    Taniguchi, Miki; Nishiyama, Akio; Sasauchi, Kenichi; Ito, Yusuke; Akamatsu, Fumiteru

    In order to develop a small-scale gasifier in which biomass can be converted to energy with high efficiency, we planned a gasification process that consists of two parts: pyrolysis part (rotary kiln) and gasification part (downdraft gasifier). We performed fundamental experiments on gasification part and discussed the appropriate conditions such as air supply location, air ratio, air temperature and hearth load. We considered the results by calculating reaction rates of representative reactions on char gasification part and found that water gas reaction is dominant in the reduction area and its behavior gives important information to decide the adequate length of the char layer.

  7. Rate constants for chemical reactions in high-temperature nonequilibrium air

    NASA Technical Reports Server (NTRS)

    Jaffe, R. L.

    1986-01-01

    In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.

  8. Reaction Rates for the Formation of Deuterium Tritide from Deuterium and Tritium

    SciTech Connect

    McConville, G. T.; Menke, D. A.; Ellefson, R. E.

    1985-04-01

    The rates of formation of DT in a mixture of D2 and T2 have been measured as a function of initial T2 concentration, pressure, temperature,and methane concentration in a stainless steel reaction container which had been treated to inhibit protium ingrowth. An attempt has been made to explain the experimental resuts on the basis of ion-molecule chain reactions. Some of the observations are consistent with a gas-phase ion, ground-state molecule reaction, but some of the more interesting observations require more complicated models. The addition of excited state molecules or heterogeneous catalytic effects are possibilities that will need further experiments for confirmation.

  9. The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

    NASA Astrophysics Data System (ADS)

    Maher, Kate; Steefel, Carl I.; White, Art F.; Stonestrom, Dave A.

    2009-05-01

    depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO 2(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.

  10. The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

    USGS Publications Warehouse

    Maher, K.; Steefel, Carl; White, A.F.; Stonestrom, D.A.

    2009-01-01

    the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO2(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws. ?? 2009 Elsevier Ltd.

  11. Matching of experimental and statistical-model thermonuclear reaction rates at high temperatures

    NASA Astrophysics Data System (ADS)

    Newton, Joseph; Longland, Richard; Iliadis, Christian

    2009-05-01

    Reliable reaction rates at high stellar temperatures are necessary for the study of advanced stellar burning stages, supernovae and x-ray bursts. We suggest a new procedure for extrapolating experimental thermonuclear reaction rates to these higher temperatures (T > 1 GK) using statistical model (Hauser-Feshbach) results. Current, generally accepted, procedures involve the use of the Gamow peak, which has been shown to be unreliable for narrow resonances at high stellar temperatures [1]. Our new approach defines the effective thermonuclear energy range (ETER) by using the 8^th, 50^th and 92^nd percentiles of the cumulative distribution of fractional resonant reaction contributions. The ETER is then used to define a reliable temperature for matching experimental rates to Hauser-Feshbach rates. The resulting matching temperature is often well above the previous result using the Gamow peak concept. Our new method should provide more accurate extrapolated rates since Hauser-Feshbach rates are more reliable at higher temperatures. These ideas are applied to 21 (p,γ), (p,α) and (α,γ) reactions on a range of A = 20-40 target nuclei and results will be presented. [0pt] [1] J. R. Newton, C. Iliadis, A. E. Champagne, A. Coc, Y. Parpottas and R. Ugalde, Phys. Rev. C 75, 045801 (2007).

  12. Does nitrogen fertilizer application rate to corn affect nitrous oxide emissions from the rotated soybean crop?

    PubMed

    Iqbal, Javed; Mitchell, David C; Barker, Daniel W; Miguez, Fernando; Sawyer, John E; Pantoja, Jose; Castellano, Michael J

    2015-05-01

    Little information exists on the potential for N fertilizer application to corn ( L.) to affect NO emissions during subsequent unfertilized crops in a rotation. To determine if N fertilizer application to corn affects NO emissions during subsequent crops in rotation, we measured NO emissions for 3 yr (2011-2013) in an Iowa, corn-soybean [ (L.) Merr.] rotation with three N fertilizer rates applied to corn (0 kg N ha, the recommended rate of 135 kg N ha, and a high rate of 225 kg N ha); soybean received no N fertilizer. We further investigated the potential for a winter cereal rye ( L.) cover crop to interact with N fertilizer rate to affect NO emissions from both crops. The cover crop did not consistently affect NO emissions. Across all years and irrespective of cover crop, N fertilizer application above the recommended rate resulted in a 16% increase in mean NO flux rate during the corn phase of the rotation. In 2 of the 3 yr, N fertilizer application to corn (0-225 kg N ha) did not affect mean NO flux rates from the subsequent unfertilized soybean crop. However, in 1 yr after a drought, mean NO flux rates from the soybean crops that received 135 and 225 kg N ha N application in the corn year were 35 and 70% higher than those from the soybean crop that received no N application in the corn year. Our results are consistent with previous studies demonstrating that cover crop effects on NO emissions are not easily generalizable. When N fertilizer affects NO emissions during a subsequent unfertilized crop, it will be important to determine if total fertilizer-induced NO emissions are altered or only spread across a greater period of time. PMID:26024252

  13. Triple-alpha reaction rate studied with the Faddeev three-body formalism

    SciTech Connect

    Ishikawa, Souichi

    2012-11-12

    The triple-alpha (3{alpha}) reaction, {sup 4}He+{sup 4}He+{sup 4}He{yields}{sup 12}C+{gamma}, which plays a significant role in the stellar evolution scenarios, is studied in terms of a three-alpha (3-{alpha}) model. The reaction rate of the process is calculated via an inverse process, 3-{alpha} photodisintegration of a {sup 12}C nucleus. Both of 3-{alpha} bound and-continuum states are calculated by a Faddeev method with accommodating the long range Coulomb interaction. With being adjusted to the empirical E2-strength for {sup 12}C(0{sub 2}{sup +}){yields}{sup 12}C(2{sub 1}{sup +}) transition, results of the 3{alpha} reaction rate <{alpha}{alpha}{alpha}> at higher temperature (T > 10{sup 8} K), where the reaction proceeds mainly through the {sup 8}Be and {sup 12}C(0{sub 2}{sup +}) resonant states, almost agree with those of the Nuclear Astrophysics Compilation of Reaction Rates (NACRE). On the other hand, calculated values of <{alpha}{alpha}{alpha}> are about 10{sup 3} times larger than the NACRE rate at a low temperature (T= 10{sup 7} K), which means our results are remarkably smaller than recent CDCC results.

  14. Determination of Global Reaction Rate During Laser-Induced Decomposition at Static High Pressures

    NASA Astrophysics Data System (ADS)

    Russell, Thomas. P.; Pangilinan, Gerardo I.

    1998-03-01

    The laser induced decomposition of hexahydro-1,3,5-trinitro-1,3,5 triazine (C_3H_6N_6O_6, RDX), trinitro azetidine (C_3H_4N_3O_6, TNAZ) and ammonium perchlorate (NH_4ClO_4, AP) at static high pressure in the range of 0.6 - 2.0 GPa is presented. The samples are loaded in a gem anvil cell and the reaction is induced with a single laser pulse (514 nm, 6 μs duration, 3-22 J/cm^2). The dynamic chemical processes are probed using time resolved uv-Vis absorption spectroscopy, during and up to 20 μs after the laser pulse. In all three materials, decomposition is characterized by a time-dependent increase in absorbance from 300-500 nm. This absorption change is directly proportional to the mole fraction of reaction and provides a measurement of the global reaction rate. The reaction rate is determined to be dependent on the sample, the initial pressure, and the laser fluence. The chemical decomposition is modeled using a three term reaction rate equation encompassing initiation, growth, and coalescence. A description of the differences in the decomposition kinetics for each material will be provided. Finally, the implications of these measurements to models of macroscopic energy release rates will be addressed.

  15. The 25Al(p,g)26Si Reaction Rate in Novae

    NASA Astrophysics Data System (ADS)

    Bardayan, Dan; Blackmon, J. C.; Hix, W. R.; Liang, J. F.; Smith, M. S.; Howard, J. A.; Kozub, R. L.; Brune, C. R.; Chae, K. Y.; Lingerfelt, E. J.; Scott, J. P.; Johnson, M. S.; Jones, K. L.; Pain, S. D.; Thomas, J. S.; Livesay, R. J.; Wisser, D. W.

    The production of 26Al in novae is uncertain, in part, because of the uncertain rate of the 25 Al(p,γ)26Si reaction at novae temperatures. This reaction is thought to be dominated by a long- sought 3+ level in 26Si, and the calculated reaction rate varies by orders of magnitude depending on the energy of this resonance. We present evidence concerning the spin of a level at 5.914 MeV in 26Si from the 28Si(p,t)26Si reaction studied at the Holifield Radioactive Beam Facility at ORNL. We find that the angular distribution for this level implies either a 2+ or 3+ assignment, with only a 3+ being consistent with the mirror nucleus, 26Mg. Additionally, we have used the updated 25Al(p,γ)26Si reaction rate in a nova nucleosynthesis calculation and have addressed the effects of the remaining uncertainties in the rate on 26Al production.

  16. Impact of strange quark matter nuggets on pycnonuclear reaction rates in the crusts of neutron stars

    SciTech Connect

    Golf, B.; Hellmers, J.; Weber, F.

    2009-07-15

    This article presents an investigation into the pycnonuclear reaction rates in dense crustal matter of neutron stars contaminated with strange quark matter nuggets. The presence of such nuggets in the crustal matter of neutron stars would be a natural consequence if Witten's strange quark matter hypothesis is correct. The methodology presented in this article is a recreation of a recent representation of nuclear force interactions embedded within pycnonuclear reaction processes. The study then extends the methodology to incorporate distinctive theoretical characteristics of strange quark matter nuggets, like their low charge-per-baryon ratio, and then assesses their effects on the pycnonuclear reaction rates. Particular emphasis is put on the impact of color superconductivity on the reaction rates. Depending on whether quark nuggets are in this novel state of matter, their electric charge properties vary drastically, which turns out to have a dramatic effect on the pycnonuclear reaction rates. Future nuclear fusion network calculations may thus have the potential to shed light on the existence of strange quark matter nuggets and on whether they are in a color superconducting state, as suggested by QCD.

  17. Rates of various reactions catalyzed by ATP synthase as related to the mechanism of ATP synthesis

    SciTech Connect

    Berkich, D.A.; Williams, G.D.; Masiakos, P.T.; Smith, M.B.; Boyer, P.D.; LaNoue, K.F. )

    1991-01-05

    The forward and reverse rates of the overall reaction catalyzed by the ATP synthase in intact rat heart mitochondria, as measured with 32P, were compared with the rates of two partial steps, as measured with 18O. Such rates have been measured previously, but their relationship to one another has not been determined, nor have the partial reactions been measured in intact mitochondria. The partial steps measured were the rate of medium Pi formation from bound ATP (in state 4 this also equals the rate of medium Pi into bound ATP) and the rate of formation of bound ATP from bound Pi within the catalytic site. The rates of both partial reactions can be measured by 31P NMR analysis of the 18O distribution in Pi and ATP released from the enzyme during incubation of intact mitochondria with highly labeled (18O)Pi. Data were obtained in state 3 and 4 conditions with variation in substrate concentrations, temperature, and mitochondrial membrane electrical potential gradient (delta psi m). Although neither binding nor release of ATP is necessary for phosphate/H2O exchange, in state 4 the rate of incorporation of at least one water oxygen atom into phosphate is approximately twice the rate of the overall reaction rate under a variety of conditions. This can be explained if the release of Pi or ATP at one catalytic site does not occur, unless ATP or Pi is bound at another catalytic site. Such coupling provides strong support for the previously proposed alternating site mechanism. In state 3 slow reversal of ATP synthesis occurs within the mitochondrial matrix and can be detected as incorporation of water oxygen atoms into medium Pi even though medium (32P)ATP does not give rise to 32Pi in state 3. These data can be explained by lack of translocation of ATP from the medium to the mitochondrial matrix.

  18. Astrophysical reaction rate for Be9 formation within a three-body approach

    NASA Astrophysics Data System (ADS)

    Casal, J.; Rodríguez-Gallardo, M.; Arias, J. M.; Thompson, I. J.

    2014-10-01

    The structure of the Borromean nucleus Be9 (α+α+n) is addressed within a three-body approach using the analytical transformed harmonic oscillator method. The three-body formalism provides an accurate description of the radiative capture reaction rate for the entire temperature range relevant in astrophysics. At high temperatures, results match the calculations based on two-step sequential processes. At low temperatures, where the particles have no access to intermediate two-body resonances, the three-body direct capture leads to reaction rates larger than the sequential processes. These results support the reliability of the method for systems with several charged particles.

  19. A Qualitative Case Study of EFL Students' Affective Reactions to and Perceptions of Their Teachers' Written Feedback

    ERIC Educational Resources Information Center

    Mahfoodh, Omer Hassan A.; Pandian, Ambigapathy

    2011-01-01

    The present paper reports a qualitative case study of investigating EFL students' affective reactions to and perceptions of their teachers' written feedback. In addition, the study reported here also focuses on contextual factors that may influence students' reactions to and perceptions of their teachers' written feedback. Data were collected…

  20. Photochemistry of solutes in/on ice: reaction rate dependence on sample orientation and photon flux

    NASA Astrophysics Data System (ADS)

    Hullar, T.; Anastasio, C.

    2015-12-01

    Particularly in polar regions, photochemical reactions in snowpacks can be an important mechanism for transforming organic and inorganic compounds. Chemicals within snow and ice are found in three different compartments: distributed in the bulk ice, concentrated in liquid-like regions (LLRs) within the ice matrix (such as at grain boundaries), or present in quasi-liquid layers (QLLs) at the air-ice interface. While some previous work suggested reaction rates may vary in these different compartments, our preliminary experiments found similar reaction rates in all three compartments, as well as in aqueous solution. Previous work also suggested reaction rate constants may be independent of photon flux under certain illumination conditions. Here, we extend our investigations to measure reaction rate constants in ice samples with different orientations to the illumination source, which our work thus far suggests may impact the measured rate constants. Polycyclic aromatic hydrocarbons (PAHs) are common pollutants in snow and ice. We first prepared aqueous solutions of a single PAH. We then froze these samples using various methods previously shown to segregate the solute into known locations in the ice matrix. With simulated polar sunlight, we illuminated these samples and measured photon flux (using 2-nitrobenzaldehyde as a chemical actinometer) and photodecay of the PAH. Using this information, we normalized the rate of PAH loss to the photon flux and calculated the rate constants for PAH photodegradation under various freezing conditions, photon fluxes, and sample orientations. We will report on the impact of these variables on PAH photodegradation as well as the effect of varying the photon flux.

  1. Regulating emotions uniquely modifies reaction time, rate of force production, and accuracy of a goal-directed motor action.

    PubMed

    Beatty, Garrett F; Fawver, Bradley; Hancock, Gabriella M; Janelle, Christopher M

    2014-02-01

    We investigated how emotion regulation (ER) strategies influence the execution of a memory guided, ballistic pinch grip. Participants (N=33) employed ER strategies (expressive suppression, emotional expression, and attentional deployment) while viewing emotional stimuli (IAPS images). Upon stimulus offset, participants produced a targeted pinch force aimed at 10% of their maximum voluntary contraction. Performance measures included reaction time (RT), rate of force production, and performance accuracy. As hypothesized, attentional deployment resulted in the slowest RT, largest rate of force production, and poorest performance accuracy. In contrast, expressive suppression reduced the rate of force production and increased performance accuracy relative to emotional expression and attentional deployment. Findings provide evidence that emotion regulation strategies uniquely influence human movement. Future work should further delineate the interacting role that emotion regulation strategies have in modulating both affective experience and motor performance. PMID:24576703

  2. How Does the Driver’s Perception Reaction Time Affect the Performances of Crash Surrogate Measures?

    PubMed Central

    Kuang, Yan; Qu, Xiaobo; Weng, Jinxian; Etemad-Shahidi, Amir

    2015-01-01

    With the merit on representing traffic conflict through examining the crash mechanism and causality proactively, crash surrogate measures have long been proposed and applied to evaluate the traffic safety. However, the driver’s Perception-Reaction Time (PRT), an important variable in crash mechanism, has not been considered widely into surrogate measures. In this regard, it is important to know how the PRT affects the performances of surrogate indicators. To this end, three widely used surrogate measures are firstly modified by involving the PRT into their crash mechanisms. Then, in order to examine the difference caused by the PRT, a comparative study is carried out on a freeway section of the Pacific Motorway, Australia. This result suggests that the surrogate indicators’ performances in representing rear-end crash risks are improved with the incorporating of the PRT for the investigated section. PMID:26398416

  3. The affect of a clearcut environment on woody debris respiration rate dynamics, Harvard Forest, Massachusetts

    NASA Astrophysics Data System (ADS)

    Vanderhoof, M. K.; Williams, C. L.

    2011-12-01

    At an ecosystem scale, the distribution of carbon is largely a function of stand development and disturbance processes. Clearcut logging remains a common practice both in the United States and globally and typically results in elevated storage of carbon in onsite woody debris and detritus. The residence time and decomposition rate of this woody debris and detritus will affect the rate of CO2 efflux to the atmosphere and thus affect the long term consequences of such disturbances on carbon flux and storage. The removal of a forest canopy also affects a site's microclimate including the albedo, air temperature, air humidity, as well as soil temperature and moisture, many of the same factors that affect the rate of woody debris decomposition. Thus it could be expected that differences in woody debris characteristics (e.g. size, abundance, state of decay), as well as differences in microclimate, between mature and recently clearcut forest sites, would result in differences in piece and site-level woody debris decomposition rates. Although woody debris stocks post-harvest have been well characterized, few studies have explored post-disturbance woody debris respiration rates, which directly measures carbon emissions from woody debris, distinguishing decomposition from mass loss due to fragmentation or leaching. This study addressed the question: does a clearcut environment in a temperate forest affect the rate of decomposition of coarse woody debris? The rate of respiration of downed spruce logs were repeatedly measured in-situ using an LI-6250 gas analyzer in Harvard Forest, Petersham, Massachusetts. Treatments included clear-cut, shaded clear-cut, mature spruce stand, and transfer (from clearcut to spruce stand). Gas analyzer measurements were accompanied by measurements of log temperature and percent water, soil temperature, moisture and pH, as well as light levels, air temperature and humidity to determine dominant drivers of respiration rates.

  4. Direct use of the mass output of a thermobalance for controlling the reaction rate of solid-state reactions

    NASA Astrophysics Data System (ADS)

    Diánez, M. J.; Pérez Maqueda, L. A.; Criado, J. M.

    2004-08-01

    Sample controlled thermal analysis equipment has been developed constituted by an electrobalance in which the mass output (TG signal) is directly used for monitoring the temperature of thermal decomposition reactions under constant rate thermal analysis (CRTA) or stepwise isothermal analysis (SIA) control. The sample weight is programmed to follow a preset linear decrease as a function of the time by means of a conventional controller, that at the time control a second conventional temperature programmer. The CRTA control is achieved by controlling the temperature is such a way that if the mass input is higher than the setpoint, the temperature increases at a predefined heating rate; while if the mass input is lower than the setpoint, the temperature decreases at a predefined cooling rate. The SIA control is achieved by selecting the run-hold command from the menu of the digital input of the temperature programmer. In such a case, the programmed linear heating schedule is in progress while the sample weight is higher than the setpoint and an isothermal dwell is maintained as soon as the weight becomes lower than the setpoint. The direct use of the mass output for the control provides a higher sensitivity for selecting very low values of constant reaction rates than the more conventional methods using the DTG output as control parameter. The thermal degradation of polyvinye chloride (PVC) has been used for checking the behavior of the equipment here developed, showing that the dehydrochlorination of PVC is controlled either by a nucleation and growth of nuclei or by a random scission of the main chain of the polymer.

  5. Degradation of (14)C-labeled few layer graphene via Fenton reaction: Reaction rates, characterization of reaction products, and potential ecological effects.

    PubMed

    Feng, Yiping; Lu, Kun; Mao, Liang; Guo, Xiangke; Gao, Shixiang; Petersen, Elijah J

    2015-11-01

    Graphene has attracted considerable commercial interest due to its numerous potential applications. It is inevitable that graphene will be released into the environment during the production and usage of graphene-enabled consumer products, but the potential transformations of graphene in the environment are not well understood. In this study, (14)C-labeled few layer graphene (FLG) enabled quantitative measurements of FLG degradation rates induced by the iron/hydrogen peroxide induced Fenton reaction. Quantification of (14)CO2 production from (14)C-labeled FLG revealed significant degradation of FLG after 3 days with high H2O2 (200 mmol L(-1)) and iron (100 μmol L(-1)) concentrations but substantially lower rates under environmentally relevant conditions (0.2-20 mmol L(-1) H2O2 and 4 μmol L(-1) Fe(3+)). Importantly, the carbon-14 labeling technique allowed for quantification of the FLG degradation rate at concentrations nearly four orders of magnitude lower than those typically used in other studies. These measurements revealed substantially faster degradation rates at lower FLG concentrations and thus studies with higher FLG concentrations may underestimate the degradation rates. Analysis of structural changes to FLG using multiple orthogonal methods revealed significant FLG oxidation and multiple reaction byproducts. Lastly, assessment of accumulation of the degraded FLG and intermediates using aquatic organism Daphnia magna revealed substantially decreased body burdens, which implied that the changes to FLG caused by the Fenton reaction may dramatically impact its potential ecological effects. PMID:26210029

  6. A coupled mechanical and chemical damage model for concrete affected by alkali–silica reaction

    SciTech Connect

    Pignatelli, Rossella; Comi, Claudia; Monteiro, Paulo J.M.

    2013-11-15

    To model the complex degradation phenomena occurring in concrete affected by alkali–silica reaction (ASR), we formulate a poro-mechanical model with two isotropic internal variables: the chemical and the mechanical damage. The chemical damage, related to the evolution of the reaction, is caused by the pressure generated by the expanding ASR gel on the solid concrete skeleton. The mechanical damage describes the strength and stiffness degradation induced by the external loads. As suggested by experimental results, degradation due to ASR is considered to be localized around reactive sites. The effect of the degree of saturation and of the temperature on the reaction development is also modeled. The chemical damage evolution is calibrated using the value of the gel pressure estimated by applying the electrical diffuse double-layer theory to experimental values of the surface charge density in ASR gel specimens reported in the literature. The chemo-damage model is first validated by simulating expansion tests on reactive specimens and beams; the coupled chemo-mechanical damage model is then employed to simulate compression and flexure tests results also taken from the literature. -- Highlights: •Concrete degradation due to ASR in variable environmental conditions is modeled. •Two isotropic internal variables – chemical and mechanical damage – are introduced. •The value of the swelling pressure is estimated by the diffuse double layer theory. •A simplified scheme is proposed to relate macro- and microscopic properties. •The chemo-mechanical damage model is validated by simulating tests in literature.

  7. Does organizational culture affect out-patient DNA (did not attend) rates?

    PubMed

    Jackson, S

    1997-01-01

    Government interest in health service "did not attend" (DNA) rates was seen to occur by accident, following which efforts to reduce DNAs have tended to concentrate on operational rather than strategic issues. Considers the effect hospital culture has had on DNA rates from an organizational and patient perspective. Identifies some of the key cultural issues that impacted on DNA rates by utilizing observation and telephone survey research methods. Concludes that, in the main, the lack of customer-oriented organizational culture was seen to affect DNA rates adversely within one NHS provider trust. PMID:10179096

  8. Reaction rate modeling in the deflagration to detonation transition of granular energetic materials

    SciTech Connect

    Son, S.F.; Asay, B.W.; Bdzil, J.B.; Kober, E.M.

    1996-07-01

    The problem of accidental initiation of detonation in granular material has been the initial focus of the Los Alamos explosives safety program. Preexisting models of deflagration-to-detonation transition (DDT) in granular explosives, especially the Baer and Nunziato (BN) model, have been examined. The main focus of this paper is the reaction rate model. Comparison with experiments are made using the BN rate model. Many features are replicated by the simulations. However, some qualitative features, such as inert plug formation in DDT tube-test experiments and other trends, are not produced in the simulations. By modifying the reaction rate model the authors show inert plug formation that more closely replicates the qualitative features of experimental observations. Additional improvements to the rate modeling are suggested.

  9. Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

    SciTech Connect

    Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.; Zachara, John M.; Zhu, Weihuang

    2013-03-15

    Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on the temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.

  10. Rate constant calculations of H-atom abstraction reactions from ethers by HȮ2 radicals.

    PubMed

    Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J

    2014-02-27

    In this work, we detail hydrogen atom abstraction reactions from six ethers by the hydroperoxyl radical, including dimethyl ether, ethyl methyl ether, propyl methyl ether, isopropyl methyl ether, butyl methyl ether, and isobutyl methyl ether, in order to test the effect of the functional group on the rate constant calculations. The Møller-Plesset (MP2) method with the 6-311G(d,p) basis set has been employed in the geometry optimizations and frequency calculations of all of the species involved in the above reaction systems. The connections between each transition state and the corresponding local minima have been determined by intrinsic reaction coordinate calculations. Energies are reported at the CCSD(T)/cc-pVTZ level of theory and include the zero-point energy corrections. As a benchmark in the electronic energy calculations, the CCSD(T)/CBS extrapolation was used for the reactions of dimethyl ether + HȮ2 radicals. A systematic calculation of the high-pressure limit rate constants has been performed using conventional transition-state theory, including asymmetric Eckart tunneling corrections, in the temperature range of 500-2000 K. The one dimensional hindrance potentials obtained at MP2/6-311G(d,p) for the reactants and transition states have been used to describe the low frequency torsional modes. Herein, we report the calculated individual, average, and total rate constants. A branching ratio analysis for every reaction site has also been performed. PMID:24483837

  11. Evaluation of reaction rates in streambed sediments with seepage flow: a novel code

    NASA Astrophysics Data System (ADS)

    Boano, Fulvio; De Falco, Natalie; Arnon, Shai

    2015-04-01

    Streambed interfaces represent hotspots for nutrient transformations because they host different microbial species which perform many heterotrophic and autotrophic reactions. The evaluation of these reaction rates is crucial to assess the fate of nutrients in riverine environments, and it is often performed through the analysis of concentrations from water samples collected along vertical profiles. The most commonly employed evaluation tool is the Profile code developed by Berg et al. (1998), which determines reaction rates by fitting observed concentrations to a diffusion-reaction equation that neglects the presence of water flow within sediments. However, hyporheic flow is extremely common in streambeds, where solute transport is often controlled by advection rather than diffusion. There is hence a pressing need to develop new methods that can be applied even to advection-dominated sediments. This contribution fills this gap by presenting a novel approach that extends the method proposed by Berg et al. (1998). This new approach includes the influence of vertical solute transport by upwelling or downwelling water, and it is this suited to the typical flow conditions of stream sediments. The code is applied to vertical profiles of dissolved oxygen from a laboratory flume designed to mimic the complex flow conditions of real streams. The results show that it is fundamental to consider water flow to obtain reliable estimates of reaction rates in streambeds. Berg, P., N. Risgaard-Petersen, and S. Rysgaard, 1998, Interpretation of measured concentration profiles in the sediment porewater, Limnology and Oceanography, 43:1500-1510.

  12. Modeling of atmospheric OH reaction rates using newly developed variable distance weighted zero order connectivity index

    NASA Astrophysics Data System (ADS)

    Markelj, Jernej; Pompe, Matevž

    2016-04-01

    A new variable distance weighted zero order connectivity index was used for development of structure-activity relationship for modeling reactivity of OH radical with alkanes and non-conjugated alkenes in the atmosphere. The proposed model is based on the assumptions that the total reaction rate can be obtained by summing all partial reaction rates and that all reaction sites are interrelated by influencing each other. The results suggest that these assumptions are justified. The model was compared with the EPA implemented model in the studied application domain and showed superior prediction capabilities. Further, optimized values of the weights that were used in our model permit some insight into mechanisms that govern the reaction OH + alkane/alkene. The most important conclusion is that the branching degree of the forming radical seems to play a major role in site specific reaction rates. Relative qualitative structural interpretation is possible, e.g. allylic site is suggested to be much more reactive than even tertiary sp3 carbon. Novel modeling software MACI, which was developed in our lab and is now available for research purposes, was used for calculations. Various variable topological indices that are again starting to be recognized because of their great potentials in simplicity, fast calculations, very good correlations and structural information, were implemented in the program.

  13. Do candidate reactions relate to job performance or affect criterion-related validity? A multistudy investigation of relations among reactions, selection test scores, and job performance.

    PubMed

    McCarthy, Julie M; Van Iddekinge, Chad H; Lievens, Filip; Kung, Mei-Chuan; Sinar, Evan F; Campion, Michael A

    2013-09-01

    Considerable evidence suggests that how candidates react to selection procedures can affect their test performance and their attitudes toward the hiring organization (e.g., recommending the firm to others). However, very few studies of candidate reactions have examined one of the outcomes organizations care most about: job performance. We attempt to address this gap by developing and testing a conceptual framework that delineates whether and how candidate reactions might influence job performance. We accomplish this objective using data from 4 studies (total N = 6,480), 6 selection procedures (personality tests, job knowledge tests, cognitive ability tests, work samples, situational judgment tests, and a selection inventory), 5 key candidate reactions (anxiety, motivation, belief in tests, self-efficacy, and procedural justice), 2 contexts (industry and education), 3 continents (North America, South America, and Europe), 2 study designs (predictive and concurrent), and 4 occupational areas (medical, sales, customer service, and technological). Consistent with previous research, candidate reactions were related to test scores, and test scores were related to job performance. Further, there was some evidence that reactions affected performance indirectly through their influence on test scores. Finally, in no cases did candidate reactions affect the prediction of job performance by increasing or decreasing the criterion-related validity of test scores. Implications of these findings and avenues for future research are discussed. PMID:23937298

  14. Reaction rate constants of H-abstraction by OH from large ketones: measurements and site-specific rate rules.

    PubMed

    Badra, Jihad; Elwardany, Ahmed E; Farooq, Aamir

    2014-06-28

    Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (C=O) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (C=O), and the prime is used to differentiate different neighboring environments of a methylene group): PMID:24817270

  15. Solid-gas reaction with adsorption as the rate limiting step.

    PubMed

    Wróbel, Rafał; Arabczyk, Walerian

    2006-07-27

    The model of nucleation where adsorption of reactant is a rate-limiting step has been considered. Assuming the adsorption range model, a numerical simulation has been made. The dependency of bulk concentration and surface coverage versus time and thermogravimetric curves are presented. The crystallite size is suggested to be the key factor of the nucleation rate. Theoretical considerations have been compared with the experimental results of the iron nitriding reaction. PMID:16854036

  16. Estimating the effective rate of fast chemical reactions with turbulent mixing of reactants

    SciTech Connect

    Vorotilin, V. P. Yanovskii, Yu. G.

    2015-07-15

    On the basis of representation of a turbulent fluid as an aggregation of independent turbulent particles (vortexes), we derive relations for the effective rate of chemical reactions and obtain a closed system of equations describing reactions with turbulent mixing of reactants. A variant of instantaneous reactions is considered that explains the proposed approach simply. In particular, the turbulent mixing events according to this approach are uniquely related to the acts of chemical interaction, which makes it possible to exclude from consideration the mixing of inert impurities–the most difficult point of the theory formulated using classical notions. The obtained system of equations is closed without introducing arbitrarily adopted correlations, by naturally introducing the concept of effective reaction and writing the equations of conservation for both the concentrations of reactants and their volumes.

  17. Estimating the effective rate of fast chemical reactions with turbulent mixing of reactants

    NASA Astrophysics Data System (ADS)

    Vorotilin, V. P.; Yanovskii, Yu. G.

    2015-07-01

    On the basis of representation of a turbulent fluid as an aggregation of independent turbulent particles (vortexes), we derive relations for the effective rate of chemical reactions and obtain a closed system of equations describing reactions with turbulent mixing of reactants. A variant of instantaneous reactions is considered that explains the proposed approach simply. In particular, the turbulent mixing events according to this approach are uniquely related to the acts of chemical interaction, which makes it possible to exclude from consideration the mixing of inert impurities-the most difficult point of the theory formulated using classical notions. The obtained system of equations is closed without introducing arbitrarily adopted correlations, by naturally introducing the concept of effective reaction and writing the equations of conservation for both the concentrations of reactants and their volumes.

  18. New Approach for Investigating Reaction Dynamics and Rates with Ab Initio Calculations.

    PubMed

    Fleming, Kelly L; Tiwary, Pratyush; Pfaendtner, Jim

    2016-01-21

    Herein, we demonstrate a convenient approach to systematically investigate chemical reaction dynamics using the metadynamics (MetaD) family of enhanced sampling methods. Using a symmetric SN2 reaction as a model system, we applied infrequent metadynamics, a theoretical framework based on acceleration factors, to quantitatively estimate the rate of reaction from biased and unbiased simulations. A systematic study of the algorithm and its application to chemical reactions was performed by sampling over 5000 independent reaction events. Additionally, we quantitatively reweighed exhaustive free-energy calculations to obtain the reaction potential-energy surface and showed that infrequent metadynamics works to effectively determine Arrhenius-like activation energies. Exact agreement with unbiased high-temperature kinetics is also shown. The feasibility of using the approach on actual ab initio molecular dynamics calculations is then presented by using Car-Parrinello MD+MetaD to sample the same reaction using only 10-20 calculations of the rare event. Owing to the ease of use and comparatively low-cost of computation, the approach has extensive potential applications for catalysis, combustion, pyrolysis, and enzymology. PMID:26690335

  19. Rate constant for the reaction Cl + HO2NO2 yielding products. [in stratospheric chemistry

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Leu, M. T.

    1985-01-01

    The rates for the reaction of Cl atoms iwth HO2NO2 were calculated from data obtained by the use of the discharge flow/resonance fluorescence (DF/RF) and the discharge flow/mass spectrometric (DF/MS) techniques. The total rate constant, k1, for the overall reaction: 1a (Cl + HO2NO2 yielding HCl + NO2 +O2), 1b (yielding HO2 + ClNO2), and the two possible additional channels was found to be less than 1.0 x 10 to the -13th cu cm/s at 296 K. The value of (k1a + k1b) was found to be 3.4 + or - 1.4) x 10 to the -14th cu cm/s. Thus, the reaction of Cl with peroxynitric acid is too slow, by a factor of 100, to contribute significantly to the hydrogen abstraction by Cl in the stratosphere.

  20. Toward a reaction rate model of condensed-phase RDX decomposition under high temperatures

    NASA Astrophysics Data System (ADS)

    Schweigert, Igor

    2015-06-01

    Shock ignition of energetic molecular solids is driven by microstructural heterogeneities, at which even moderate stresses can result in sufficiently high temperatures to initiate material decomposition and chemical energy release. Mesoscale modeling of these ``hot spots'' requires a reaction rate model that describes the energy release with a sub-microsecond resolution and under a wide range of temperatures. No such model is available even for well-studied energetic materials such as RDX. In this presentation, I will describe an ongoing effort to develop a reaction rate model of condensed-phase RDX decomposition under high temperatures using first-principles molecular dynamics, transition-state theory, and reaction network analysis. This work was supported by the Naval Research Laboratory, by the Office of Naval Research, and by the DoD High Performance Computing Modernization Program Software Application Institute for Multiscale Reactive Modeling of Insensitive Munitions.

  1. Reaction rates and kinetic isotope effects of H2 + OH → H2O + H.

    PubMed

    Meisner, Jan; Kästner, Johannes

    2016-05-01

    We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ⋅ 10(-20) to 4 ⋅ 10(-17) cm(3) s(-1), demonstrating that even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures. PMID:27155636

  2. Reaction rates and kinetic isotope effects of H2 + OH → H2O + H

    NASA Astrophysics Data System (ADS)

    Meisner, Jan; Kästner, Johannes

    2016-05-01

    We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ṡ 10-20 to 4 ṡ 10-17 cm3 s-1, demonstrating that even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures.

  3. Rate constant for the reaction of atomic oxygen with phosphine at 298 K

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Payne, W. A.; Nava, D. F.

    1987-01-01

    The rate constant for the reaction of atomic oxygen with phosphine has been measured at 298 K using flash photolysis combined with time-resolved detection of O(3P) via resonance fluorescence. Atomic oxygen was produced by flash photolysis of N2O or NO highly diluted in argon. The results were shown to be independent of (PH3), (O), total pressure and the source of O(3P). The mean value of all the experiments is k1 = (3.6 + or -0.8) x 10 to the -11th cu cm/s (1 sigma). Two previous measurements of k1 differed by more than an order of magnitude, and the results support the higher value obtained in a discharge flow-mass spectrometry study. A comparison with rate data for other atomic and free radical reactions with phosphine is presented, and the role of these reactions in the aeronomy or photochemistry of Jupiter and Saturn is briefly considered.

  4. Thermonuclear Reaction Rate Libraries and Software Tools for Nuclear Astrophysics Research

    NASA Astrophysics Data System (ADS)

    Smith, Michael S.; Cyburt, Richard; Schatz, Hendrik; Wiescher, Michael; Smith, Karl; Warren, Scott; Ferguson, Ryan; Lingerfelt, Eric; Buckner, Kim; Nesaraja, Caroline D.

    2008-05-01

    Thermonuclear reaction rates are a crucial input for simulating a wide variety of astrophysical environments. A new collaboration has been formed to ensure that astrophysical modelers have access to reaction rates based on the most recent experimental and theoretical nuclear physics information. To reach this goal, a new version of the REACLIB library has been created by the Joint Institute for Nuclear Astrophysics (JINA), now available online at http://www.nscl.msu.edu/~nero/db. A complementary effort is the development of software tools in the Computational Infrastructure for Nuclear Astrophysics, online at nucastrodata.org, to streamline, manage, and access the workflow of the reaction evaluations from their initiation to peer review to incorporation into the library. Details of these new projects will be described.

  5. Effect of Strain Rate on Cathodic Reaction During Stress Corrosion Cracking of X70 Pipeline Steel in a Near-Neutral pH Solution

    NASA Astrophysics Data System (ADS)

    Liu, Z. Y.; Li, X. G.; Cheng, Y. F.

    2011-10-01

    The effect of strain rate on cathodic reactions of X70 pipeline steel during stress corrosion cracking in a near-neutral pH solution was investigated by electrochemical impedance spectroscope and potentiodynamic polarization curve measurements as well as slow strain rate tests. A local additional potential model was used to understand mechanistically the role of strain rate in electrochemical cathodic reaction. It was found that an application of elastic stress would not affect the electrochemical stable state of the steel specimen at a macroscopic scale. Under a weak cathodic polarization, the interfacial charge-transfer process occurring on steel contains both cathodic and anodic reactions. Since the anodic reaction process is still significant, localized dissolution could occur even at such a cathodic potential, resulting in generation of corrosion pits. These pits could be the start sites to initiate stress corrosion cracks. Strain rate affects the corrosion reaction, which is associated with the generation of dislocation emergence points and slip steps on the specimen surface, resulting in a negative local additional potential to enhance the cathodic reaction locally.

  6. Factors affecting the corrosion rates of ceramics in coal combustion systems

    SciTech Connect

    Hurley, J.P.

    1995-08-01

    The concentrations of approximately a dozen elements in the products of coal combustion affect the corrosion rates of ceramics used to construct the combustion system. The elements, including H, O, Na, Mg, Al, Si, P, S, Cl, K, Ca, and Fe, affect corrosion rates in three ways: as primary corrodants of the materials, as secondary corrodants that affect the activities of the primary corrodants, and by affecting the mass transport rate of the primary corrodants. A full factorial study of corrosion rates performed by varying the concentrations of these elements would involve X{sup n} tests, where X is the number of variations of each element and n is the number of different elements. For three variations (low, medium, and high concentrations) of each of 12 elements, the number of tests is 531,441 for a single temperature and pressure condition. The numbers can be reduced with the use of a fractional factorial test matrix, but the most effective way to perform corrosion tests is to base them on realistic system conditions. In this paper, the effects of the composition and physical state of the products of coal combustion on ceramic corrosion rates are given along with suggestions of appropriate test conditions for specific system components.

  7. Factors Affecting the Timing of Signal Detection of Adverse Drug Reactions.

    PubMed

    Hashiguchi, Masayuki; Imai, Shungo; Uehara, Keiko; Maruyama, Junya; Shimizu, Mikiko; Mochizuki, Mayumi

    2015-01-01

    We investigated factors affecting the timing of signal detection by comparing variations in reporting time of known and unknown ADRs after initial drug release in the USA. Data on adverse event reactions (AERs) submitted to U.S. FDA was used. Six ADRs associated with 6 drugs (rosuvastatin, aripiprazole, teriparatide, telithromycin, exenatide, varenicline) were investigated: Changes in the proportional reporting ratio, reporting odds ratio, and information component as indexes of signal detection were followed every 3 months after each drugs release, and the time for detection of signals was investigated. The time for the detection of signal to be detected after drug release in the USA was 2-10 months for known ADRs and 19-44 months for unknown ones. The median lag time for known and unknown ADRs was 99.0-122.5 days and 185.5-306.0 days, respectively. When the FDA released advisory information on rare but potentially serious health risks of an unknown ADR, the time lag to report from the onset of ADRs to the FDA was shorter. This study suggested that one factor affecting signal detection time is whether an ADR was known or unknown at release. PMID:26641634

  8. Reaction Rate Acceleration and Tg Depression of Polycyanurate Under Nanopore Confinement

    NASA Astrophysics Data System (ADS)

    Lopez, Evelyn; Simon, Sindee L.

    2015-03-01

    Material properties such as Tg and the reaction kinetics are known to deviate from the bulk when subjected to nano-sized confinement. Previous work from our laboratory on the trimerization of cyanate esters found that the reaction kinetics were faster for a monofunctional reactant compared to a difunctional monomer, whereas the Tg depression was greater for the crosslinked product of the latter compared to the low molecular weight trimer of the former. The origin of the changes in nanoconfined reaction rates differs from those that govern changes in the Tg. The research objective is to further explore the effect that confinement has on reaction kinetics and Tg using a mixture consisting of mono- and di- cyanate ester monomers. The product is an uncrosslinked polycyanurate with Mn = 5240 g/mol and PDI = 1.78. The confinement mediums are controlled pore glasses with diameters ranging from 8.1 to 111.1 nm. The nanopore-confined material was synthesized in-situ and the reaction kinetics are followed by DSC; after the reaction, the Tg values of the nanoconfined polymer where also measured by DSC. An acceleration factor of 13 and a Tg depression of 38 °C are observed for the material confined in the smallest 8.1 nm-diameter pores. The Tg depression is between those of the trimer and network previously studied, while the acceleration of the reaction rate is lower. Our results are consistent with the reaction acceleration arising from packing effects at the pore wall and the Tg depression arising from intrinsic size effects.

  9. Oscillations in the reaction rate of nitric oxide reduction by ammonia over polycrystalline platinum foil catalysts

    SciTech Connect

    Katona, T. |; Somorjai, G.A.

    1992-06-25

    Self-sustained oscillations were obtained in the No + NH{sub 3} reaction at atmospheric pressure with reactant partial pressures of 133-600 Pa (1-4.5 Torr), in the temperature range of 603-673 K. The effects of reaction parameters, temperature, partial pressure, and reactant gas velocity were studied. The onset temperature of the oscillations (603 K) was slightly dependent on the partial pressure of nitric oxide in the feed gas. Near this temperature the oscillations were uncontrolled (chaotic), while increasing the temperature resulted in periodic oscillations in the reaction rates. The oscillation phenomena were studied in both isothermic and adiabatic modes. The oscillations, when initiated by a temperature increase, start up only after an induction period during which the rates of NO consumption and N{sub 2} formation sharply increase as opposed to the slow enhancement of the rate of N{sub 2}O formation. The two reaction branches found at the high- and low-temperature regimes in the batch mode have product distributions which are similar to those found at the extremes of the amplitudes of rate oscillations. 36 refs., 13 figs.

  10. Probing the Rate-Determining Step of the Claisen-Schmidt Condensation by Competition Reactions

    ERIC Educational Resources Information Center

    Mak, Kendrew K. W.; Chan, Wing-Fat; Lung, Ka-Ying; Lam, Wai-Yee; Ng, Weng-Cheong; Lee, Siu-Fung

    2007-01-01

    Competition experiments are a useful tool for preliminary study of the linear free energy relationship of organic reactions. This article describes a physical organic experiment for upper-level undergraduates to identify the rate-determining step of the Claisen-Schmidt condensation of benzaldehyde and acetophenone by studying the linear free…

  11. Calibration of reaction rates for the CREST reactive-burn model

    NASA Astrophysics Data System (ADS)

    Handley, Caroline

    2015-06-01

    In recent years, the hydrocode-based CREST reactive-burn model has had success in modelling a range of shock initiation and detonation propagation phenomena in polymer bonded explosives. CREST uses empirical reaction rates that depend on a function of the entropy of the non-reacted explosive, allowing the effects of initial temperature, porosity and double-shock desensitisation to be simulated without any modifications to the model. Until now, the sixteen reaction-rate coefficients have been manually calibrated by trial and error, using hydrocode simulations of a subset of sustained-shock initiation gas-gun experiments and the detonation size-effect curve for the explosive. This paper will describe the initial development of an automatic method for calibrating CREST reaction-rate coefficients, using the well-established Particle Swarm Optimisation (PSO) technique. The automatic method submits multiple hydrocode simulations for each ``particle'' and analyses the results to determine the ``misfit'' to gas-gun and size-effect data. Over ~40 ``generations,'' the PSO code finds a best set of reaction-rate coefficients that minimises the misfit. The method will be demonstrated by developing a new CREST model for EDC32, a conventional high explosive.

  12. Measurement of proton transfer reaction rates in a microwave cavity discharge flowing afterglow

    NASA Astrophysics Data System (ADS)

    Brooke, George M., IV

    The reaction rate coefficients between the hydronium ion and the molecules ethene (C2H4), propene (C 3H6), 1-butene (C4H8) and hydrogen sulfide (H2S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is spatially separated from the flow tube, eliminating many of the problems inherent with the original FA devices. In addition to measuring reaction rate coefficients, the MCD-FA was shown to be an effective tool for measuring trace compounds in atmospheric air. This method has many advantages over current detection techniques since compounds can be detected in almost real time, large mass ranges can be scanned quickly, and repeated calibration is not required. Preliminary measurements were made of car exhaust and exhaled alveolar air. Car exhaust showed the presence of numerous hydrocarbons, such as butene, benzene and toluene while the exhaled alveolar air showed the presence of various volatile organic compounds such as methanol and acetone.

  13. Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment

    DOE R&D Accomplishments Database

    Marcus, R. A.

    1964-01-01

    In its usual classical form activated complex theory assumes a particular expression for the kinetic energy of the reacting system -- one associated with a rectilinear motion along the reaction coordinate. The derivation of the rate expression given in the present paper is based on the general kinetic energy expression.

  14. Relative Reaction Rates of Sulfamic Acid and Hydroxylamine with Nitric Acid

    SciTech Connect

    Karraker, D.G.

    2001-03-28

    This report describes a study of comparative reaction rates where the reductant is in excess, as in the 1B bank in the Purex process. The results of this work apply to planned plant tests to partially substitute HAN for the ferrous sulfamate reductant in the Purex 1B bank.

  15. Effect of Conceptual Change Approach on Students' Understanding of Reaction Rate Concepts

    ERIC Educational Resources Information Center

    Kingir, Sevgi; Geban, Omer

    2012-01-01

    The purpose of the present study was to investigate the effect of conceptual change text oriented instruction compared to traditional instruction on 10th grade students' understanding of reaction rate concepts. 45 students from two classes of the same teacher in a public high school participated in this study. Students in the experimental group…

  16. Rate of reaction of superoxide radical with chloride-containing species

    SciTech Connect

    Long, C.A.; Bielski, B.H.J.

    1980-01-01

    This paper evaluates the rate constants for the reaction of superoxide radical with five common chloride-containing species (Cl/sup -/, ClO/sup -/, ClO/sub 2//sup -/, ClO/sub 3//sup -/, and ClO/sub 4//sup -/ and proposes a mechanism for those which react.

  17. Should thermostatted ring polymer molecular dynamics be used to calculate thermal reaction rates?

    SciTech Connect

    Hele, Timothy J. H.; Suleimanov, Yury V.

    2015-08-21

    We apply Thermostatted Ring Polymer Molecular Dynamics (TRPMD), a recently proposed approximate quantum dynamics method, to the computation of thermal reaction rates. Its short-time transition-state theory limit is identical to rigorous quantum transition-state theory, and we find that its long-time limit is independent of the location of the dividing surface. TRPMD rate theory is then applied to one-dimensional model systems, the atom-diatom bimolecular reactions H + H{sub 2}, D + MuH, and F + H{sub 2}, and the prototypical polyatomic reaction H + CH{sub 4}. Above the crossover temperature, the TRPMD rate is virtually invariant to the strength of the friction applied to the internal ring-polymer normal modes, and beneath the crossover temperature the TRPMD rate generally decreases with increasing friction, in agreement with the predictions of Kramers theory. We therefore find that TRPMD is approximately equal to, or less accurate than, ring polymer molecular dynamics for symmetric reactions, and for certain asymmetric systems and friction parameters closer to the quantum result, providing a basis for further assessment of the accuracy of this method.

  18. Rate Coefficients for the OH + (CHO)2 (Glyoxal) Reaction Between 240 and 400 K

    NASA Astrophysics Data System (ADS)

    Feierabend, K. J.; Talukdar, R. K.; Zhu, L.; Ravishankara, A. R.; Burkholder, J. B.

    2006-12-01

    Glyoxal (CHO)2, the simplest dialdehyde, is an end product formed in the atmospheric oxidation of biogenic hydrocarbons, for example, isoprene. As such, glyoxal plays a role in regional air quality and ozone production in certain locations. Glyoxal is lost in the atmosphere via UV photolysis and reaction with OH. However, the currently available rate coefficient data for the OH + glyoxal reaction is limited to a single room- temperature measurement made using the relative rate method. A determination of the rate coefficient temperature dependence is therefore needed for a more complete interpretation of the atmospheric processing of glyoxal. This study reports the rate coefficient for the OH + (CHO)2 reaction measured under pseudo- first-order conditions in OH ([(CHO)2] > 1000 [OH]0). OH radicals were produced using 248 nm pulsed laser photolysis of H2O2 or HNO3 and detected by pulsed laser induced fluorescence. The concentration of glyoxal in the reactor was determined using three independent techniques; gas flow rates as well as in situ UV and IR absorption. The total pressure in the reactor was varied from 40 to 300 Torr (He), and the rate coefficient was found to be independent of pressure over the temperature range studied. The rate coefficient exhibits a negative temperature dependence between 240 and 400 K consistent with the dependence previously observed for many other aldehydes. Our room-temperature rate coefficient is smaller than the relative rate value that is currently recommended for use in atmospheric model calculations. Our measured rate coefficients are discussed with respect to those for other aldehydes. The atmospheric implications of our work will also be discussed.

  19. Neural correlates of dueling affective reactions to win–win choices

    PubMed Central

    Shenhav, Amitai; Buckner, Randy L.

    2014-01-01

    Win–win choices cause anxiety, often more so than decisions lacking the opportunity for a highly desired outcome. These anxious feelings can paradoxically co-occur with positive feelings, raising important implications for individual decision styles and general well-being. Across three studies, people chose between products that varied in personal value. Participants reported feeling most positive and most anxious when choosing between similarly high-valued products. Behavioral and neural results suggested that this paradoxical experience resulted from parallel evaluations of the expected outcome (inducing positive affect) versus the cost of choosing a response (inducing anxiety). Positive feelings were reduced when there was no high-value option, and anxiety was reduced when only one option was highly valued. Dissociable regions within the striatum and the medial prefrontal cortex (mPFC) tracked these dueling affective reactions during choice. Ventral regions, associated with stimulus valuation, tracked positive feelings and the value of the best item. Dorsal regions, associated with response valuation, tracked anxiety. In addition to tracking anxiety, the dorsal mPFC was associated with conflict during the current choice, and activity levels across individual items predicted whether that choice would later be reversed during an unexpected reevaluation phase. By revealing how win–win decisions elicit responses in dissociable brain systems, these results help resolve the paradox of win–win choices. They also provide insight into behaviors that are associated with these two forms of affect, such as why we are pulled toward good options but may still decide to delay or avoid choosing among them. PMID:25024178

  20. Reaction rate sensitivity of 44Ti production in massive stars and implications of a thick target yield measurement of 40Ca(alpha,gamma)44Ti

    SciTech Connect

    Hoffman, R D; Sheets, S A; Burke, J T; Scielzo, N D; Rauscher, T; Norman, E B; Tumey, S; Brown, T A; Grant, P G; Hurst, A M; Phair, L; Stoyer, M A; Wooddy, T; Fisker, J L; Bleuel, D

    2010-02-16

    We evaluate two dominant nuclear reaction rates and their uncertainties that affect {sup 44}Ti production in explosive nucleosynthesis. Experimentally we develop thick-target yields for the {sup 40}Ca({alpha},{gamma}){sup 44}Ti reaction at E{sub {alpha}} = 4.13, 4.54, and 5.36 MeV using {gamma}-ray spectroscopy. At the highest beam energy, we also performed an activation measurement which agrees with the thick target result. From the measured yields a stellar reaction rate was developed that is smaller than current statistical-model calculations and recent experimental results, which would suggest lower {sup 44}Ti production in scenarios for the {alpha}-rich freeze out. Special attention has been paid to assessing realistic uncertainties of stellar reaction rates produced from a combination of experimental and theoretical cross sections. With such methods, we also develop a re-evaluation of the {sup 44}Ti({alpha},p){sup 47}V reaction rate. Using these two rates we carry out a sensitivity survey of {sup 44}Ti synthesis in eight expansions representing peak temperature and density conditions drawn from a suite of recent supernova explosion models. Our results suggest that the current uncertainty in these two reaction rates could lead to as large an uncertainty in {sup 44}Ti synthesis as that produced by different treatments of stellar physics.

  1. Transport and reaction processes affecting the attenuation of landfill gas in cover soils.

    PubMed

    Molins, S; Mayer, K U; Scheutz, C; Kjeldsen, P

    2008-01-01

    Methane and trace organic gases produced in landfill waste are partly oxidized in the top 40 cm of landfill cover soils under aerobic conditions. The balance between the oxidation of landfill gases and the ingress of atmospheric oxygen into the soil cover determines the attenuation of emissions of methane, chlorofluorocarbons, and hydrochlorofluorocarbons to the atmosphere. This study was conducted to investigate the effect of oxidation reactions on the overall gas transport regime and to evaluate the contributions of various gas transport processes on methane attenuation in landfill cover soils. For this purpose, a reactive transport model that includes advection and the Dusty Gas Model for simulation of multicomponent gas diffusion was used. The simulations are constrained by data from a series of counter-gradient laboratory experiments. Diffusion typically accounts for over 99% of methane emission to the atmosphere. Oxygen supply into the soil column is driven exclusively by diffusion, whereas advection outward offsets part of the diffusive contribution. In the reaction zone, methane consumption reduces the pressure gradient, further decreasing the significance of advection near the top of the column. Simulations suggest that production of water or accumulation of exopolymeric substances due to microbially mediated methane oxidation can significantly reduce diffusive fluxes. Assuming a constant rate of methane production within a landfill, reduction of the diffusive transport properties, primarily due to exopolymeric substance production, may result in reduced methane attenuation due to limited O(2) -ingress. PMID:18268309

  2. Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

    USGS Publications Warehouse

    Green, C.T.; Böhlke, J.K.; Bekins, B.A.; Phillips, S.P.

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field-scale (apparent) estimated reaction rates and isotopic fractionations and local-scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O 2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample-based estimates of "apparent" parameters with "true" (intrinsic) values. For this aquifer, non-Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2 threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport. ?? 2010 by the American Geophysical Union.

  3. Product distributions, rate constants, and mechanisms of LiH +H reactions

    NASA Astrophysics Data System (ADS)

    Defazio, Paolo; Petrongolo, Carlo; Gamallo, Pablo; González, Miguel

    2005-06-01

    We present a quantum-mechanical investigation of the LiH depletion reaction LiH +H→Li+H2 and of the H exchange reaction LiH +H'→LiH'+H. We report product distributions, rate constant, and mechanism of the former, and rate constant and mechanism of the latter reaction. We use the potential-energy surface by Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)], the real-wave-packet method by Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)], and the J-shifting approximation. The H21 nuclear-spin statistics and progressions of vib-rotational states (v',j') rule both initial-state-resolved and thermal product distributions, which have saw-toothed shapes with odd j' preferred with respect to even j'. At high collision energies and temperatures, we obtain a regular 3-to-1 intensity alternation of rotational states. At low collision energies and temperatures, the degeneracy and density of many H2 levels can, however, give more irregular distributions. During the collision, the energy flows from the reactant translational mode to the product vibration and recoil ones. The rate constants of both reactions are not Arrhenius type because the reactions are barrier-less. The low-temperature, LiH depletion rate constant is larger than the H exchange one, whereas the contrary holds at high temperature. The real-time mechanisms show the nuclear rearrangements of the nonreactive channel and of the reactive ones, and point out that the LiH depletion is preferred over the H exchange at short times. This confirms the rate-constant results.

  4. Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

    PubMed

    Habershon, Scott

    2016-04-12

    In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles. PMID:26938837

  5. Refinement of the aeronomically determined rate coefficient for the reaction of N2/+/ with O

    NASA Technical Reports Server (NTRS)

    Torr, D. G.

    1979-01-01

    An earlier aeronomic determination of the rate coefficient for the reaction N2(+) + O yields NO(+) + N using Atmosphere Explorer data indicated a small increase in the rate coefficient with ion temperature, contrary to laboratory observations. This was incorrectly attributed to neglect of an increase in the N2(+) recombination rate with vibrational excitation. Recent aeronomical results have shown that the rate coefficient for charge exchange of O(+)(2D) with N2 is about an order of magnitude smaller at thermal temperatures than at energies greater than 0.5 eV (i.e., energies at which laboratory measurements have been made). It is shown that the use of the smaller charge exchange rate coefficient coupled with recent results on N2 quenching of O(+)(2D) yields a temperature dependence in excellent agreement with the laboratory results for the rate coefficient.

  6. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions.

    PubMed

    Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian; Bica, Katharina

    2016-05-21

    A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions. PMID:27121134

  7. Reaction and internal energy relaxation rates in viscous thermochemically non-equilibrium gas flows

    SciTech Connect

    Kustova, E. V.; Oblapenko, G. P.

    2015-01-15

    In the present paper, reaction and energy relaxation rates as well as the normal stress are studied for viscous gas flows with vibrational and chemical non-equilibrium. Using the modified Chapman-Enskog method, multi-temperature models based on the Treanor and Boltzmann vibrational distributions are developed for the general case taking into account all kinds of vibrational energy transitions, exchange reactions, dissociation, and recombination. Integral equations specifying the first-order corrections to the normal mean stress and reaction rates are derived, as well as approximate systems of linear equations for their numerical computation. Generalized thermodynamic driving forces associated with all non-equilibrium processes are introduced. It is shown that normal stresses and rates of non-equilibrium processes can be expressed in terms of the same driving forces; the symmetry of kinetic coefficients in these expressions is proven. The developed general model is applied to a particular case of a pure N{sub 2} viscous flow with slow VT relaxation. Normal stress and rates of vibrational relaxation are studied for various ratios of vibrational and translational temperatures. The cross effects between different vibrational transitions in viscous flows are evaluated, along with the influence of anharmonicity and flow compressibility on the first-order corrections to the relaxation rate. Limits of validity for the widely used Landau–Teller model of vibrational relaxation are indicated.

  8. Rate Constant and Reaction Coordinate of Trp-Cage Folding in Explicit Water

    PubMed Central

    Juraszek, Jarek; Bolhuis, Peter G.

    2008-01-01

    We report rate constant calculations and a reaction coordinate analysis of the rate-limiting folding and unfolding process of the Trp-cage mini-protein in explicit solvent using transition interface sampling. Previous transition path sampling simulations revealed that in this (un)folding process the protein maintains its compact configuration, while a (de)increase of secondary structure is observed. The calculated folding rate agrees reasonably with experiment, while the unfolding rate is 10 times higher. We discuss possible origins for this mismatch. We recomputed the rates with the forward flux sampling method, and found a discrepancy of four orders of magnitude, probably caused by the method's higher sensitivity to the choice of order parameter with respect to transition interface sampling. Finally, we used the previously computed transition path-sampling ensemble to screen combinations of many order parameters for the best model of the reaction coordinate by employing likelihood maximization. We found that a combination of the root mean-square deviation of the helix and of the entire protein was, of the set of tried order parameters, the one that best describes the reaction coordination. PMID:18676648

  9. Estimating Reaction Rate Coefficients Within a Travel-Time Modeling Framework

    SciTech Connect

    Gong, R; Lu, C; Luo, Jian; Wu, Wei-min; Cheng, H.; Criddle, Craig; Kitanidis, Peter K.; Gu, Baohua; Watson, David B; Jardine, Philip M; Brooks, Scott C

    2011-03-01

    A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transport over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics.

  10. Rate constant for the reaction of atomic chlorine with formaldehyde from 200 to 500 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Nava, D. F.; Payne, W. A.

    1979-01-01

    The absolute rate constant for the reaction of atomic chlorine with formaldehyde has been measured from 200 to 500 K using the flash photolysis-resonance fluorescence technique. The results were independent of substantial variations in (H2CO), total pressure (Ar), and flash intensity (i.e., initial (Cl)). The rate constant was shown to be invariant with temperature, the best representation for this temperature range being k-sub-1 = (7.48 + or - 0.50) times 10 to the -11 cu cm/molecule sec, where the error is one standard deviation. This result is compared with the only previous determination of k-sub-1, which was a relative value obtained at 298 K. The rate constant is theoretically discussed, and the potential importance of the reaction in stratospheric chemistry is considered.

  11. Does a Rater's Familiarity with a Candidate's Pronunciation Affect the Rating in Oral Proficiency Interviews?

    ERIC Educational Resources Information Center

    Carey, Michael D.; Mannell, Robert H.; Dunn, Peter K.

    2011-01-01

    This study investigated factors that could affect inter-examiner reliability in the pronunciation assessment component of speaking tests. We hypothesized that the rating of pronunciation is susceptible to variation in assessment due to the amount of exposure examiners have to nonnative English accents. An inter-rater variability analysis was…

  12. Self-Reported ADHD Symptoms among College Students: Item Positioning Affects Symptom Endorsement Rates

    ERIC Educational Resources Information Center

    Mitchell, John T.; Knouse, Laura E.; Nelson-Gray, Rosemery O.; Kwapil, Thomas R.

    2009-01-01

    Objective: The effect of manipulating item positioning on self-reported ADHD symptoms was examined. We assessed whether listing DSM-IV ADHD symptoms serially or interspersed affected (a) the correlation between ADHD symptoms and (b) the rate of symptom endorsement. Method: In Study 1, an undergraduate sample (n = 102) completed a measure that…

  13. Heart Rate Variability – a Tool to Differentiate Positive and Negative Affective States in Pigs?

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The causal neurophysiological processes, such as autonomic nervous system activity, that mediate behavioral and physiological reactivity to an environment have largely been ignored. Heart rate variability (HRV) analysis is a clinical diagnostic tool used to assess affective states (stressful and ple...

  14. Rate constants for the slow Mu + propane abstraction reaction at 300 K by diamagnetic RF resonance.

    PubMed

    Fleming, Donald G; Cottrell, Stephen P; McKenzie, Iain; Ghandi, Khashayar

    2015-08-14

    The study of kinetic isotope effects for H-atom abstraction rates by incident H-atoms from the homologous series of lower mass alkanes (CH4, C2H6 and, here, C3H8) provides important tests of reaction rate theory on polyatomic systems. With a mass of only 0.114 amu, the most sensitive test is provided by the rates of the Mu atom. Abstraction of H by Mu can be highly endoergic, due to the large zero-point energy shift in the MuH bond formed, which also gives rise to high activation energies from similar zero-point energy corrections at the transition state. Rates are then far too slow near 300 K to be measured by conventional TF-μSR techniques that follow the disappearance of the spin-polarised Mu atom with time. Reported here is the first measurement of a slow Mu reaction rate in the gas phase by the technique of diamagnetic radio frequency (RF) resonance, where the amplitude of the MuH product formed in the Mu + C3H8 reaction is followed with time. The measured rate constant, kMu = (6.8 ± 0.5) × 10(-16) cm(3) s(-1) at 300 K, is surprisingly only about a factor of three slower than that expected for H + C3H8, indicating a dominant contribution from quantum tunneling in the Mu reaction, consistent with elementary transition state theory calculations of the kMu/kH kinetic isotope effect. PMID:26165545

  15. Determination of reaction rates and activation energy in aerobic composting processes for yard waste.

    PubMed

    Uma, R N; Manjula, G; Meenambal, T

    2007-04-01

    The reaction rates and activation energy in aerobic composting processes for yard waste were determined using specifically designed reactors. Different mixture ratios were fixed before the commencement of the process. The C/N ratio was found to be optimum for a mixture ratio of 1:6 containing one part of coir pith to six parts of other waste which included yard waste, yeast sludge, poultry yard waste and decomposing culture (Pleurotosis). The path of stabilization of the wastes was continuously monitored by observing various parameters such as temperature, pH, Electrical Conductivity, C.O.D, VS at regular time intervals. Kinetic analysis was done to determine the reaction rates and activation energy for the optimum mixture ratio under forced aeration condition. The results of the analysis clearly indicated that the temperature dependence of the reaction rates followed the Arrhenius equation. The temperature coefficients were also determined. The degradation of the organic fraction of the yard waste could be predicted using first order reaction model. PMID:18476403

  16. Solvation effect on kinetic rate constant of reactions in supercritical solvents

    SciTech Connect

    Chialvo, A.A.; Cummings, P.T. |; Kalyuzhnyi, Yu.V.

    1998-03-01

    A statistical mechanical analysis of the solvation effects on the kinetic rate constants of reactions in near and supercritical solvents is presented to understand the experimental findings regarding the thermodynamic pressure effects. This is an extension of the solvation formalism of Chialvo and Cummings to the analysis of the microscopic basis for the macroscopic pressure and temperature effects on the kinetic rate constants of reactions conducted in the compressible region of the solvent phase diagram. This analysis is illustrated with integral equations calculations involving Lennard-Jones infinitely dilute quaternary systems to describe the species in solution during the reaction of triplet benzophenone ({sup 3}BP) with a cosolvent (either O{sub 2} or 1,4-cyclohexadiene) in supercritical CO{sub 2} along the supercritical isotherms T{sub r} = 1.01 and 1.06. The role of the species molecular asymmetries and consequently their solvation behavior in determining the thermodynamic pressure and temperature effects on the kinetic rate constant of reactions at near-critical conditions are discussed.

  17. Benchmark experiments for validation of reaction rates determination in reactor dosimetry

    NASA Astrophysics Data System (ADS)

    Rataj, J.; Huml, O.; Heraltova, L.; Bily, T.

    2014-11-01

    The precision of Monte Carlo calculations of quantities of neutron dosimetry strongly depends on precision of reaction rates prediction. Research reactor represents a very useful tool for validation of the ability of a code to calculate such quantities as it can provide environments with various types of neutron energy spectra. Especially, a zero power research reactor with well-defined core geometry and neutronic properties enables precise comparison between experimental and calculated data. Thus, at the VR-1 zero power research reactor, a set of benchmark experiments were proposed and carried out to verify the MCNP Monte Carlo code ability to predict correctly the reaction rates. For that purpose two frequently used reactions were chosen: He-3(n,p)H-3 and Au-197(n,γ)Au-198. The benchmark consists of response measurement of small He-3 gas filled detector in various positions of reactor core and of activated gold wires placed inside the core or to its vicinity. The reaction rates were calculated in MCNP5 code utilizing a detailed model of VR-1 reactor which was validated for neutronic calculations at the reactor. The paper describes in detail the experimental set-up of the benchmark, the MCNP model of the VR-1 reactor and provides a comparison between experimental and calculated data.

  18. Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Wilson, E., Jr.

    1998-01-01

    Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.

  19. Theoretical investigation on H abstraction reaction mechanisms and rate constants of Isoflurane with the OH radical

    NASA Astrophysics Data System (ADS)

    Ren, Hongjiang; Li, Xiaojun

    2015-12-01

    The mechanism of H abstraction reactions for Isoflurane with the OH radical was investigated using density functional theory and G3(MP2) duel theory methods. The geometrical structures of all the species were fully optimised at B3LYP/6-311++G** level of theory. Thermochemistry data were obtained by utilising the high accurate model chemistry method G3(MP2) combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for the reaction channels analysis. All the reaction channels were confirmed throughout the intrinsic reaction coordinate analysis. The results show that two channels were obtained, which correspond to P(1) and P(2) with the respective activation barriers of 63.03 and 54.82 kJ/mol. The rate constants for the two channels over a wide temperature range of 298.15-2000 K were predicted and the calculated data are in agreement with the experimental one. The results show that P(2) is the dominant reaction channel under 800 K and above 800 K, it can be found that P(1) will be more preferable reaction channel.

  20. Aqueous Complexation Reactions Governing the Rate and Extent of Biogeochemical U(VI) Reduction

    SciTech Connect

    Scott C. Brooks; Wenming Dong; Sue Carroll; James K. Fredrickson; Kenneth M. Kemner; Shelly D. Kelly

    2006-06-01

    The proposed research will elucidate the principal biogeochemical reactions that govern the concentration, chemical speciation, and reactivity of the redox-sensitive contaminant uranium. The results will provide an improved understanding and predictive capability of the mechanisms that govern the biogeochemical reduction of uranium in subsurface environments. In addition, the work plan is designed to: (1) Generate fundamental scientific understanding on the relationship between U(VI) chemical speciation and its susceptibility to biogeochemical reduction reactions. (2) Elucidate the controls on the rate and extent of contaminant reactivity. (3) Provide new insights into the aqueous and solid speciation of U(VI)/U(IV) under representative groundwater conditions.

  1. A new theoretical approach to thermonuclear radiative-capture reaction rate

    SciTech Connect

    Funaki, Yasuro; Yabana, Kazuhiro; Akahori, Takahiko

    2012-11-12

    We propose a new computational method for astrophysical reaction rate of radiative capture process, which does not require any solution of scattering problem. It is tested for twobody radiative caputure reaction {sup 16}O({alpha},{gamma}){sup 20}Ne and a comparison is made with an ordinary method solving two-body scattering problem. The method is shown to work well in practice and thus will be useful for problems in which an explicit construction of scattering solution is difficult such as the triple-alpha capture process.

  2. Rates for neutron-capture reactions on tungsten isotopes in iron meteorites. [Abstract only

    NASA Technical Reports Server (NTRS)

    Masarik, J.; Reedy, R. C.

    1994-01-01

    High-precision W isotopic analyses by Harper and Jacobsen indicate the W-182/W-183 ratio in the Toluca iron meteorite is shifted by -(3.0 +/- 0.9) x 10(exp -4) relative to a terrestrial standard. Possible causes of this shift are neutron-capture reactions on W during Toluca's approximately 600-Ma exposure to cosmic ray particles or radiogenic growth of W-182 from 9-Ma Hf-182 in the silicate portion of the Earth after removal of W to the Earth's core. Calculations for the rates of neutron-capture reactions on W isotopes were done to study the first possibility. The LAHET Code System (LCS) which consists of the Los Alamos High Energy Transport (LAHET) code and the Monte Carlo N-Particle(MCNP) transport code was used to numerically simulate the irradiation of the Toluca iron meteorite by galactic-cosmic-ray (GCR) particles and to calculate the rates of W(n, gamma) reactions. Toluca was modeled as a 3.9-m-radius sphere with the composition of a typical IA iron meteorite. The incident GCR protons and their interactions were modeled with LAHET, which also handled the interactions of neutrons with energies above 20 MeV. The rates for the capture of neutrons by W-182, W-183, and W-186 were calculated using the detailed library of (n, gamma) cross sections in MCNP. For this study of the possible effect of W(n, gamma) reactions on W isotope systematics, we consider the peak rates. The calculated maximum change in the normalized W-182/W-183 ratio due to neutron-capture reactions cannot account for more than 25% of the mass 182 deficit observed in Toluca W.

  3. Seemingly irrational driving behavior model: The effect of habit strength and anticipated affective reactions.

    PubMed

    Chung, Yi-Shih

    2015-09-01

    An increasing amount of evidence suggests that aberrant driving behaviors are not entirely rational. On the basis of the dual-process theory, this study postulates that drivers may learn to perform irrational aberrant driving behaviors, and these behaviors could be derived either from a deliberate or an intuitive decision-making approach. Accordingly, a seemingly irrational driving behavior model is proposed; in this model, the theory of planned behavior (TPB) was adopted to represent the deliberate decision-making mechanism, and habit strength was incorporated to reflect the intuitive decision process. A multiple trivariate mediation structure was designed to reflect the process through which driving behaviors are learned. Anticipated affective reactions (AARs) were further included to examine the effect of affect on aberrant driving behaviors. Considering the example of speeding behaviors, this study developed scales and conducted a two-wave survey of students in two departments at a university in Northern Taiwan. The analysis results show that habit strength consists of multiple aspects, and frequency of past behavior cannot be a complete repository for accumulating habit strength. Habit strength appeared to be a crucial mediator between intention antecedents (e.g., attitude) and the intention itself. Including habit strength in the TPB model enhanced the explained variance of speeding intention by 26.7%. In addition, AARs were different from attitudes; particularly, young drivers tended to perform speeding behaviors to reduce negative feelings such as regret. The proposed model provides an effective alternative approach for investigating aberrant driving behaviors; corresponding countermeasures are discussed. PMID:26056969

  4. Accurate label-free reaction kinetics determination using initial rate heat measurements

    PubMed Central

    Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Jacobs, Denise; Hagen, Wilfred R.

    2015-01-01

    Accurate label-free methods or assays to obtain the initial reaction rates have significant importance in fundamental studies of enzymes and in application-oriented high throughput screening of enzyme activity. Here we introduce a label-free approach for obtaining initial rates of enzyme activity from heat measurements, which we name initial rate calorimetry (IrCal). This approach is based on our new finding that the data recorded by isothermal titration calorimetry for the early stages of a reaction, which have been widely ignored, are correlated to the initial rates. Application of the IrCal approach to various enzymes led to accurate enzyme kinetics parameters as compared to spectroscopic methods and enabled enzyme kinetic studies with natural substrate, e.g. proteases with protein substrates. Because heat is a label-free property of almost all reactions, the IrCal approach holds promise in fundamental studies of various enzymes and in use of calorimetry for high throughput screening of enzyme activity. PMID:26574737

  5. Substituent effects on the reaction rates of hydrogen abstraction in the pyrolysis of phenethyl phenyl ethers

    SciTech Connect

    Beste, Ariana; Buchanan III, A C

    2010-01-01

    We report reaction profiles and forward rate constants for hydrogen abstraction reactions occurring in the pyrolysis of methoxy-substituted derivatives of phenethyl phenyl ether (PhCH{sub 2}CH{sub 2}OPh, PPE), where the substituents are located on the aryl ether ring (PhCH{sub 2}CH{sub 2}OPh-X). We use density functional theory in combination with transition-state theory, and anharmonic corrections are included within the independent mode approximation. PPE is the simplest model of the abundant {beta}-O-4 linkage in lignin. The mechanism of PPE pyrolysis and overall product selectivities have been studied experimentally by one of us, which was followed by computational analysis of key individual hydrogen-transfer reaction steps. In the previous work, we have been able to use a simplified kinetic model based on quasi-steady-state conditions to reproduce experimental {alpha}/{beta} selectivities for PPE and PPEs with substituents on the phenethyl ring (X-PhCH{sub 2}CH{sub 2}OPh). This model is not applicable to PPE derivatives where methoxy substituents are located on the phenyl ring adjacent to the ether oxygen because of the strongly endothermic character of the hydrogen abstraction by substituted phenoxy radicals as well as the decreased kinetic chain lengths resulting from enhanced rates of the initial C?O homolysis step. Substituents decelerate the hydrogen abstraction by the phenoxy radical, while the influence on the benzyl abstraction is less homogeneous. The calculations provide insight into the contributions of steric and polar effects in these important hydrogen-transfer steps. We emphasize the importance of an exhaustive conformational space search to calculate rate constants and product selectivities. The computed rate constants will be used in future work to numerically simulate the pyrolysis mechanism, pending the calculation of the rate constants of all participating reactions.

  6. Light elements burning reaction rates at stellar temperatures as deduced by the Trojan Horse measurements

    SciTech Connect

    Lamia, L.; Spitaleri, C.; La Cognata, M.; Palmerini, S.; Sergi, M. L.; Puglia, S. M. R.

    2015-02-24

    Experimental nuclear astrophysics aims at determining the reaction rates for astrophysically relevant reactions at their Gamow energies. For charged-particle induced reactions, the access to these energies is usually hindered, in direct measurements, by the presence of the Coulomb barrier between the interacting particles or by electron screening effects, which make hard the determination of the bare-nucleus S(E)-factor of interest for astrophysical codes. The use of the Trojan Horse Method (THM) appears as one of the most suitable tools for investigating nuclear processes of interest for astrophysics. Here, in view of the recent TH measurements, the main destruction channels for deuterium ({sup 2}H), for the two lithium {sup 6,7}Li isotopes, for the {sup 9}Be and the one for the two boron {sup 10,11}B isotopes will be discussed.

  7. On the Rate and Mechanism of Proton Transfer Reactions in Proteins

    NASA Astrophysics Data System (ADS)

    Xie, Aihua; Li, Yunxing; Manda, Edward; Nie, Beining; Hoff, Wouter; Martin, Richard

    2009-03-01

    One of the fundamental processes in molecular biology is proton transfer reactions in proteins. Proton transfer is essential for the biological functions of proteins responsible in bioenergetics, biological signaling, and enzymatic catalysis. The mechanism of proton transfer is of great interests in order to understand the structural basis of biological functions. Despite of extensive experimental and computational efforts, it remains elusive what causes a proton to move from the proton donor to the proton acceptor. We will report a proof of concept study regarding a general mechanism of internal proton transfer reactions in proteins. Density functional theory, B3LYP/6-311+G(2d,p), is employed in this study. The results of our study provide deep insights into the structural basis to the rate and mechanism of proton transfer reactions in proteins, such as bacteriorhodopsin and green fluorescence protein.

  8. Light elements burning reaction rates at stellar temperatures as deduced by the Trojan Horse measurements

    NASA Astrophysics Data System (ADS)

    Lamia, L.; Spitaleri, C.; La Cognata, M.; Palmerini, S.; Puglia, S. M. R.; Sergi, M. L.

    2015-02-01

    Experimental nuclear astrophysics aims at determining the reaction rates for astrophysically relevant reactions at their Gamow energies. For charged-particle induced reactions, the access to these energies is usually hindered, in direct measurements, by the presence of the Coulomb barrier between the interacting particles or by electron screening effects, which make hard the determination of the bare-nucleus S(E)-factor of interest for astrophysical codes. The use of the Trojan Horse Method (THM) appears as one of the most suitable tools for investigating nuclear processes of interest for astrophysics. Here, in view of the recent TH measurements, the main destruction channels for deuterium (2H ), for the two lithium 6,7Li isotopes, for the 9Be and the one for the two boron 10,11B isotopes will be discussed.

  9. Rate coefficients of hydroxyl radical reactions with pesticide molecules and related compounds: A review

    NASA Astrophysics Data System (ADS)

    Wojnárovits, László; Takács, Erzsébet

    2014-03-01

    Rate coefficients published in the literature on hydroxyl radical reactions with pesticides and related compounds are discussed together with the experimental methods and the basic reaction mechanisms. Recommendations are made for the most probable values. Most of the molecules whose rate coefficients are discussed have aromatic ring: their rate coefficients are in the range of 2×109-1×1010 mol-1 dm3 s-1. The rate coefficients show some variation with the electron withdrawing-donating nature of the substituent on the ring. The rate coefficients for triazine pesticides (simazine, atrazine, prometon) are all around 2.5×109 mol-1 dm3 s-1. The values do not show variation with the substituent on the s-triazine ring. The rate coefficients for the non-aromatic molecules which have C=C double bonds or several C-H bonds may also be above 1×109 mol-1 dm3 s-1. However, the values for molecules without C=C double bonds or several C-H bonds are in the 1×107-1×109 mol-1 dm3 s-1 range.

  10. Does overall reinforcer rate affect discrimination of time-based contingencies?

    PubMed

    Cowie, Sarah; Davison, Michael; Blumhardt, Luca; Elliffe, Douglas

    2016-05-01

    Overall reinforcer rate appears to affect choice. The mechanism for such an effect is uncertain, but may relate to reinforcer rate changing the discrimination of the relation between stimuli and reinforcers. We assessed whether a quantitative model based on a stimulus-control approach could be used to account for the effects of overall reinforcer rate on choice under changing time-based contingencies. On a two-key concurrent schedule, the likely availability of a reinforcer reversed when a fixed time had elapsed since the last reinforcer, and the overall reinforcer rate was varied across conditions. Changes in the overall reinforcer rate produced a change in response bias, and some indication of a change in discrimination. These changes in bias and discrimination always occurred quickly, usually within the first session of a condition. The stimulus-control approach provided an excellent account of the data, suggesting that changes in overall reinforcer rate affect choice because they alter the frequency of reinforcers obtained at different times, or in different stimulus contexts, and thus change the discriminated relation between stimuli and reinforcers. These findings support the notion that temporal and spatial discriminations can be understood in terms of discrimination of reinforcers across time and space. PMID:27151836

  11. Disruption of insulin signalling affects the neuroendocrine stress reaction in Drosophila females.

    PubMed

    Rauschenbach, Inga Y; Karpova, Evgenia K; Adonyeva, Natalya V; Andreenkova, Olga V; Faddeeva, Natalya V; Burdina, Elena V; Alekseev, Alexander A; Menshanov, Petr N; Gruntenko, Nataly E

    2014-10-15

    Juvenile hormone (JH) and dopamine are involved in the stress response in insects. The insulin/insulin-like growth factor signalling pathway has also recently been found to be involved in the regulation of various processes, including stress tolerance. However, the relationships between the JH, dopamine and insulin signalling pathways remain unclear. Here, we study the role of insulin signalling in the regulation of JH and dopamine metabolism under normal and heat stress conditions in Drosophila melanogaster females. We show that suppression of the insulin-like receptor (InR) in the corpus allatum, a specialised endocrine gland that synthesises JH, causes an increase in dopamine level and JH-hydrolysing activity and alters the activities of enzymes that produce as well as those that degrade dopamine [alkaline phosphatase (ALP), tyrosine hydroxylase (TH) and dopamine-dependent arylalkylamine N-acetyltransferase (DAT)]. We also found that InR suppression in the corpus allatum modulates dopamine, ALP, TH and JH-hydrolysing activity in response to heat stress and that it decreases the fecundity of the flies. JH application restores dopamine metabolism and fecundity in females with decreased InR expression in the corpus allatum. Our data provide evidence that the insulin/insulin-like growth factor signalling pathway regulates dopamine metabolism in females of D. melanogaster via the system of JH metabolism and that it affects the development of the neuroendocrine stress reaction and interacts with JH in the control of reproduction in this species. PMID:25214494

  12. Children's affective reactions and coping under threat of missile attack: a semiprojective assessment procedure.

    PubMed

    Zeidner, M; Klingman, A; Itskowitz, R

    1993-06-01

    This study reports on 170 Israeli school children at risk for missile attack during the Persian Gulf War. The Bar-Ilan Picture Test for Children (Itskowitz & Strauss, 1982, 1986) was specially adapted to the war situation specifically to measure children's affective reactions and coping strategies. Children with a greater sense of control and social support, and more complex defenses, tended to demonstrate better coping strategies. Children who were less defensive showed higher levels of anxiety under stress. Children scoring higher in social support showed greater perceived control over their immediate environment and more verbal expressivity with respect to the crisis situation. Girls scored higher than boys on emotional and verbal expressiveness. These data, elicited through semiprojective procedures, are consistent with much of the prior research based mainly on objective scales or self-report questionnaires. Overall, the results lend additional validity to the nexus of relations (largely established through conventional objective scales) between resources, coping, and outcomes in a naturalistic stressor situation. PMID:8336260

  13. Receptor clustering affects signal transduction at the membrane level in the reaction-limited regime

    NASA Astrophysics Data System (ADS)

    Caré, Bertrand R.; Soula, Hédi A.

    2013-01-01

    Many types of membrane receptors are found to be organized as clusters on the cell surface. We investigate the potential effect of such receptor clustering on the intracellular signal transduction stage. We consider a canonical pathway with a membrane receptor (R) activating a membrane-bound intracellular relay protein (G). We use Monte Carlo simulations to recreate biochemical reactions using different receptor spatial distributions and explore the dynamics of the signal transduction. Results show that activation of G by R is severely impaired by R clustering, leading to an apparent blunted biological effect compared to control. Paradoxically, this clustering decreases the half maximal effective dose (ED50) of the transduction stage, increasing the apparent affinity. We study an example of inter-receptor interaction in order to account for possible compensatory effects of clustering and observe the parameter range in which such interactions slightly counterbalance the loss of activation of G. The membrane receptors’ spatial distribution affects the internal stages of signal amplification, suggesting a functional role for membrane domains and receptor clustering independently of proximity-induced receptor-receptor interactions.

  14. Rate constants for reactions between atmospheric reservoir species. 2. H sub 2 O

    SciTech Connect

    Hatakeyama, Shiro; Leu, Mingtaun )

    1989-07-27

    The kinetics of the reactions of H{sub 2}O with ClONO{sub 2}, N{sub 2}O{sub 5}, O{sub 3}, and COCl{sub 2} have been investigated by using a large-volume static cell and a Fourier transform infrared spectrometer at 296 K. Upper limits for the homogeneous gas-phase reaction rate constants of the ClONO{sub 2} + H{sub 2}O, N{sub 2}O{sub 5} + H{sub 2}O, O{sub 3} + H{sub 2}O, and COCl{sub 2} + H{sub 2}O reactions were found to be 3.4 {times} 10{sup {minus}21}, 2.8 {times} 10{sup {minus}21}, 1.1 {times} 10{sup {minus}22}, and 1.2 {times} 10{sup {minus}23}, respectively (all in units of cm{sup 3} s{sup {minus}1}), based on the observed decay rates of ClONO{sub 2}, N{sub 2}O{sub 5}, O{sub 3}, and COCl{sub 2}. Product analyses gave 0.82 {plus minus} 0.07 for the yield of HNO{sub 3} in the ClONO{sub 2} + H{sub 2}O {yields} HOCl + HNO{sub 3} reaction and 1.1 {plus minus} 0.3 for the yield of HNO{sub 3} from the N{sub 2}O{sub 5} + H{sub 2}O {yields} 2HNO{sub 3} reaction. The quoted error represents one standard deviation of the measurement. An attempt was also made to monitor possible reaction products such as H{sub 2}O{sub 2} for the O{sub 3} + H{sub 2}O reaction, and CO{sub 2} or HCl for the COCl{sub 2} + H{sub 2}O reaction. These results may be important in the elucidation of the springtime Antarctic ozone depletion over the past decade. The implication for NO{sub x} chemistry in the nighttime troposphere based on their results of the N{sub 2}O{sub 5} + H{sub 2}O reaction will be discussed.

  15. A review of modifying factors affecting usage of diagnostic rating scales in concussion management.

    PubMed

    Dessy, Alexa; Rasouli, Jonathan; Gometz, Alex; Choudhri, Tanvir

    2014-07-01

    Sport-related concussion has gained increasing recognition as a result of recent legislation, public health initiatives and media coverage. Moreover, there have been substantial paradigm shifts in the management of concussion. This article will discuss the variables that affect the use of diagnostic rating scales such as ImPACT and SCAT in the current management of concussed individuals. Specifically, patient-specific modifying factors affecting test interpretation, including age, gender, fitness level, psychiatric conditions, learning disorders and other components of medical history will be addressed, as well as methodological concerns with baseline testing. PMID:24908218

  16. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension

    NASA Astrophysics Data System (ADS)

    Greene, Samuel M.; Shan, Xiao; Clary, David C.

    2016-06-01

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.

  17. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension.

    PubMed

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2016-06-28

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods. PMID:27369506

  18. Investigation of Mixing and Chemical Reaction Interactions Using Rate-Controlled Constrained-Equilibrium

    NASA Astrophysics Data System (ADS)

    Hadi, Fatemeh; Janbozorgi, Mohammad; Sheikhi, Reza H.; Metghalchi, Hameed

    2014-11-01

    The Rate-Controlled Constrained-Equilibrium (RCCE) method is applied to study the interaction between mixing and chemical reaction in a constant pressure Partially-Stirred Reactor (PaSR). The objective is to understand the influence of mixing on RCCE predictions. The RCCE is a computationally efficient method based on thermodynamics to implement the combustion chemistry. In the RCCE the dynamics of reacting systems is described by a small number of rate-controlling reactions and slowly-varying constraints. The method is applied to study methane combustion via 12 constraints and 133 reaction steps. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The RCCE predictions are assessed by comparing with those of detailed kinetics model, in which the same kinetics, involving 29 species and 133 reaction steps, is integrated directly. Chemical kinetics and mixing interactions are studied for different residence and mixing time scales. Results show that the RCCE accurately represents the effect of mixing with different mixing strengths. An assessment of numerical performance of the RCCE is also performed. It is shown that the method is effective to reduce the stiffness of the kinetics and thus allows simulations with much lower computation costs.

  19. Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

    SciTech Connect

    Peters, Catherine A

    2013-02-28

    Geochemical reactions in deep subsurface environments are complicated by the consolidated nature and mineralogical complexity of sedimentary rocks. Understanding the kinetics of these reactions is critical to our ability to make long-term predictions about subsurface processes such as pH buffering, alteration in rock structure, permeability changes, and formation of secondary precipitates. In this project, we used a combination of experiments and numerical simulation to bridge the gap between our knowledge of these reactions at the lab scale and rates that are meaningful for modeling reactive transport at core scales. The focus is on acid-driven mineral dissolution, which is specifically relevant in the context of CO2-water-rock interactions in geological sequestration of carbon dioxide. The project led to major findings in three areas. First, we modeled reactive transport in pore-network systems to investigate scaling effects in geochemical reaction rates. We found significant scaling effects when CO2 concentrations are high and reaction rates are fast. These findings indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. Second, we used mathematical modeling to investigate the extent to which SO2, if co-injected with CO2, would acidify formation brines. We found that there exist realistic conditions in which the impact on brine acidity will be limited due to diffusion rate-limited SO2 dissolution from the CO2 phase, and the subsequent pH shift may also be limited by the lack of availability of oxidants to produce sulfuric acid. Third, for three Viking sandstones (Alberta sedimentary basin, Canada), we employed backscattered electron microscopy and energy dispersive X-ray spectroscopy to statistically characterize mineral contact with pore space. We determined that for reactive minerals in sedimentary consolidated rocks, abundance alone is not a good predictor of

  20. Rate of reactions between D 2O and Ca xAl yO z

    NASA Astrophysics Data System (ADS)

    Christensen, A. Nørlund; Lehmann, M. S.

    1984-02-01

    The rate of the reaction between D 2O and the calcium aluminum oxides Ca 3Al 2O 6, Ca 5Al 6O 14, CaAl 2O 4, and CaAl 4O 7 was investigated by on-line neutron diffraction powder methods at temperatures from room temperature to 100°C. The rate of the reaction increases with increasing calcium content of the compounds and with increasing temperature for each of the compounds. The crystallographic stable hydrate Ca 3Al 2(OD) 12 is obtained from CaAl 4O 7 and CaAl 2O 4 at temperatures above 63°C, from Ca 5Al 6O 14 at temperatures above 49°C, and from Ca 3Al 2O 6 at temperatures as low as 7°C.

  1. Reacting gas mixtures in the state-to-state approach: The chemical reaction rates

    SciTech Connect

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-12-09

    In this work chemically reacting mixtures of viscous flows are analyzed within the framework of Boltzmann equation. By applying a modified Chapman-Enskog method to the system of Boltzmann equations general expressions for the rates of chemical reactions and vibrational energy transitions are determined as functions of two thermodynamic forces: the velocity divergence and the affinity. As an application chemically reacting mixtures of N{sub 2} across a shock wave are studied, where the first lowest vibrational states are taken into account. Here we consider only the contributions from the first four single quantum vibrational-translational energy transitions. It is shown that the contribution to the chemical reaction rate related to the affinity is much larger than that of the velocity divergence.

  2. Absolute rate of the reaction of bromine atoms with ozone from 200-360 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Lee, J. H.; Payne, W. A.; Stief, L. J.

    1978-01-01

    The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at lambda 165nm.O3 was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3, total pressure and limited variations in flash intensity. The measured rate constants obeyed the Arrhenius expression, where the error quoted is two standard deviations. Results are compared with previous determinations which employed the discharge flow-mass spectrometric technique.

  3. Absolute rate of the reaction of bromine atoms with ozone from 200 to 360 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Lee, J. H.; Payne, W. A.; Stief, L. J.

    1978-01-01

    The rate constant for the reaction Br + O3 yields BrO + O2 has been measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at a wavelength of 165 nm. O3 concentration was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3 concentration, total pressure (Ar), and limited variations in flash intensity (i.e., initial Br concentration). The measured rate constants obey the Arrhenius expression, k = (7.74 plus or minus 0.50) x 10 to the -12th exp(-603 plus or minus 16/T) cu cm/molecule/sec, where the error quoted is two standard deviations.

  4. Absolute rate parameters for the reaction of atomic hydrogen with hydrazine

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Payne, W. A.

    1976-01-01

    Absolute rate parameters for the reaction of atomic hydrogen with hydrazine H + N2H4 yields H2 + N2H3 have been determined in a direct manner using flash photolysis of dilute mixtures of hydrazine in helium and time dependent observation of H via resonance fluorescence. By measuring the H-atom decay under pseudo-first-order conditions, the bimolecular rate constant K sub 1 was obtained over the temperature range 228-400 K. The data were fitted with good linearity to the Arrhenius expression K sub 1 = (9.87 plus or minus 1.17) x 10 to the -12th exp(-2380 plus or minus 100/RT) cu cm/molecule/s. The data were shown to be free of any contributions from secondary reactions involving H as a reactant or product.

  5. 23Na (α,p )26Mg Reaction Rate at Astrophysically Relevant Energies

    NASA Astrophysics Data System (ADS)

    Howard, A. M.; Munch, M.; Fynbo, H. O. U.; Kirsebom, O. S.; Laursen, K. L.; Diget, C. Aa.; Hubbard, N. J.

    2015-07-01

    The production of 26Al in massive stars is sensitive to the 23Na (α,p )26Mg cross section. Recent experimental data suggest the currently recommended cross sections are underestimated by a factor of ˜40 . We present here differential cross sections for the 23Na (α,p )26Mg reaction measured in the energy range Ec .m .=1.7 - 2.5 MeV . Concurrent measurements of Rutherford scattering provide absolute normalizations that are independent of variations in target properties. Angular distributions are measured for both p0 and p1 permitting the determination of total cross sections. The results show no significant deviation from the statistical model calculations upon which the recommended rates are based. We therefore retain the previous recommendation without the increase in cross section and resulting stellar reaction rates by a factor of 40, impacting the 26Al yield from massive stars by more than a factor of 3.

  6. Computational Approach for Ranking Mutant Enzymes According to Catalytic Reaction Rates

    PubMed Central

    Kumarasiri, Malika; Baker, Gregory A.; Soudackov, Alexander V.

    2009-01-01

    A computationally efficient approach for ranking mutant enzymes according to the catalytic reaction rates is presented. This procedure requires the generation and equilibration of the mutant structures, followed by the calculation of partial free energy curves using an empirical valence bond potential in conjunction with biased molecular dynamics simulations and umbrella integration. The individual steps are automated and optimized for computational efficiency. This approach is used to rank a series of 15 dihydrofolate reductase mutants according to the hydride transfer reaction rate. The agreement between the calculated and experimental changes in the free energy barrier upon mutation is encouraging. The computational approach predicts the correct direction of the change in free energy barrier for all mutants, and the correlation coefficient between the calculated and experimental data is 0.82. This general approach for ranking protein designs has implications for protein engineering and drug design. PMID:19235997

  7. Hydrolysis of lanthanide dicarbides: Rates of reaction of cubic and tetragonal solid solutions with water

    SciTech Connect

    McColm, I.J. )

    1993-05-01

    Two series of solid solutions, Ho[sub 1[minus]x]La[sub x]C[sub 2] and Nd[sub 1[minus]x]LaC[sub 2], have been made and their X-ray unit cell parameters measured. The Ho[sub 1[minus]x]La[sub x]C[sub 2] series contains two tetragonal phases and a cubic solid solution series which has enabled the reaction rate constants for the water hydrolysis reaction of a cubic dicarbide phase to be determined for the first time. By comparing the linear rate constants and the activation energies across the two series the nature of bonding in general and the structure of the cubic phase are elucidated. A comparison with microhardness data is made and the change in M-C[sub 2] bonding as a function of composition is considered. 10 refs., 9 figs., 3 tabs.

  8. Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

    NASA Technical Reports Server (NTRS)

    Leu, M. T.; Lin, C. L.; Demore, W. B.

    1977-01-01

    The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

  9. Quantitative determination of the steady-state kinetics of multienzyme reactions using the algebraic rate equations for the component single-enzyme reactions.

    PubMed Central

    Stoner, C D

    1993-01-01

    Methods are given whereby the steady-state kinetic characteristics of multienzyme reactions consisting of individual single-enzyme reactions linked by freely diffusible intermediates can be determined quantitatively from the experimentally determined complete algebraic rate equations for the individual reactions. The approach is based on the fact that a valid steady-state rate equation for such a multienzyme reaction, in terms of the rate equations for the individual reactions, can be obtained simply from knowledge of the relative rates of the individual reactions when the multienzyme reaction is in the steady state. A number of model multienzyme reactions, which differ as to structural arrangement of the individual reactions, are examined by this approach. Simple mathematical methods which are applicable to most of these models are given for direct calculation of dependent variables. It is either pointed out or demonstrated with Mathematica that the rate equations for all of these models can be handled very easily with the aid of a personal computer equipped with appropriate equation-solving software. Since the approach permits evaluation of all dependent variables for any specific combination of values for the kinetic parameters and independent variables, numerical values for the flux control coefficients of the individual enzymes can be obtained by direct calculation for a wide variety of conditions and can be compared with those obtained according to the methods of Metabolic Control Analysis. Several such comparisons have been made and in all cases identical results were obtained. The intuitive notion that the individual enzymes of a multienzyme reaction would be equally rate limiting if the total amount of enzyme were being used with maximum efficiency is tested and shown to be incorrect. In the course of this test the flux control coefficient for the individual enzymes were found to be appropriate indicators of relative rate limitation or control by the

  10. Turnover rate, reaction order, and elementary steps for the hydrodechlorination of chlorofluorocarbon compounds on palladium catalysts

    SciTech Connect

    Thompson, C.D.; Rioux, R.M.; Chen, N.; Ribeiro, F.H.

    2000-04-13

    The rates of hydrodechlorination catalyzed by Pd supported on carbon for four chlorofluorocarbons spanned a range of 7 orders of magnitude. The rates scaled up to the bond strength of the carbon-chlorine bond for the gas-phase reactant. This finding demonstrates that the rate-determining step involves the scission of the C-Cl bond and suggests, through Polanyi and linear free-energy relationships, that rates for other compounds can be estimated if the C-Cl bond strength is known. The reaction orders for the most abundant products are approximately first-order for the chlorine-containing compound, half-order in H{sub 2}, and inverse first-order in HCl. The reaction steps consistent with these orders include a rate-determining step involving the adsorption of the chlorofluorocarbon to a single site (which could be a single surface palladium atom) and equilibrated steps between gas-phase H{sub 2}, gas-phase HCl, and adsorbed hydrogen and chlorine atoms. The rates on the supported catalysts are comparable to the ones reported before on a Pd foil, indicating that the support does not play a role in the reaction. The product distribution is independent of conversion, implying that the various products are formed from a single visit of the reactant on the surface and not from readsorption of gas-phase products. The four compounds studied were chloropentafluoroethane (CF{sub 3}-CF{sub 2}Cl), 2-chloro-1,1,1,2-tetrafluoroethane (CF{sub 3}-CFClH), 1,1-dichlorotetrafluoroethane (CF{sub 3}-CFCl{sub 2}), and 1,1,1-trichloro-2,2,2-trifluoroethane (CF{sub 3}-CCl{sub 3}).

  11. Speaking rate affects the perception of duration as a suprasegmental lexical-stress cue.

    PubMed

    Reinisch, Eva; Jesse, Alexandra; McQueen, James M

    2011-06-01

    Three categorization experiments investigated whether the speaking rate of a preceding sentence influences durational cues to the perception of suprasegmental lexical-stress patterns. Dutch two-syllable word fragments had to be judged as coming from one of two longer words that matched the fragment segmentally but differed in lexical stress placement. Word pairs contrasted primary stress on either the first versus the second syllable or the first versus the third syllable. Duration of the initial or the second syllable of the fragments and rate of the preceding context (fast vs. slow) were manipulated. Listeners used speaking rate to decide about the degree of stress on initial syllables whether the syllables' absolute durations were informative about stress (Experiment Ia) or not (Experiment Ib). Rate effects on the second syllable were visible only when the initial syllable was ambiguous in duration with respect to the preceding rate context (Experiment 2). Absolute second syllable durations contributed little to stress perception (Experiment 3). These results suggest that speaking rate is used to disambiguate words and that rate-modulated stress cues are more important on initial than noninitial syllables. Speaking rate affects perception of suprasegmental information. PMID:21848077

  12. A Review of the Thermodynamic, Transport, and Chemical Reaction Rate Properties of High-temperature Air

    NASA Technical Reports Server (NTRS)

    Hansen, C Frederick; Heims, Steve P

    1958-01-01

    Thermodynamic and transport properties of high temperature air, and the reaction rates for the important chemical processes which occur in air, are reviewed. Semiempirical, analytic expressions are presented for thermodynamic and transport properties of air. Examples are given illustrating the use of these properties to evaluate (1) equilibrium conditions following shock waves, (2) stagnation region heat flux to a blunt high-speed body, and (3) some chemical relaxation lengths in stagnation region flow.

  13. Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

    NASA Technical Reports Server (NTRS)

    Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1978-01-01

    Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically.

  14. Rate constants for reactions of ClO/x/ of atmospheric interest

    NASA Technical Reports Server (NTRS)

    Watson, R. T.

    1977-01-01

    Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

  15. The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

    NASA Technical Reports Server (NTRS)

    Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

    2004-01-01

    The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

  16. Rate of the reaction of atomic hydrogen with propyne over an extended pressure and temperature range

    NASA Technical Reports Server (NTRS)

    Whytock, D. A.; Payne, W. A.; Stief, L. J.

    1976-01-01

    The technique of flash photolysis coupled with time resolved detection of H via resonance fluorescence has been used to obtain rate constants for the reaction of atomic hydrogen with propyne at temperatures from 215 to 460 K and at pressures in the range 5-600 torr. The rate constants are strongly pressure dependent and the high pressure limiting values give rise to the Arrhenius expression K = approximately 6 x 10 to the minus 11th exp(-2450T) cu cm per molecule per sec. The results are discussed and compared with those of previous studies

  17. Foaming and the Rate of the Carbon-Iron Oxide Reaction in Slag

    NASA Astrophysics Data System (ADS)

    Corbari, Rodrigo; Matsuura, Hiroyuki; Halder, Sabuj; Walker, Matthew; Fruehan, Richard J.

    2009-12-01

    Foaming in the electric arc furnace is achieved by injecting carbon into slag, where the resulting reaction of the carbon with FeO dissolved in the slag generates gas (CO) that causes the slag to foam. In this research, the rate of the reaction of FeO in slag with carbon and the resulting foam height were measured. In these experiments, the FeO content of the slag ranged from 15 to 45 mass pct, and several different types of carbon were used including graphite, coals, and chars. The rate of the slag-carbon reaction and the consequent CO generation increased with FeO content of the slag from 15 to 45 mass pct. However, the slag foam height reached a maximum at about 25 mass pct FeO and decreased at higher FeO contents. The decrease in foaming is apparently due to a decrease in the foam index or foamability caused by a decrease in viscosity and an increase in density of the slag with FeO content. The results of this work indicate that the foam height is influenced more significantly by the decrease in the foam index compared to the increase in the CO gas generation rate at higher FeO contents. The decrease in the foam index with FeO agrees with that predicted from the slag properties.

  18. Rates and mechanisms of the atomic oxygen reaction with nickel at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Christian, J. D.; Gilbreath, W. P.

    1973-01-01

    The oxidation of nickel by atomic oxygen at pressure from 1 to 45 N/sq m between 1050 and 1250 K was investigated. In these ranges, the oxidation was found to follow the parobolic rate law, viz., K sub p = 0.0000114 exp(-13410/T) g squared/cm4/sec for films of greater than 1 micron thickness and was pressure independent. The activation enthalpy for the oxidation reaction was 112 + or - 11 kj/mole (27 + or - 3 kcal/mole). Of a number of possible mechanisms and defect structures considered, it was shown that the most likely was a saturated surface defect model for atomic oxidation, based on reaction activation enthalpies, impurity effects, pressure independence, and magnitudes of rates. A model judged somewhat less likely was one having doubly ionized cationic defects rate controlling in both atomic and molecular oxygen. From comparisons of the appropriate processes, the following enthalpy values were derived: enthalpy of activation (Ni diffusion in Ni0) = 110 + or - 30 kj/mole and standard enthalpy change for reaction formation (doubly ionized cation vacancies in Ni0 from atomic oxygen)= -9 + or - 25 kj/mole.

  19. Ejaculate and type of freezing extender affect rates of fertilization of horse oocytes in vitro.

    PubMed

    Roasa, L M; Choi, Y H; Love, C C; Romo, S; Varner, D D; Hinrichs, K

    2007-09-01

    In vitro fertilization (IVF) was performed on in vitro-matured equine oocytes in three experiments. Frozen-thawed sperm were prepared using swim-up separation and heparin treatment. In Experiment 1, fertilization was achieved with sperm from only one frozen ejaculate of four obtained from the same stallion. Within this ejaculate, fertilization rates were higher with fresh media, as compared to media held for 6-8 days before use (39.6% versus 7.3%, respectively; P<0.001). The type of bovine serum albumin used affected fertilization rates (4% versus 39.6%; P<0.001). To determine if IVF rates were influenced by factors associated with the freezing process (Experiment 2), a single ejaculate from a second stallion was frozen using eight variations in timing of steps in the freezing protocol. There were no differences among treatments in fertilization rates (range, 0-3%). In Experiment 3, fertilization rates of semen frozen in an extender containing 21.5% egg yolk were lower than fertilization rates of semen from the same ejaculate but frozen with a 3% egg-yolk extender (0% versus 15%, respectively; P<0.01). We inferred that rates of equine IVF with frozen-thawed sperm were influenced by ejaculate, the composition and age of the media used, and freezing extender. To our knowledge, this is the first report of ejaculate or extender differences affecting in vitro fertilization in this species. These factors may help to explain the great variability in fertilization rates reported with equine IVF, both among and within laboratories. PMID:17614128

  20. Keeping Pace with Your Eating: Visual Feedback Affects Eating Rate in Humans.

    PubMed

    Wilkinson, Laura L; Ferriday, Danielle; Bosworth, Matthew L; Godinot, Nicolas; Martin, Nathalie; Rogers, Peter J; Brunstrom, Jeffrey M

    2016-01-01

    Deliberately eating at a slower pace promotes satiation and eating quickly has been associated with a higher body mass index. Therefore, understanding factors that affect eating rate should be given high priority. Eating rate is affected by the physical/textural properties of a food, by motivational state, and by portion size and palatability. This study explored the prospect that eating rate is also influenced by a hitherto unexplored cognitive process that uses ongoing perceptual estimates of the volume of food remaining in a container to adjust intake during a meal. A 2 (amount seen; 300 ml or 500 ml) x 2 (amount eaten; 300 ml or 500 ml) between-subjects design was employed (10 participants in each condition). In two 'congruent' conditions, the same amount was seen at the outset and then subsequently consumed (300 ml or 500 ml). To dissociate visual feedback of portion size and actual amount consumed, food was covertly added or removed from a bowl using a peristaltic pump. This created two additional 'incongruent' conditions, in which 300 ml was seen but 500 ml was eaten or vice versa. We repeated these conditions using a savoury soup and a sweet dessert. Eating rate (ml per second) was assessed during lunch. After lunch we assessed fullness over a 60-minute period. In the congruent conditions, eating rate was unaffected by the actual volume of food that was consumed (300 ml or 500 ml). By contrast, we observed a marked difference across the incongruent conditions. Specifically, participants who saw 300 ml but actually consumed 500 ml ate at a faster rate than participants who saw 500 ml but actually consumed 300 ml. Participants were unaware that their portion size had been manipulated. Nevertheless, when it disappeared faster or slower than anticipated they adjusted their rate of eating accordingly. This suggests that the control of eating rate involves visual feedback and is not a simple reflexive response to orosensory stimulation. PMID:26828922

  1. Keeping Pace with Your Eating: Visual Feedback Affects Eating Rate in Humans

    PubMed Central

    Bosworth, Matthew L.; Godinot, Nicolas; Martin, Nathalie; Rogers, Peter J.; Brunstrom, Jeffrey M.

    2016-01-01

    Deliberately eating at a slower pace promotes satiation and eating quickly has been associated with a higher body mass index. Therefore, understanding factors that affect eating rate should be given high priority. Eating rate is affected by the physical/textural properties of a food, by motivational state, and by portion size and palatability. This study explored the prospect that eating rate is also influenced by a hitherto unexplored cognitive process that uses ongoing perceptual estimates of the volume of food remaining in a container to adjust intake during a meal. A 2 (amount seen; 300ml or 500ml) x 2 (amount eaten; 300ml or 500ml) between-subjects design was employed (10 participants in each condition). In two ‘congruent’ conditions, the same amount was seen at the outset and then subsequently consumed (300ml or 500ml). To dissociate visual feedback of portion size and actual amount consumed, food was covertly added or removed from a bowl using a peristaltic pump. This created two additional ‘incongruent’ conditions, in which 300ml was seen but 500ml was eaten or vice versa. We repeated these conditions using a savoury soup and a sweet dessert. Eating rate (ml per second) was assessed during lunch. After lunch we assessed fullness over a 60-minute period. In the congruent conditions, eating rate was unaffected by the actual volume of food that was consumed (300ml or 500ml). By contrast, we observed a marked difference across the incongruent conditions. Specifically, participants who saw 300ml but actually consumed 500ml ate at a faster rate than participants who saw 500ml but actually consumed 300ml. Participants were unaware that their portion size had been manipulated. Nevertheless, when it disappeared faster or slower than anticipated they adjusted their rate of eating accordingly. This suggests that the control of eating rate involves visual feedback and is not a simple reflexive response to orosensory stimulation. PMID:26828922

  2. Rate and product measurements for the reactions of OH with I/sub 2/ and ICl at 298 K: separation of gas-phase and surface reaction components

    SciTech Connect

    Loewenstein, L.M.; Anderson, J.G.

    1985-12-05

    The kinetic behavior of OH with I/sub 2/ and ICl is reported within the context of a series of radical-halogen reactions to investigate the mechanism of such reactions through studies of reactivity trends. Atomic I and Cl products of the title reactions are measured by resolved resonance fluorescence vapor lamps. IO and ClO are detected by chemically converting them, using NO, to I and Cl, respectively. The rate constant of the reaction H + ICl has been measured at 298 K; its only product channel is I + HCl. Magnitudes of the rate constants of these OH reactions substantiate the reactivity trends in the OH-halogen system based on an electron-transfer mechanism from the highest occupied molecular orbital of the halogen to the lowest unoccupied orbital of the hydroxyl. The rapidity of the OH + I/sub 2/ reaction makes it a possible source of HOI for photochemical studies. 31 references, 11 figures, 2 tables.

  3. A reinvestigation of the rate of the C/+/ + H2 radiative association reaction. [interstellar chemistry

    NASA Technical Reports Server (NTRS)

    Herbst, E.

    1982-01-01

    It is noted that new experimental results and statistical theories have prompted a reinvestigation of the rate coefficient of the interstellar reaction in which C(+) + H2 yields CH2(+) + h(nu) in the 10-100 K temperature range. The results presented here indicate a rate coefficient between 10 to the -16 and 10 to the -15 cu cm/s at all temperatures studied. In applying the modified thermal and phase space theories, it is expected that they will be as accurate as for radiative association as for three-body association, provided the ab initio value for the radiative decay rate is correct. It is expected that the calculated values of the rate coefficient will be accurate to within an order of magnitude and will have the correct temperature dependence.

  4. Relative rate constants for the reactions of OH with methane and methyl chloroform

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1992-01-01

    Atmospheric lifetimes of methane and methyl chloroform are largely determined by the rates of their reactions with hydroxyl radical. The relative lifetimes for this loss path are inversely proportional to the ratio of the corresponding rate coefficients. The relative rate constants were measured in a slow-flow, temperature-controlled photochemical reactor, and were based on rates of disappearance of the parent compounds as measured by FTIR spectroscopy. The temperature range was 277-356 K. Hydroxyl radicals were generated by 254 nm photolysis of O3 in the presence of water vapor. The preferred Arrhenius expression for the results is k(CH3CCl3)/k(CH4) = 0.62 exp (291/T), corresponding to a value of 1.65 at 298 K and 1.77 at 277 K. The respective uncertainties are 5 and 7 percent.

  5. Investigation of heating rate effect on solid-phase interaction in Li2CO3 - Fe2O3 reaction mixture

    NASA Astrophysics Data System (ADS)

    Lysenko, E. N.; Nikolaev, E. V.; Vasendina, E. A.

    2015-04-01

    The influence of heating rate on solid-phase interaction in Li2CO3 - Fe2O3 reaction mixture was investigated by thermal analysis method. The powder mixture components were in the ratio corresponding to LiFe5O8 ferrite. The ferrite synthesis was performed by thermal heating of mixture reagents in thermal analyzer up to 800 °C in air at various heating rates in the ranges (5-50) °C/min. The results showed that the heating rate affects the solid-phase interaction in Li2CO3 - Fe2O3 reaction mixture. The reaction phase formation is accompanied by heat endothermic effect, which was observed in the DSC curve in the form of a complex broad peak. For all samples, this complex peaks were decomposed into simpler peaks, and thereby, the enthalpies of the individual phase transitions were determined. It was shown that the heating rate affects the values of enthalpy and temperatures of heat endothermic effects, so that the high heating rate shifts the proceeding of reaction to higher temperatures.

  6. Does livestock grazing affect sediment deposition and accretion rates in salt marshes?

    NASA Astrophysics Data System (ADS)

    Nolte, Stefanie; Müller, Frauke; Schuerch, Mark; Wanner, Antonia; Esselink, Peter; Bakker, Jan P.; Jensen, Kai

    2013-12-01

    Accretion rates, defined as the vertical growth of salt marshes measured in mm per year, may be influenced by grazing livestock in two ways: directly, by increasing soil compaction through trampling, and indirectly, by reducing aboveground biomass and thus decreasing sediment deposition rates measured in g/m² per year. Although accretion rates and the resulting surface elevation change largely determine the resilience of salt marshes to sea-level rise (SLR), the effect of livestock grazing on accretion rates has been little studied. Therefore, this study aimed to investigate the effect of livestock grazing on salt-marsh accretion rates. We hypothesise that accretion will be lower in grazed compared to ungrazed salt marshes. In four study sites along the mainland coast of the Wadden Sea (in the south-eastern North Sea), accretion rates, sediment deposition rates, and soil compaction of grazed and ungrazed marshes were analysed using the 137Cs radionuclide dating method. Accretion rates were on average 11.6 mm yr-1 during recent decades and thus higher than current and projected rates of SLR. Neither accretion nor sediment deposition rates were significantly different between grazing treatments. Meanwhile, soil compaction was clearly affected by grazing with significantly higher dry bulk density on grazed compared to ungrazed parts. Based on these results, we conclude that other factors influence whether grazing has an effect on accretion and sediment deposition rates and that the effect of grazing on marsh growth does not follow a direct causal chain. It may have a great importance when interacting with other biotic and abiotic processes on the marsh.

  7. Multilevel factor analysis of smokers' real-time negative affect ratings while quitting.

    PubMed

    Bold, Krysten W; Witkiewitz, Katie; McCarthy, Danielle E

    2016-09-01

    Smoking is a serious public health problem, and accurate real-time assessment of risk factors associated with smoking is critical to understanding smoking relapse. Negative affect is often described as a critical risk factor related to smoking relapse, and ecological momentary assessment (EMA) methods have been widely used to study real-time relations between negative affect and smoking. However, the factor structure of momentary negative affect ratings is unknown. The current investigation examined the multilevel factor structure and internal consistency of an EMA measure of negative affect. Daily assessments were collected for 1 week prequit and 3 weeks postquit from 113 adult daily smokers receiving nicotine replacement therapy and counseling to quit smoking. Results supported a 2-factor model with correlated but distinct agitation and distress factors, rather than a single-factor model of negative affect. The agitation factor was indicated by these items: impatient, tense/anxious, restless. The distress factor was indicated by these items: sad/depressed, upset, distressed. The 2-factor model had acceptable model fit and consistent factor loadings across 3 separate cessation phases: prequit, postquit with recent smoking, and postquit without recent smoking. The 2 factors were highly correlated, showed good internal consistency, and showed strong associations with theoretically relevant smoking and affect variables. Agitation was more strongly related to urge to smoke, and distress was more strongly related to recent stress. This study provides support for a 2-factor model of an EMA measure of negative affect and highlights distinct facets that may be useful for future investigations of affect and smoking. (PsycINFO Database Record PMID:27536999

  8. Nocturnal Light Pulses Lower Carbon Dioxide Production Rate without Affecting Feed Intake in Geese

    PubMed Central

    Huang, De-Jia; Yang, Shyi-Kuen

    2016-01-01

    This study was conducted to investigate the effect of nocturnal light pulses (NLPs) on the feed intake and metabolic rate in geese. Fourteen adult Chinese geese were penned individually, and randomly assigned to either the C (control) or NLP group. The C group was exposed to a 12L:12D photoperiod (12 h light and 12 h darkness per day), whereas the NLP group was exposed to a 12L:12D photoperiod inserted by 15-min lighting at 2-h intervals in the scotophase. The weight of the feed was automatically recorded at 1-min intervals for 1 wk. The fasting carbon dioxide production rate (CO2 PR) was recorded at 1-min intervals for 1 d. The results revealed that neither the daily feed intake nor the feed intakes during both the daytime and nighttime were affected by photoperiodic regimen, and the feed intake during the daytime did not differ from that during the nighttime. The photoperiodic treatment did not affect the time distribution of feed intake. However, NLPs lowered (p<0.05) the mean and minimal CO2 PR during both the daytime and nighttime. Both the mean and minimal CO2 PR during the daytime were significantly higher (p<0.05) than those during the nighttime. We concluded that NLPs lowered metabolic rate of the geese, but did not affect the feed intake; both the mean and minimal CO2 PR were higher during the daytime than during the nighttime. PMID:26950871

  9. Nocturnal Light Pulses Lower Carbon Dioxide Production Rate without Affecting Feed Intake in Geese.

    PubMed

    Huang, De-Jia; Yang, Shyi-Kuen

    2016-03-01

    This study was conducted to investigate the effect of nocturnal light pulses (NLPs) on the feed intake and metabolic rate in geese. Fourteen adult Chinese geese were penned individually, and randomly assigned to either the C (control) or NLP group. The C group was exposed to a 12L:12D photoperiod (12 h light and 12 h darkness per day), whereas the NLP group was exposed to a 12L:12D photoperiod inserted by 15-min lighting at 2-h intervals in the scotophase. The weight of the feed was automatically recorded at 1-min intervals for 1 wk. The fasting carbon dioxide production rate (CO2 PR) was recorded at 1-min intervals for 1 d. The results revealed that neither the daily feed intake nor the feed intakes during both the daytime and nighttime were affected by photoperiodic regimen, and the feed intake during the daytime did not differ from that during the nighttime. The photoperiodic treatment did not affect the time distribution of feed intake. However, NLPs lowered (p<0.05) the mean and minimal CO2 PR during both the daytime and nighttime. Both the mean and minimal CO2 PR during the daytime were significantly higher (p<0.05) than those during the nighttime. We concluded that NLPs lowered metabolic rate of the geese, but did not affect the feed intake; both the mean and minimal CO2 PR were higher during the daytime than during the nighttime. PMID:26950871

  10. Assessing the Effects of New Reaction Rates and Convection Theory on Studies of Supernova Progenitors

    NASA Astrophysics Data System (ADS)

    Starrfield, Sumner

    We request funding to carry out a systematic evaluation of nuclear reaction rates and convection on the pre-explosion evolution of core-collapse (SN II) and thermonuclear (SN Ia) supernovae. We will use MESA (Modules for Experiments in Stellar Astrophysics) a new stellar evolution computer code that is co-authored by Co-PI Timmes. One goal of this proposal is to determine the effects of new thermonuclear reaction rates, taken from the next-generation library STARLIB developed by Co-PI Iliadis, on the resulting evolution. Another goal is to test the effects of the latest convection theory, microphysics changes, and numerical techniques on the results. STARLIB is a first-of-its-kind nuclear reaction rate library and, unlike all other libraries, it contains the full reaction rate probability densities at all stellar temperatures. It is publicly available as of June 2013. Consequently, we are now in a unique position to model stellar evolution and nucleosynthesis in a quantitative manner that makes predictions for key observations by NASA ground-based and satellite observatories. We will use two complementary strategies. First, we will take the modern and multiple prescriptions of convection that are implemented in MESA, together with the recommended thermonuclear reaction rates provided by STARLIB, to generate new hydrodynamic simulations of SN Ia and SN II progenitor evolution. Second, we will take the temperature-density-time trajectories from the evolutionary results and do Monte Carlo post-processing nucleosynthesis calculations by sampling over the reaction rate probability densities. This procedure could not be applied previously and has only become feasible with the availability of STARLIB. Calculations of pre-supernova evolution with the STARLIB reaction rates and new convection prescriptions will provide, for the first time, statistically rigorous estimates for both their evolutionary structures and resulting nucleosynthesis. Significant insight into pre

  11. Factors affecting the rate of hydrolysis of phenylboronic acid in lab-scale precipitate reactor studies

    SciTech Connect

    Bannochie, C.J.; Marek, J.C.; Eibling, R.E.; Baich, M.A.

    1992-10-01

    Removing aromatic carbon from an aqueous slurry of cesium-137 and other alkali tetraphenylborates by acid hydrolysis will be an important step in preparing high-level radioactive waste for vitrification at the Savannah River Site`s Defense Waste Processing Facility (DWPF). Kinetic data obtained in bench-scale precipitate hydrolysis reactors suggest changes in operating parameters to improve product quality in the future plant-scale radioactive operation. The rate-determining step is the removal of the fourth phenyl group, i.e. hydrolysis of phenylboronic acid. Efforts to maximize this rate have established the importance of several factors in the system, including the ratio of copper(II) catalyst to formic acid, the presence of nitrite ion, reactions of diphenylmercury, and the purge gas employed in the system.

  12. Factors affecting the rate of hydrolysis of phenylboronic acid in lab-scale precipitate reactor studies

    SciTech Connect

    Bannochie, C.J.; Marek, J.C.; Eibling, R.E.; Baich, M.A.

    1992-01-01

    Removing aromatic carbon from an aqueous slurry of cesium-137 and other alkali tetraphenylborates by acid hydrolysis will be an important step in preparing high-level radioactive waste for vitrification at the Savannah River Site's Defense Waste Processing Facility (DWPF). Kinetic data obtained in bench-scale precipitate hydrolysis reactors suggest changes in operating parameters to improve product quality in the future plant-scale radioactive operation. The rate-determining step is the removal of the fourth phenyl group, i.e. hydrolysis of phenylboronic acid. Efforts to maximize this rate have established the importance of several factors in the system, including the ratio of copper(II) catalyst to formic acid, the presence of nitrite ion, reactions of diphenylmercury, and the purge gas employed in the system.

  13. Reaction rate of a composite core-shell nanoreactor with multiple nanocatalysts.

    PubMed

    Galanti, Marta; Fanelli, Duccio; Angioletti-Uberti, Stefano; Ballauff, Matthias; Dzubiella, Joachim; Piazza, Francesco

    2016-07-27

    We present a detailed theory for the total reaction rate constant of a composite core-shell nanoreactor, consisting of a central solid core surrounded by a hydrogel layer of variable thickness, where a given number of small catalytic nanoparticles are embedded at prescribed positions and are endowed with a prescribed surface reaction rate constant. Besides the precise geometry of the assembly, our theory accounts explicitly for the diffusion coefficients of the reactants in the hydrogel and in the bulk as well as for their transfer free energy jump upon entering the hydrogel shell. Moreover, we work out an approximate analytical formula for the overall rate constant, which is valid in the physically relevant range of geometrical and chemical parameters. We discuss in depth how the diffusion-controlled part of the rate depends on the essential variables, including the size of the central core. In particular, we derive some simple rules for estimating the number of nanocatalysts per nanoreactor for an efficient catalytic performance in the case of small to intermediate core sizes. Our theoretical treatment promises to provide a very useful and flexible tool for the design of superior performing nanoreactor geometries with optimized nanoparticle load. PMID:27411947

  14. Characterization of the reaction rate coefficient of DNA with the hydroxyl radical

    SciTech Connect

    Milligan, J.R.; Ward, J.F.; Aguilera, J.A.

    1996-11-01

    Using agarose gel electrophoresis, we have measured the yield of single-strand breaks (SSBs) induced by {sup 137}Cs {gamma} irradiation in a variety of plasmid DNA substrates ranging in size from 2.7 kb to 38 kb irradiated in aerobic aqueous solution in the presence of the hydroxyl radical scavenger dimethyl sulfoxide (DMSO). Under these conditions DNA SSBs are caused mainly by the hydroxyl radical. Using the competition between DMSO and DNA for the hydroxyl radical, we have estimated the rate coefficient for the reaction of the hydroxyl radical with DNA. The results cannot be characterized by conventional steady-state competition kinetics. However, it is possible to describe the second-order rate constant for the reaction as a function of the scavenging capacity of the solution. The second-order rate constant increases with increasing scavenging capacity, rising from about 5x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 5} s{sup -1} to about 10{sup 10} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 10} s{sup -1}. This dependence of the second-order rate constant on the scavenging capacity appears to be more pronounced for larger plasmids. 17 refs., 4 figs.

  15. Equation of state and reaction rate for condensed-phase explosives

    NASA Astrophysics Data System (ADS)

    Wescott, B. L.; Stewart, D. Scott; Davis, W. C.

    2005-09-01

    The wide-ranging equation of state is a nonideal equation of state based on empirical fitting forms argued from thermodynamic considerations that yield the proper physical features of detonation. The complete equation of state forms are presented and the equation of state and a reaction rate are calibrated for the condensed-phase explosive PBX-9502. Experimental overdriven Hugoniot data are used to calibrate the products equation of state off the principal isentrope passing through the Chapman-Jouguet state. Shock Hugoniot data are used to calibrate the reactants equation of state. The normal detonation shock speed-shock curvature data (Dn-κ) from rate-stick measurements and shock initiation data from wedge tests are used to calibrate the reaction rate. Simulations are carried out that predict detailed particle velocity transients that are measured experimentally with embedded electromagnetic gauge measurements from gas-gun experiments. Multidimensional simulations of steady detonation in a right circular cylinder rate stick are carried out and compared with experiment.

  16. Nova Nucleosynthesis with a New 18F(p,alpha) Reaction Rate

    NASA Astrophysics Data System (ADS)

    Smith, Michael; Kozub, Raymond; Brune, Carl; Starrfield, Sumner

    2005-04-01

    The long-lived radionuclide ^18F is synthesized in nova outbursts and its decay may serve as an observational tracer of the explosion mechanism. Because the ^18F(p,α)^15O reaction is the dominant destruction mechanism for ^18F, the flux of gamma rays from ^18F decay is very sensitive to the rate of this reaction. A revised ^18F(p,α)^15O rate was determined from recent ORNL measurements of ^1H(^18F,p)^18F and ^2H(^18F,p)^19F, combined with a reanalysis of archival ^15N(α,α)^15N data. We used this new rate in nova element synthesis calculations and compared new predictions of the synthesized abundance ^18F (and other nuclides) to that obtained using the two most recent (p,α) rates. We used a post- processing approach with temperature and density histories of 28 zones of ejected material determined from separate hydrodynamics calculations. The implications for satellite observations of novae will be discussed. These calculations were performed and visualized with the Computational Infrastructure for Nuclear Astrophysics, an online suite of codes available at nucastrodata.org.

  17. A study of the photocatalytic effects of aqueous suspensions of platinized semiconductor materials on the reaction rates of candidate redox reactions

    NASA Technical Reports Server (NTRS)

    Miles, A. M.

    1982-01-01

    The effectiveness of powdered semiconductor materials in photocatalyzing candidate redox reactions was investigated. The rate of the photocatalyzed oxidation of cyanide at platinized TiO2 was studied. The extent of the cyanide reaction was followed directly using an electroanalytical method (i.e. differential pulse polarography). Experiments were performed in natural or artificial light. A comparison was made of kinetic data obtained for photocatalysis at platinized powders with rate data for nonplatinized powders.

  18. Parental age affects somatic mutation rates in the progeny of flowering plants.

    PubMed

    Singh, Amit Kumar; Bashir, Tufail; Sailer, Christian; Gurumoorthy, Viswanathan; Ramakrishnan, Anantha Maharasi; Dhanapal, Shanmuhapreya; Grossniklaus, Ueli; Baskar, Ramamurthy

    2015-05-01

    In humans, it is well known that the parental reproductive age has a strong influence on mutations transmitted to their progeny. Meiotic nondisjunction is known to increase in older mothers, and base substitutions tend to go up with paternal reproductive age. Hence, it is clear that the germinal mutation rates are a function of both maternal and paternal ages in humans. In contrast, it is unknown whether the parental reproductive age has an effect on somatic mutation rates in the progeny, because these are rare and difficult to detect. To address this question, we took advantage of the plant model system Arabidopsis (Arabidopsis thaliana), where mutation detector lines allow for an easy quantitation of somatic mutations, to test the effect of parental age on somatic mutation rates in the progeny. Although we found no significant effect of parental age on base substitutions, we found that frameshift mutations and transposition events increased in the progeny of older parents, an effect that is stronger through the maternal line. In contrast, intrachromosomal recombination events in the progeny decrease with the age of the parents in a parent-of-origin-dependent manner. Our results clearly show that parental reproductive age affects somatic mutation rates in the progeny and, thus, that some form of age-dependent information, which affects the frequency of double-strand breaks and possibly other processes involved in maintaining genome integrity, is transmitted through the gametes. PMID:25810093

  19. Parental Age Affects Somatic Mutation Rates in the Progeny of Flowering Plants1

    PubMed Central

    Singh, Amit Kumar; Bashir, Tufail; Sailer, Christian; Gurumoorthy, Viswanathan; Ramakrishnan, Anantha Maharasi; Dhanapal, Shanmuhapreya; Grossniklaus, Ueli; Baskar, Ramamurthy

    2015-01-01

    In humans, it is well known that the parental reproductive age has a strong influence on mutations transmitted to their progeny. Meiotic nondisjunction is known to increase in older mothers, and base substitutions tend to go up with paternal reproductive age. Hence, it is clear that the germinal mutation rates are a function of both maternal and paternal ages in humans. In contrast, it is unknown whether the parental reproductive age has an effect on somatic mutation rates in the progeny, because these are rare and difficult to detect. To address this question, we took advantage of the plant model system Arabidopsis (Arabidopsis thaliana), where mutation detector lines allow for an easy quantitation of somatic mutations, to test the effect of parental age on somatic mutation rates in the progeny. Although we found no significant effect of parental age on base substitutions, we found that frameshift mutations and transposition events increased in the progeny of older parents, an effect that is stronger through the maternal line. In contrast, intrachromosomal recombination events in the progeny decrease with the age of the parents in a parent-of-origin-dependent manner. Our results clearly show that parental reproductive age affects somatic mutation rates in the progeny and, thus, that some form of age-dependent information, which affects the frequency of double-strand breaks and possibly other processes involved in maintaining genome integrity, is transmitted through the gametes. PMID:25810093

  20. Charge-exchange reactions and electron-capture rates for presupernova stellar evolution

    NASA Astrophysics Data System (ADS)

    Zegers, Remco

    2015-04-01

    Weak reaction rates such as electron captures and beta decays play major roles in a variety of astrophysical phenomena, such as core-collapse and thermonuclear supernovae and accreting neutron stars. Consequently, the use of accurate weak reaction rates in astrophysical simulations to understand these phenomena is important. Unfortunately, the number of relevant nuclei is typically very large, and, except for a few special cases, it is impossible to rely on experimental results only: theoretical models must be used to estimate the weak reaction rates. These models can then be benchmarked and improved on the basis of a limited number of experimental data. The most important nuclear structure input that is required for calculating weak reaction rates are Gamow-Teller transition strengths. Although these can be extracted from beta and electron-capture decay data, the energy window accessible by such experiments is limited, if accessible at all. However, at the high temperatures and densities that occur in massive stars prior to the cataclysmic demise, transitions to final states at high excitation energies are important. In addition, to properly test theory, full Gamow-Teller transition strength distributions are very valuable. Fortunately, nature is kind: charge-exchange experiments at intermediate energies can provide the relevant strength distributions over a wide energy window and a variety of charge-exchange probes, such as (p,n), (n,p), (d,2 He) and (t,3 He) have been used to extract strengths of relevance for astrophysics (and for other purposes). This presentation will focus on efforts to validate electron capture rates calculated based on nuclear structure models for nuclei with masses ranging from A ~ 40-65, and on studies aimed at testing astrophysical sensitivities to uncertainties/deviations in the theoretical rates. These efforts include experiments with unstable isotopes, and special gamma-ray coincidence techniques to localize very weak, but

  1. Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

    NASA Technical Reports Server (NTRS)

    DeMore, W.B.

    1996-01-01

    Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

  2. Measuring OH Reaction Rate Constants and Estimating the Atmospheric Lifetimes of Trace Gases.

    NASA Astrophysics Data System (ADS)

    Orkin, Vladimir; Kurylo, Michael

    2015-04-01

    Reactions with hydroxyl radicals and photolysis are the main processes dictating a compound's residence time in the atmosphere for a majority of trace gases. In case of very short-lived halocarbons their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the comprehensive modeling of a compound's impact on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP), each of which are dependent on the atmospheric lifetime of the compound. We have demonstrated the ability to conduct very high accuracy determinations of OH reaction rate constants over the temperature range of atmospheric interest, thereby decreasing the uncertainty of kinetic data to 2-3%. The atmospheric lifetime of a well-mixed compound due to its reaction with tropospheric hydroxyl radicals can be estimated by using a simple scaling procedure that is based on the results of field observations of methyl chloroform concentrations and detailed modeling of the OH distribution in the atmosphere. The currently available modeling results of the atmospheric fate of various trace gases allow for an improved understanding of the ability and accuracy of simplified semi-empirical estimations of atmospheric lifetimes. These aspects will be illustrated in this presentation for a variety of atmospheric trace gases.

  3. Measuring OH Reaction Rate Constants and Estimating the Atmospheric Lifetimes of Trace Gases.

    NASA Astrophysics Data System (ADS)

    Orkin, V. L.; Kurylo, M. J., III

    2014-12-01

    Reactions with hydroxyl radicals and photolysis are the main processes dictating a compound's residence time in the atmosphere for a majority of trace gases. In case of very short-lived halocarbons their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the comprehensive modeling of a compound's impact on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP), each of which are dependent on the atmospheric lifetime of the compound. We have demonstrated the ability to conduct very high accuracy determinations of OH reaction rate constants over the temperature range of atmospheric interest, thereby decreasing the uncertainty of kinetic data to 2-3%. The atmospheric lifetime of a tropospherically well-mixed compound due to its reaction with tropospheric hydroxyl radicals can be estimated by using a simple scaling procedure that is based on the results of field observations of methyl chloroform concentrations and detailed modeling of the OH distribution in the atmosphere. The currently available modeling results of the atmospheric fate of various trace gases allow for an improved understanding of the ability and accuracy of simplified semi-empirical estimations of atmospheric lifetimes. These aspects will be illustrated in this presentation for a variety of atmospheric trace gases.

  4. Reaction kinetics, P-T-t paths and rates of tectonic processes

    SciTech Connect

    Bohlen, S.R.; Hankins, W.B.; Eckert, J.O. Jr.; Kirby, S.H.; Liu, J. ); Hacker, B.R.; Mosenfelder, J.L. . Dept. of Geology)

    1992-01-01

    The interpretation of portions of P-T-time (t) paths in metamorphic rocks assumes that continuous and discontinuous reactions record local equilibrium as P-T conditions change, implying that the kinetics of many reactions are rapid relative to dT/dt and dP/dt. Occurrence of eclogite veins in granulites from Bergen, Norway as well as occurrences of coesite and diamond in crustal rocks imply that, under certain conditions, this assumption is wrong. Knowledge of the kinetics of important reactions under appropriate conditions would provide limits on the duration of relatively narrowly defined P-T conditions, allow inference of the rates of exhumation of rocks containing high-pressure phases, and allow the calculation of the time required for the conversion of gabbro to eclogite in the lower crust as a function of P-T-t. The authors are currently assessing the rates of key phase transformations: calcite to aragonite, albite to jadeite + quartz, coesite to quartz, opx[sub Fs[sup 80

  5. Effective reaction rate for porous surfaces under strong shear: Beyond Damkohler

    NASA Astrophysics Data System (ADS)

    Shaqfeh, Eric S. G.; Shah, Preyas

    2014-11-01

    Traditonally, surface reactive porous media are modeled via an effective reaction/mass transfer rate based on the original ansatz of Damkohler, i.e, reaction limited transport at the microscale in the absence of flow. We are interested in modeling the microscale mass transfer to porous surfaces occuring in leaky tumor vasculature, where the Damkohler number can be O(1) and the Peclet number may be large. We model it as a uniform bath of a species in unbound shear flow over a wall with first order reactive circular patches (pores). We analyze the flux through a single pore using both analytic and boundary element simulations and observe the formation of a 3-D depletion region (wake) downstream of the pore. Wake sharing between adjacent pores in a multibody setting such as 2 pores aligned in the shear direction leads to a smaller flux per pore. Obtaining this interaction length scale and using the renormalized periodic Green's function, we study the flux through a periodic and disordered distribution of pores. This flux appears as the reaction rate in an effective boundary condition, valid up to non-dilute pore area fractions, and applicable at a wall-normal effective slip distance. It replaces the details of the surface and can be used directly in large scale physics simulations.

  6. Absolute rate constants of alkoxyl radical reactions in aqueous solution. [Tert-butyl hydroperoxide

    SciTech Connect

    Erben-Russ, M.; Michel, C.; Bors, W.; Saran, M.

    1987-04-23

    The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA) was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.

  7. Contribution of 19F resonances on 18O( p, α)15N reaction rate

    NASA Astrophysics Data System (ADS)

    Benmeslem, Meriem; Chafa, Azzedine; Barhoumi, Slimane; Tribeche, Mouloud

    2014-08-01

    The 18O( p, α)15N reaction influences the isotopes production such as 19F, 18O, and 15N which can be used to test the models of stellar evolution. 19F is synthesized in both asymptotic giant branch (AGB) and metal-rich Wolf-Rayet (WR) stars. Using R-matrix theory we allow new values of resonances parameters in 19F. We show that the most important contribution to the differential and total cross section at low energies, comes from the levels in 19F situated at resonances energies E R =151, 680 and 840 keV with spin and parity 1/2+. The total width of the 680 keV resonance is badly known. So, we have focused on this broad resonance corresponding to the 8.65 MeV level in 19F. We delimit the temperature range in which each resonance contribution to the total reaction rate occurs by analyzing the ratio ( N A < σν> i / N A < σν>). This allowed us to show that the 680 and 840 keV broad resonances strongly dominate the reaction rate over the stellar temperature range T 9=0.02-0.06 and T 9=0.5-5. Finally, these results were compared to NACRE and Iliadis astrophysical compilations.

  8. Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

    NASA Technical Reports Server (NTRS)

    Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1976-01-01

    Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

  9. THE IMPACT OF HELIUM-BURNING REACTION RATES ON MASSIVE STAR EVOLUTION AND NUCLEOSYNTHESIS

    SciTech Connect

    West, Christopher; Heger, Alexander; Austin, Sam M. E-mail: alexander.heger@monash.edu

    2013-05-20

    We study the sensitivity of presupernova evolution and supernova nucleosynthesis yields of massive stars to variations of the helium-burning reaction rates within the range of their uncertainties. The current solar abundances from Lodders are used for the initial stellar composition. We compute a grid of 12 initial stellar masses and 176 models per stellar mass to explore the effects of independently varying the {sup 12}C({alpha}, {gamma}){sup 16}O and 3{alpha} reaction rates, denoted R{sub {alpha},12} and R{sub 3{alpha}}, respectively. The production factors of both the intermediate-mass elements (A = 16-40) and the s-only isotopes along the weak s-process path ({sup 70}Ge, {sup 76}Se, {sup 80}Kr, {sup 82}Kr, {sup 86}Sr, and {sup 87}Sr) were found to be in reasonable agreement with predictions for variations of R{sub 3{alpha}} and R{sub {alpha},12} of {+-}25%; the s-only isotopes, however, tend to favor higher values of R{sub 3{alpha}} than the intermediate-mass isotopes. The experimental uncertainty (one standard deviation) in R{sub 3{alpha}}(R{sub {alpha},12}) is approximately {+-}10%({+-}25%). The results show that a more accurate measurement of one of these rates would decrease the uncertainty in the other as inferred from the present calculations. We also observe sharp changes in production factors and standard deviations for small changes in the reaction rates, due to differences in the convection structure of the star. The compactness parameter was used to assess which models would likely explode as successful supernovae, and hence contribute explosive nucleosynthesis yields. We also provide the approximate remnant masses for each model and the carbon mass fractions at the end of core-helium burning as a key parameter for later evolution stages.

  10. Reaction Time of Facial Affect Recognition in Asperger's Disorder for Cartoon and Real, Static and Moving Faces

    ERIC Educational Resources Information Center

    Miyahara, Motohide; Bray, Anne; Tsujii, Masatsugu; Fujita, Chikako; Sugiyama, Toshiro

    2007-01-01

    This study used a choice reaction-time paradigm to test the perceived impairment of facial affect recognition in Asperger's disorder. Twenty teenagers with Asperger's disorder and 20 controls were compared with respect to the latency and accuracy of response to happy or disgusted facial expressions, presented in cartoon or real images and in…

  11. Toward Making the Invisible Visible Using a Scale: Prospective Teachers' Thoughts and Affective Reactions to Feedback

    ERIC Educational Resources Information Center

    Akkuzu, Nalan; Uyulgan, Melis Arzu

    2014-01-01

    This paper presents the development and initial validation of a feedback scale which measures the thoughts and affective reactions of prospective teachers concerning feedback on their teaching experiences. To reach this goal, data from 512 prospective teachers were used to test the internal consistency, exploratory and confirmative factor…

  12. Reactions to Anglo- and Hispanic-American-Accented Speakers: Affect, Identity, Persuasion, and the English-Only Controversy.

    ERIC Educational Resources Information Center

    Giles, Howard; And Others

    1995-01-01

    Examined the reactions of 83 Anglo-American undergraduates to Anglo- and Hispanic-American-accented speakers supporting or opposing the English-only movement in California. Results found that respondents were happier when the Anglo source argued against rather than for English exclusivity, and that respondents' happiness was not affected by…

  13. Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

    USGS Publications Warehouse

    Wang, Bronwen; Burau, Richard G.

    1995-01-01

    Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

  14. A reaction-diffusion-based coding rate control mechanism for camera sensor networks.

    PubMed

    Yamamoto, Hiroshi; Hyodo, Katsuya; Wakamiya, Naoki; Murata, Masayuki

    2010-01-01

    A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal. PMID:22163620

  15. Development of the GEM-MSTPC for studies of astrophysical nuclear reaction rates

    SciTech Connect

    Yamaguchi, K.; Arai, I.; Ishiyama, H.; Watanabe, Y. X.; Tanaka, M. H.; Miyatake, H.; Hirayama, Y.; Imai, N.; Fuchi, Y.; Jeong, S. C.; Nomura, T.; Mizoi, Y.; Das, S. K.; Fukuda, T.; Hashimoto, T.; Yamaguchi, H.; Kubono, S.; Hayakawa, S.; Makii, H.; Mitsuoka, S.

    2010-08-12

    We have developed an active-target type gas-detector, a Gas Electron Multiplier Multiple-Sampling and Tracking Proportional Chamber (GEM-MSTPC) operating with low-pressure He-base mixed gas, where He is used as a target for studies of astrophysical nuclear reaction rates. Different kinds of 400 {mu}m thick GEMs were examined. The gain stability was examined with a configuration of GEMs of 400 {mu}m in thickness fabricated in different ways, against the injection rate of low-energy heavy ions of 10{sup 5} particles per second. The gain of GEM with Cu electrodes coated by Au was observed to be stable up to the injection rate of 10{sup 5} particles per second.

  16. The rate constant for the reaction of oxygen /3P/ atoms with dichlorine monoxide

    NASA Technical Reports Server (NTRS)

    Miziolek, A. W.; Molina, M. J.

    1978-01-01

    A fast flow discharge apparatus was used to measure the rate constant for the reaction of ground state oxygen atoms with dichlorine monoxide in the temperature range 236-295 K. The air afterflow technique (NO2 chemiluminescence) was used for detection of oxygen atoms. The Arrhenius expression for the rate constant was found to be 2.7 plus or minus 0.3 times 10 to the -11th power exp(-560 plus or minus 80/T) cu cm per molecule per sec. At 295 K the rate constant is 4.1 plus or minus 0.5 times 10 to the -12th power cu cm per molecule per sec.

  17. Channel specific rate constants for reactions of O(1D) with HCl and HBr

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Wells, J. R.; Ravishankara, A. R.

    1986-01-01

    The absolute rate coefficients and product yields for reactions of O(1D) with HCl(1) and HBr(2) at 287 K are presently determined by means of the time-resolved resonance fluorescence detection of O(3P) and H(2S) in conjunction with pulsed laser photolysis of O3/HX/He mixtures. Total rate coefficients for O(1D) removal are found to be, in units of 10 to the -10th cu cm/molecule per sec, k(1) = 1.50 + or - 0.18 and k(2) 1.48 + or - 0.16; the absolute accuracy of these rate coefficients is estimated to be + or - 20 percent.

  18. CNO and 6Li from big-bang nucleosynthesis-Impact of unmeasured reaction rates

    NASA Astrophysics Data System (ADS)

    Madsen, Jes

    1990-04-01

    Rates for a number of nuclear reactions not studied in the laboratory are crucial for predicting the outcome of big-bang nucleosynthesis. It is shown in the present investigation that the mass fraction of CNO elements produced in neutron-rich zones in inhomogeneous nucleosynthesis (other parameters fixed) spans almost 3 orders of magnitude depending on the unmeasured rate of 8Li(α,n)11B. The possibility of producing observable quantities of primordial 6Li via 3H(3He,γ)6Li is discussed for the first time, and finally it is reported that helium production through 2H(2H, γ)4He is negligible in all nucleosynthesis scenarios, in spite of recent measurements increasing the low-energy rate by a factor 32.

  19. A Reaction-Diffusion-Based Coding Rate Control Mechanism for Camera Sensor Networks

    PubMed Central

    Yamamoto, Hiroshi; Hyodo, Katsuya; Wakamiya, Naoki; Murata, Masayuki

    2010-01-01

    A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal. PMID:22163620

  20. Internal Thermodynamical Equilibrium And Consequences For Rate Law Expressions For Elementary Chemical And Physical Reactions

    NASA Astrophysics Data System (ADS)

    Jesudason, Christopher G.

    2009-07-01

    By viewing reactant species to be in a state of thermodynamical equilibrium with its various members which constitutes a set within a set of topological parameters various states of internal equilibrium within the same species would exist subject to the Gibbs thermodynamical criteria. Some examples from actual ab initio computer simulations show that there exists an empirical relationship between the activity coefficient ratio and the so-called reactivity coefficients, defined as a measure of departure of the rate constant with varying concentration of reactants in a system at equilibrium, where forward and backward rates can still be measured. These ideas are applied to charged reaction dynamics where a generalization of the Brönsted and Bjerrum rate expression is obtained.

  1. Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

    PubMed

    Minakata, Daisuke; Crittenden, John

    2011-04-15

    The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs. PMID:21410278

  2. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

    PubMed

    Gallis, Michael A; Bond, Ryan B; Torczynski, John R

    2009-09-28

    Recently proposed 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 investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases. PMID:19791885

  3. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows

    NASA Astrophysics Data System (ADS)

    Gallis, Michael A.; Bond, Ryan B.; Torczynski, John R.

    2009-09-01

    Recently proposed 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 investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.

  4. A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

    NASA Technical Reports Server (NTRS)

    Foy, E.; Ronan, G.; Chinitz, W.

    1982-01-01

    A principal element to be derived from modeling turbulent reacting flows is an expression for the reaction rates of the various species involved in any particular combustion process under consideration. A temperature-derived most-likely probability density function (pdf) was used to describe the effects of temperature fluctuations on the Arrhenius reaction rate constant. A most-likely bivariate pdf described the effects of temperature and species concentrations fluctuations on the reaction rate. A criterion is developed for the use of an "appropriate" temperature pdf. The formulation of models to calculate the mean turbulent Arrhenius reaction rate constant and the mean turbulent reaction rate is considered and the results of calculations using these models are presented.

  5. Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

    NASA Technical Reports Server (NTRS)

    Hoobler, Ray J.; Leone, Stephen R.

    1997-01-01

    Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

  6. Size dependence of surface thermodynamic properties of nanoparticles and its determination method by reaction rate constant

    NASA Astrophysics Data System (ADS)

    Li, Wenjiao; Xue, Yongqiang; Cui, Zixiang

    2016-08-01

    Surface thermodynamic properties are the fundamental properties of nanomaterials, and these properties depend on the size of nanoparticles. In this paper, relations of molar surface thermodynamic properties and surface heat capacity at constant pressure of nanoparticles with particle size were derived theoretically, and the method of obtaining the surface thermodynamic properties by reaction rate constant was put forward. The reaction of nano-MgO with sodium bisulfate solution was taken as a research system. The influence regularities of the particle size on the surface thermodynamic properties were discussed theoretically and experimentally, which show that the experimental regularities are in accordance with the corresponding theoretical relations. With the decreasing of nanoparticle size, the molar surface thermodynamic properties increase, while the surface heat capacity decreases (the absolute value increases). In addition, the surface thermodynamic properties are linearly related to the reciprocal of nanoparticle diameter, respectively.

  7. Rate of reaction of the hydrogen atom with nitrous oxide in ambient water

    NASA Astrophysics Data System (ADS)

    Kazmierczak, Lukasz; Swiatla-Wojcik, Dorota; Szala-Bilnik, Joanna; Wolszczak, Marian

    2016-08-01

    The reaction of the hydrogen atom with nitrous oxide has been investigated by pulse radiolysis of N2O-saturated 0.1 M HCl solution at room temperature (24±1 °C). The value of (9±2)×104 M-1 s-1 obtained for the reaction rate constant is between the early estimates 1×104 M-1 s-1 by Czapski and Jortner (1960) and 4.3×105 M-1 s-1 by Thomas (1969), and is much lower than 2×106 M-1 s-1 used recently (Janik et al., 2007; Ismail et al., 2013; Liu et al., 2015; Meesungnoen et al., 2015).

  8. Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers

    SciTech Connect

    Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

    1993-08-03

    A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

  9. Estimates of neutron reaction rates in three portable He-3 proportional counters

    SciTech Connect

    Descalle, M; Labov, S

    2007-03-01

    The goal of this study is to obtain Monte Carlo estimates of neutron reaction rates for the {sup 3}He(n,p){sup 3}H reaction in two portable He-3 proportional counters in several configurations to quantify contributions from the environment, and optimize the tube characteristics. The smallest tube (0.5-inch diameter, 2-inch long, P = 10 atm) will not meet requirements. The largest tube (1-inch diameter, 4-inch long, P = 6 or 10 atm) will meet requirements and the tube length could be decreased to 2-inch at 6 atm and 1-inch at 10 atm. The 'medium' tube (3/4-inch diameter, 2-inch long, P = 10 atm) will meet requirements for the parallelepiped body, but will not for the cylindrical body.

  10. Do Case Rates Affect Physicians' Clinical Practice in Radiation Oncology?: An Observational Study

    PubMed Central

    Loy, Bryan A.; Shkedy, Clive I.; Powell, Adam C.; Happe, Laura E.; Royalty, Julie A.; Miao, Michael T.; Smith, Gary L.; Long, James W.; Gupta, Amit K.

    2016-01-01

    Case rate payments combined with utilization monitoring may have the potential to improve the quality of care by reducing over and under-treatment. Thus, a national managed care organization introduced case rate payments at one multi-site radiation oncology provider while maintaining only fee-for-service payments at others. This study examined whether the introduction of the payment method had an effect on radiation fractions administered when compared to clinical guidelines. The number of fractions of radiation therapy delivered to patients with bone metastases, breast, lung, prostate, and skin cancer was assessed for concordance with clinical guidelines. The proportion of guideline-based care ascertained from the payer's claims database was compared before (2011) and after (2013) the payment method introduction using relative risks (RR). After the introduction of case rates, there were no significant changes in guideline-based care in breast, lung, and skin cancer; however, patients with bone metastases and prostate cancer were significantly more likely to have received guideline-based care (RR = 2.0 and 1.1, respectively, p<0.05). For the aggregate of all cancers, the under-treatment rate significantly declined (p = 0.008) from 4% to 0% after the introduction of case rate payments, while the over-treatment rate remained steady at 9%, with no significant change (p = 0.20). These findings suggest that the introduction of case rate payments did not adversely affect the rate of guideline-based care at the provider examined. Additional research is needed to isolate the effect of the payment model and assess implications in other populations. PMID:26870963

  11. Do Case Rates Affect Physicians' Clinical Practice in Radiation Oncology?: An Observational Study.

    PubMed

    Loy, Bryan A; Shkedy, Clive I; Powell, Adam C; Happe, Laura E; Royalty, Julie A; Miao, Michael T; Smith, Gary L; Long, James W; Gupta, Amit K

    2016-01-01

    Case rate payments combined with utilization monitoring may have the potential to improve the quality of care by reducing over and under-treatment. Thus, a national managed care organization introduced case rate payments at one multi-site radiation oncology provider while maintaining only fee-for-service payments at others. This study examined whether the introduction of the payment method had an effect on radiation fractions administered when compared to clinical guidelines. The number of fractions of radiation therapy delivered to patients with bone metastases, breast, lung, prostate, and skin cancer was assessed for concordance with clinical guidelines. The proportion of guideline-based care ascertained from the payer's claims database was compared before (2011) and after (2013) the payment method introduction using relative risks (RR). After the introduction of case rates, there were no significant changes in guideline-based care in breast, lung, and skin cancer; however, patients with bone metastases and prostate cancer were significantly more likely to have received guideline-based care (RR = 2.0 and 1.1, respectively, p<0.05). For the aggregate of all cancers, the under-treatment rate significantly declined (p = 0.008) from 4% to 0% after the introduction of case rate payments, while the over-treatment rate remained steady at 9%, with no significant change (p = 0.20). These findings suggest that the introduction of case rate payments did not adversely affect the rate of guideline-based care at the provider examined. Additional research is needed to isolate the effect of the payment model and assess implications in other populations. PMID:26870963

  12. Structural and dynamical control of the reaction rate in protein electron transfer

    NASA Astrophysics Data System (ADS)

    Balabin, Ilya A.

    Electron transfer (ET) reactions in proteins are key steps in many vital bioenergetic processes, and the reaction rate is known to be highly sensitive to the protein structure in some cases. For most bioenergetic reactions, as described by the Fermi Golden rule, the rate is proportional to a product of the average square of the effective electronic donor to acceptor coupling and a Franck-Condon factor, which accounts for the nuclear control of the energy gap. The nuclear factor is reasonably well described in Marcus theory and its modifications, and this work is focused on the mechanisms that control the effective coupling. About ten years ago, the Pathways model described for the first time how protein environment may control the effective coupling. In this work, a novel theoretical approach is developed to explore the mechanisms of structural and dynamical control beyond the qualitative level of the Pathways model. In Chapter 1, the assumptions of the Pathways model, its limitations and effects of the structure and the electronic Hamiltonian are investigated for model chain-like bridges using the Dyson's equations. In Chapter II, the framework to explore the sensitivity of the effective coupling to quality of the electronic Hamiltonian, the interference among the dominant pathways and the bridge dynamics is presented. This analysis employs the Green's function technique and includes combined molecular dynamics and electronic structure calculations. Finally, in Chapter III, this framework is tested on the bacterial photosynthetic reaction center, and the mechanisms of the structural and dynamical control for different ET steps are discussed.

  13. Effects of arsenic incorporation on jarosite dissolution rates and reaction products

    NASA Astrophysics Data System (ADS)

    Kendall, Matthew R.; Madden, Andrew S.; Elwood Madden, Megan E.; Hu, Qinhong

    2013-07-01

    Batch dissolution experiments were undertaken on synthetic arsenojarosites at pH 2, pH 8, and in ultra-pure water to better understand the influence of As incorporation on the kinetics and reaction products of jarosite dissolution. Incongruent jarosite dissolution was observed in all experiments. Arsenojarosite lacks the pH dependency observed in K-jarosite dissolution, likely the result of surface arsenate-iron complexes preventing protonation at low pH and repelling hydroxyls at high pH. The stronger bonding of arsenate to iron, compared to sulfate to iron, leads to an enrichment of surface layer arsenate-iron complex sites, inhibiting the dissolution of jarosite with time. The secondary reaction products formed during the dissolution of arsenojarosite include maghemite, goethite, and hematite in ultra-pure water, and ferrihydrite in pH 8 Tris buffered solution. Maghemite initially forms and transitions to hematite with time in ultra-pure water, but increasing arsenic concentrations slow this transition. At pH >3.5, arsenic from the dissolution of arsenojarosite adsorbs onto newly formed reaction products. Arsenic also inhibits the formation of goethite and reduces the crystallinity of the observed maghemite reaction products. The coprecipitation of iron oxides with increasing amounts of arsenic results in a change from spherical to "worm-like" aggregate morphology and provides a sink for arsenic released during arsenojarosite dissolution. This study shows that in open systems with a flush of fresh solution, arsenic incorporation in jarosite results in an increase in dissolution rates. In closed systems, however, increasing surface arsenate-iron complexes inhibit further dissolution of the underlying bulk material, causing a reduction in dissolution rates as arsenic incorporation increases.

  14. Reaction Rates of 64Ge(p,?)65As and 65As(p,?)66Se and the Extent of Nucleosynthesis in Type I X-Ray Bursts

    NASA Astrophysics Data System (ADS)

    Lam, Y. H.; He, J. J.; Parikh, A.; Schatz, H.; Brown, B. A.; Wang, M.; Guo, B.; Zhang, Y. H.; Zhou, X. H.; Xu, H. S.

    2016-02-01

    The extent of nucleosynthesis in models of type I X-ray bursts (XRBs) and the associated impact on the energy released in these explosive events are sensitive to nuclear masses and reaction rates around the 64Ge waiting point. Using the well known mass of 64Ge, the recently measured 65As mass, and large-scale shell model calculations, we have determined new thermonuclear rates of the 64Ge(p,γ)65As and 65As(p,γ)66Se reactions with reliable uncertainties. The new reaction rates differ significantly from previously published rates. Using the new data, we analyze the impact of the new rates and the remaining nuclear physics uncertainties on the 64Ge waiting point in a number of representative one-zone XRB models. We find that in contrast to previous work, when all relevant uncertainties are considered, a strong 64Ge rp-process waiting point cannot be ruled out. The nuclear physics uncertainties strongly affect XRB model predictions of the synthesis of 64Zn, the synthesis of nuclei beyond A = 64, the energy generation, and the burst light curve. We also identify key nuclear uncertainties that need to be addressed to determine the role of the 64Ge waiting point in XRBs. These include the remaining uncertainty in the 65As mass, the uncertainty of the 66Se mass, and the remaining uncertainty in the 65As(p,γ)66Se reaction rate, which mainly originates from uncertain resonance energies.

  15. 31Cl beta decay and the 30P31S reaction rate in nova nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Bennett, Michael; Wrede, C.; Brown, B. A.; Liddick, S. N.; Pérez-Loureiro, D.; NSCL e12028 Collaboration

    2016-03-01

    The 30P31S reaction rate is critical for modeling the final isotopic abundances of ONe nova nucleosynthesis, identifying the origin of presolar nova grains, and calibrating proposed nova thermometers. Unfortunately, this rate is essentially experimentally unconstrained because the strengths of key 31S proton capture resonances are not known, due to uncertainties in their spins and parities. Using a 31Cl beam produced at the National Superconducting Cyclotron Laboratory, we have populated several 31S states for study via beta decay and devised a new decay scheme which includes updated beta feedings and gamma branchings as well as multiple states previously unobserved in 31Cl beta decay. Results of this study, including the unambiguous identification due to isospin mixing of a new l = 0 , Jπ = 3 /2+ 31S resonance directly in the middle of the Gamow Window, will be presented, and significance to the evaluation of the 30P31S reaction rate will be discussed. Work supported by U.S. Natl. Sci. Foundation (Grants No. PHY-1102511, PHY-1404442, PHY-1419765, and PHY-1431052); U.S. Dept. of Energy, Natl. Nucl. Security Administration (Award No. DE-NA0000979); Nat. Sci. and Eng. Research Council of Canada.

  16. New reaction rates for improved primordial D /H calculation and the cosmic evolution of deuterium

    NASA Astrophysics Data System (ADS)

    Coc, Alain; Petitjean, Patrick; Uzan, Jean-Philippe; Vangioni, Elisabeth; Descouvemont, Pierre; Iliadis, Christian; Longland, Richard

    2015-12-01

    Primordial or big bang nucleosynthesis (BBN) is one of the three historically strong evidences for the big bang model. Standard BBN is now a parameter-free theory, since the baryonic density of the Universe has been deduced with an unprecedented precision from observations of the anisotropies of the cosmic microwave background radiation. There is a good agreement between the primordial abundances of 4He, D, 3He, and 7Li deduced from observations and from primordial nucleosynthesis calculations. However, the 7Li calculated abundance is significantly higher than the one deduced from spectroscopic observations and remains an open problem. In addition, recent deuterium observations have drastically reduced the uncertainty on D /H , to reach a value of 1.6%. It needs to be matched by BBN predictions whose precision is now limited by thermonuclear reaction rate uncertainties. This is especially important as many attempts to reconcile Li observations with models lead to an increased D prediction. Here, we reevaluate the d (p ,γ )3He, d (d ,n ) 3H3, and d (d ,p ) 3H reaction rates that govern deuterium destruction, incorporating new experimental data and carefully accounting for systematic uncertainties. Contrary to previous evaluations, we use theoretical ab initio models for the energy dependence of the S factors. As a result, these rates increase at BBN temperatures, leading to a reduced value of D /H =(2.45 ±0.10 )×10-5 (2 σ ), in agreement with observations.

  17. Rate Equations and Kinetic Parameters of the Reactions Involved in Pyrite Oxidation by Thiobacillus ferrooxidans.

    PubMed

    Lizama, H M; Suzuki, I

    1989-11-01

    Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 muM Fe per min per FeS(2) percent pulp density for the spontaneous pyrite dissolution, 10 muM Fe per min per mM Fe for the indirect leaching with Fe, 90 muM O(2) per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 muM O(2) per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The K(m) values for pyrite concentration were similar and were 1.9, 2.5, and 2.75% pulp density for indirect leaching, washed pyrite oxidation by T. ferrooxidans, and unwashed pyrite oxidation by T. ferrooxidans, respectively. The last reaction was competitively inhibited by increasing concentrations of cells, with a K(i) value of 0.13 mg of wet cells per ml. T. ferrooxidans cells also increased the rate of Fe production from Fe plus pyrite. PMID:16348054

  18. Temperature dependent rate coefficients for the reaction of OH radicals with dimethylbenzoquinones

    NASA Astrophysics Data System (ADS)

    Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Wenger, John C.

    2015-10-01

    Rate coefficients for the gas-phase reaction of hydroxyl (OH) radicals with two methylated benzoquinones have been measured at atmospheric pressure over the temperature range 284-313 K using the relative rate method. The following Arrhenius expressions (in cm3 molecule-1 s-1) have been obtained: k(25DMBQ) = (8.59 ± 4.70) × 10-12exp[(228 ± 163)/T] and k(26DMBQ) = (5.11 ± 2.79) × 10-12exp[(399 ± 165)/T] for 2,5-dimethylbenzoquinone (2,5DMBQ) and 2,6-dimethylbenzoquinone (2,6DMBQ), respectively, with corresponding values at 298 K: k(25DMBQ) = (2.05 ± 0.46) × 10-11 and k(26DMBQ) = (1.93 ± 0.12) × 10-11. The rate coefficients are compared to those reported for similar compounds and discussed in terms of structure-activity relationships. The results are also used to calculate atmospheric lifetimes for 2,5DMBQ and 2,6DMBQ with respect to reaction with OH radicals.

  19. Nuclear reaction rates and their influence on nucleosynthesis in the neutrino-p-process

    NASA Astrophysics Data System (ADS)

    Hatcher, Daniel; Frohlich, Carla; Perdikakis, Georgios

    2015-10-01

    The synthesis of elements heavier than iron in the early stages of galactic evolution is commonly attributed to Type II (core collapse) supernova explosions. However, the currently accepted mechanisms of heavy element synthesis through neutron capture processes (r-process and s-process) cannot explain the abundance patterns seen in very old galactic halo stars. A proposed solution to this problem is the neutrino-p-process, which takes place in the strong neutrino winds of core-collapse supernovae. In the neutrino-p-process, antineutrinos absorbed by protons yield neutrons that are quickly captured by the surrounding, proton-rich nuclei through (n,p) reactions. Such interactions allow for the nucleosynthesis of elements with atomic mass numbers greater than 64 (this includes Sr, Y, Zr and others possibly up to Sn). We study the sensitivity of the νp-process abundance pattern to (n,p), (p, γ), and (n, γ) rates for nuclei between Ni and Sn. We illustrate our findings for three different initial electron fractions and two representative trajectories. We discuss how these rates influence the abundance pattern and the nuclear flow. We observe the effects of predicted reaction rates on the abundance pattern and nuclear flow.

  20. Test of the quantum instanton approximation for thermal rate constants for some collinear reactions.

    PubMed

    Ceotto, Michele; Miller, William H

    2004-04-01

    Two variants of the recently developed quantum instanton (QI) model for calculating thermal rate constants of chemical reactions are applied to several collinear atom-diatom reactions with various skew angles. The results show that the original QI version of the model is consistently more accurate than the "simplest" quantum instanton version (both being applied here with one "dividing surface") and thus to be preferred. Also, for these examples (as with other earlier applications) the QI results agree well with the correct quantum rates (to within approximately 20% or better) for all temperatures >200 K, except for situations where dynamical corrections to transition state theory (i.e., "re-crossing" dynamics) are evident. (Since re-crossing effects are substantially reduced in higher dimensionality, this is not a cause for serious concern.) A procedure is also described which facilitates use of the METROPOLIS algorithm for evaluating all quantities that appear in the QI rate expression by Monte Carlo path integral methods. PMID:15267524

  1. Technologies that affect the weaning rate in beef cattle production systems.

    PubMed

    Dill, Matheus Dhein; Pereira, Gabriel Ribas; Costa, João Batista Gonçalves; Canellas, Leonardo Canali; Peripolli, Vanessa; Neto, José Braccini; Sant'Anna, Danilo Menezes; McManus, Concepta; Barcellos, Júlio Otávio Jardim

    2015-10-01

    We investigated the differences between weaning rates and technologies adopted by farmers in cow-calf production systems in Rio Grande do Sul State, Brazil. Interviews were carried out with 73 farmers about 48 technologies that could affect reproductive performance. Data were analyzed by multivariate analysis using a non-hierarchical cluster method. The level of significance was set at P < 0.05. Three distinct clusters of farmers were created (R (2) = 0.90), named as low (LWR), intermediate (IWR), and high (HWR) weaning rate, with 100, 91, and 96 % of the farmers identified within their respective groups and average weaning rates of 59, 72, and 83 %, respectively. IWR and HWR farmers used more improved natural pasture, fixed-time artificial insemination, selection for birth weight, and proteinated salt compared to LWR. HWR farmers used more stocking rate control, and IWR farmers used more ultrasound to evaluate reproductive performance compared to the LWR group. IWR and HWR adopted more technologies related to nutrition and reproductive aspects of the herd in comparison to LWR. We concluded that farmers with higher technology use on farm had higher weaning rates which could be used to benefit less efficient farmers. PMID:26048693

  2. Demography of forest birds in Panama: How do transients affect estimates of survival rates?

    USGS Publications Warehouse

    Brawn, J.D.; Karr, J.R.; Nichols, J.D.; Robinson, W.D.

    1998-01-01

    Estimates of annual survival rates for a multispecies sample of neotropical birds from Panama have proven controversial. Traditionally, tropical birds were thought to have high survival rates for their size, but analyses by Kart et al. (1990. Am. Nat. 136:277-91) contradicted that view, suggesting tropical birds may not have systematically high survival rates. A persistent criticism of that study has been that the estimates were biased by transient birds captured only once as they passed through the area being sampled. New models that formally adjust for transient individuals have been developed since 1990. Preliminary analyses using these models indicate that, despite some variation among species, overall estimates of survival rates for understory birds in Panama are not strongly affected by adjustments for transients. We also compare estimates of survival rates based on mark-recapture models with observations of colour-marked birds. The demographic traits of birds in the tropics (and elsewhere) vary within and among species according to combinations of historical and ongoing ecological factors. Understanding sources of this variation is the challenge for future work.

  3. Identifying Critical Road Geometry Parameters Affecting Crash Rate and Crash Type

    PubMed Central

    Othman, Sarbaz; Thomson, Robert; Lannér, Gunnar

    2009-01-01

    The objective of this traffic safety investigation was to find critical road parameters affecting crash rate (CR). The study was based on crash and road maintenance data from Western Sweden. More than 3000 crashes, reported from 2000 to 2005 on median-separated roads, were collected and combined with road geometric and surface data. The statistical analysis showed variations in CR when road elements changed confirming that road characteristics affect CR. The findings indicated that large radii right-turn curves were more dangerous than left curves, in particular, during lane changing manoeuvres. However sharper curves are more dangerous in both left and right curves. Moreover, motorway carriageways with no or limited shoulders have the highest CR when compared to other carriageway widths, while one lane carriageway sections on 2+1 roads were the safest. Road surface results showed that both wheel rut depth and road roughness have negative impacts on traffic safety. PMID:20184841

  4. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation.

    PubMed

    Andersen, M S; Larsen, F; Postma, D

    2001-10-15

    The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4 x 10(-10) mol FeS2/g x s are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase. The reaction scheme predicts the volume of O2 gas consumed to be larger than of CO2 produced. In addition the solubility of CO2 in water is about 30 times larger than of O2 causing a further decrease in total gas volume. The change in total gas volume therefore also depends on the gas/water volume ratio and the lower the ratio the more pronounced the loss of volume will be. Under field conditions the change in total volume may amount up to 20% in the absence of calcite and over 10% in the presence of calcite. Such changes in gas volume during the oxidation of pyrite are expected to result in pressure gradients causing advective transport of gaseous oxygen. PMID:11686369

  5. Redox reaction rates in shallow aquifers: Implications for nitrate transport in groundwater and streams

    USGS Publications Warehouse

    Tesoriero, Anthony J.

    2012-01-01

    Groundwater age and water chemistry data along flow paths from recharge areas to streams were used to evaluate the trends and transformations of agricultural chemicals. Results from this analysis indicate that median nitrate recharge concentrations in these agricultural areas have increased markedly over the last 50 years from 4 mg N/L in samples collected prior to 1983 to 7.5 mg N/L in samples collected since 1983. The effect that nitrate accumulation in shallow aquifers will have on drinking water quality and stream ecosystems is dependent on the rate of redox reactions along flow paths and on the age distribution of nitrate discharging to supply wells and streams.

  6. Novel technique for constraining r-process (n, γ) reaction rates.

    PubMed

    Spyrou, A; Liddick, S N; Larsen, A C; Guttormsen, M; Cooper, K; Dombos, A C; Morrissey, D J; Naqvi, F; Perdikakis, G; Quinn, S J; Renstrøm, T; Rodriguez, J A; Simon, A; Sumithrarachchi, C S; Zegers, R G T

    2014-12-01

    A novel technique has been developed, which will open exciting new opportunities for studying the very neutron-rich nuclei involved in the r process. As a proof of principle, the γ spectra from the β decay of ^{76}Ga have been measured with the SuN detector at the National Superconducting Cyclotron Laboratory. The nuclear level density and γ-ray strength function are extracted and used as input to Hauser-Feshbach calculations. The present technique is shown to strongly constrain the ^{75}Ge(n,γ)^{76}Ge cross section and reaction rate. PMID:25526121

  7. Optimal choice of dividing surface for the computation of quantum reaction rates.

    PubMed

    Predescu, Cristian; Miller, William H

    2005-04-14

    We consider the calculation of quantum mechanical rate constants for chemical reactions via algorithms that utilize short-time values of the symmetrized flux-flux correlation function. We argue that the dividing surface that makes optimal use of the short-time quantum information is the surface that minimizes the value at the origin of the symmetrized flux-flux correlation function. We also demonstrate that, in the classical limit, this quantum variational criterion produces the same dividing surface as Wigner's variational principle. Finally, we argue that the quantum variational criterion behaves in a nearly optimal fashion with respect to the minimization of the extent of re-crossing flux. PMID:16851728

  8. First Results of Reaction Propagation Rates in HMX at High Pressure

    SciTech Connect

    Farber, D L; Esposito, A; Zaug, J M; Aracne-Ruddle, C

    2001-06-15

    The authors have measured the reaction propagation rate (RPR) in weapons-grade, ultrafine octahydro-1,3,57-tetranitro-1,3,5,7-tetrazocine (HMX) powder in a diamond anvil cell over the pressure range 0.7-35 GPa. In order to have a cross-comparison of their experiments, they carried out a series of experiments on nitromethane (NM) up to 15 GPa. The results on NM are indistinguishable from previous measurements of Rice and Folz. In comparison to high-pressure, NM, the burn process for solid HMX is not spatially uniform.

  9. First Results of Reaction Propagation Rates in HMX at High Pressure

    SciTech Connect

    Farber, D L; Esposito, A; Zaug, J M; Aracne-Ruddle, C

    2001-06-15

    The authors have measured the reaction propagation rate (RPR) in weapons-grade, ultrafine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) powder in a diamond anvil cell over the pressure range 0.7-35 GPa. In order to have a cross-comparison of their experiments, they carried out a series of experiments on nitromethane (NM) up to 15 GPa. The results on NM are indistinguishable from previous measurements of Rice and Folz. In comparison to high-pressure NM, the burn process for solid HMX is between 5-10 times faster at pressures above 10 GPa.

  10. Chemical reaction rates using the semiclassical Van-Vleck initialvalue representation

    SciTech Connect

    Venkataraman, Charulatha; Miller, William H.

    2006-11-29

    A semiclassical IVR formulation using the Van-Vleck propagator has been used to calculate the flux correlation function and thereby reaction rate constants. This Van-Vleck formulation of the flux-flux correlation function is computationally as simple as the classical Wigner model. However unlike the latter, it has the ability to capture quantum interference/coherence effects. Classical trajectories are evolved starting from the dividing surface that separates reactants and products, and are evolved negatively in time. This formulation has been tested on model problems ranging from the Eckart barrier, double well to the collinear H + H{sub 2}.

  11. Measurement of (α,n) reaction cross sections of erbium isotopes for testing astrophysical rate predictions

    NASA Astrophysics Data System (ADS)

    Kiss, G. G.; Szücs, T.; Rauscher, T.; Török, Zs; Csedreki, L.; Fülöp, Zs; Gyürky, Gy; Halász, Z.

    2015-05-01

    The γ-process in core-collapse and/or type Ia supernova explosions is thought to explain the origin of the majority of the so-called p nuclei (the 35 proton-rich isotopes between Se and Hg). Reaction rates for γ-process reaction network studies have to be predicted using Hauser-Feshbach statistical model calculations. Recent investigations have shown problems in the prediction of α-widths at astrophysical energies which are an essential input for the statistical model. It has an impact on the reliability of abundance predictions in the upper mass range of the p nuclei. With the measurement of the 164,166Er(α,n)167,169Yb reaction cross sections at energies close to the astrophysically relevant energy range we tested the recently suggested low energy modification of the α+nucleus optical potential in a mass region where γ-process calculations exhibit an underproduction of the p nuclei. Using the same optical potential for the α-width which was derived from combined 162Er(α,n) and 162Er(α,γ) measurement makes it plausible that a low-energy modification of the optical α+nucleus potential is needed.

  12. Breakdown of the reaction-diffusion master equation with nonelementary rates

    NASA Astrophysics Data System (ADS)

    Smith, Stephen; Grima, Ramon

    2016-05-01

    The chemical master equation (CME) is the exact mathematical formulation of chemical reactions occurring in a dilute and well-mixed volume. The reaction-diffusion master equation (RDME) is a stochastic description of reaction-diffusion processes on a spatial lattice, assuming well mixing only on the length scale of the lattice. It is clear that, for the sake of consistency, the solution of the RDME of a chemical system should converge to the solution of the CME of the same system in the limit of fast diffusion: Indeed, this has been tacitly assumed in most literature concerning the RDME. We show that, in the limit of fast diffusion, the RDME indeed converges to a master equation but not necessarily the CME. We introduce a class of propensity functions, such that if the RDME has propensities exclusively of this class, then the RDME converges to the CME of the same system, whereas if the RDME has propensities not in this class, then convergence is not guaranteed. These are revealed to be elementary and nonelementary propensities, respectively. We also show that independent of the type of propensity, the RDME converges to the CME in the simultaneous limit of fast diffusion and large volumes. We illustrate our results with some simple example systems and argue that the RDME cannot generally be an accurate description of systems with nonelementary rates.

  13. Noise-induced convergence of the low flow rate chaos in the Belousov-Zhabotinsky reaction

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Minoru; Nakaiwa, Masaru; Akiya, Takaji; Ohmori, Takao; Yamaguchi, Tomohiko

    The effect of noise on the low flow-rate chaos in the Belousov-Zhabotinsky (BZ) reaction was studied. The chaos was simulated using the three-variable model of Györgyi and Field. Gaussian white noise was imposed on the flow-rate of the reactant solutions fed into CSTR to simulate the so-called type P noise. The range of average noise amplitudes was chosen between 0.01% and 1% related to the inverse residence time. The calculated time series were analyzed on the basis of their Fourier spectra, maximum Lyapunov exponent, Kolmogorov entropies, return maps and invariant density. We found that the noise induces partial order of the period-3-like oscillations in the low flowrate chaos.

  14. Absolute rate constants for the reaction of atomic hydrogen with ketene from 298 to 500 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Nava, D. F.; Payne, W. A.; Stief, L. J.

    1979-01-01

    Rate constants for the reaction of atomic hydrogen with ketene have been measured at room temperature by two techniques, flash photolysis-resonance fluorescence and discharge flow-resonance fluorescence. The measured values are (6.19 + or - 1.68) x 10 to the -14th and (7.3 + or - 1.3) x 10 to the -14th cu cm/molecule/s, respectively. In addition, rate constants as a function of temperature have been measured over the range 298-500 K using the FP-RF technique. The results are best represented by the Arrhenius expression k = (1.88 + or - 1.12) x 10 to the -11th exp(-1725 + or - 190/T) cu cm/molecule/s, where the indicated errors are at the two standard deviation level.

  15. Elementary reaction rate measurements at high temperatures by tunable-laser flash-absorption

    SciTech Connect

    Hessler, J.P.

    1993-12-01

    The major objective of this program is to measure thermal rate coefficients and branching ratios of elementary reactions. To perform these measurements, the authors constructed an ultrahigh-purity shock tube to generate temperatures between 1000 and 5500 K. The tunable-laser flash-absorption technique is used to measure the rate of change of the concentration of species which absorb below 50,000 cm{sup {minus}1} e.g.: OH, CH, and CH{sub 3}. This technique is being extended into the vacuum-ultraviolet spectral region where one can measure atomic species e.g.: H, D, C, O, and N; and diatomic species e.g.: O{sub 2}, CO, and OH.

  16. Solvent effects on the rate constants for reaction of trichloromethylperoxyl radicals with organic reductants

    SciTech Connect

    Alfassi, Z.B.; Huie, R.E.; Neta, P. )

    1993-07-15

    Absolute rate constants for the reactions of trichloromethylperoxyl radicals with chloropromazine and trolox have been determined by pulse radiolysis in 16 different solvents. The rate constants were found to vary over two orders of magnitude (10[sup 7]-10[sup 9] L mol[sup [minus]1] s[sup [minus]1]) and to correlate with the Hildebrand solubility parameter (cohesive energy density) of the solvent better than with any other single solvent parameter. The correlation was satisfactory for ClPz and did not improve significantly by including additional parameters. For trolox, however, the correlation was relatively poor but was improved considerably by taking into account the basicity of the solvent. This effect is due to the transfer of a proton upon the oxidation of trolox. 21 refs., 3 figs., 2 tabs.

  17. Informing Neutron-Capture Rates through (d,p) Reactions on Neutron-Rich Tin Isotopes

    NASA Astrophysics Data System (ADS)

    Manning, B.; Cizewski, J. A.; Kozub, R. L.; Ahn, S.; Allmond, J. M.; Bardayan, D. W.; Chae, K. Y.; Chipps, K. A.; Howard, M. E.; Jones, K. L.; Liang, J. F.; Matos, M.; Nunes, F. M.; Nesaraja, C. D.; O'Malley, P. D.; Pain, S. D.; Peters, W. A.; Pittman, S. T.; Ratkiewicz, A.; Schmitt, K. T.; Shapira, D.; Smith, M. S.; Titus, L.

    2014-03-01

    Level energies and spectroscopic information for neutron-rich nuclei provide important input for r-process nucleosynthesis calculations; specifically, the location and strength of single-neutron l = 1 states when calculating neutron-capture rates. Surman and collaborators have performed sensitivity studies to show that varying neutron-capture rates can significantly alter final r-process abundances. However, there are many nuclei important to the r-process that cannot be studied. Extending studies to more neutron-rich nuclei will help constrain the nuclear shell-model in extrapolating to nuclei even further from stability. The (d,p) reaction has been measured with radioactive ion beams of 126Sn and 128Sn to complete the set of (d,p) studies on even mass tin isotopes from doubly-magic 132 to stable 124Sn. Work supported in part by the U.S. Department of Energy and National Science Foundation.

  18. PH-dependence of the steady-state rate of a two-step enzymic reaction.

    PubMed

    Brocklehurst, K; Dixon, H B

    1976-04-01

    1. The pH-dependence is considered of a reaction between E and S that proceeds through an intermediate ES under "Briggs-Haldane' conditions, i.e. there is a steady state in ES and [S]o greater than [E]T, where [S]o is the initial concentration of S and [E]T is the total concentration of all forms of E. Reactants and intermediates are assumed to interconvert in three protonic states (E equilibrium ES; EH equilibrium EHS; EH2 equilibrium EH2S), but only EHS provides products by an irreversible reaction whose rate constant is kcat. Protonations are assumed to be so fast that they are all at equilibrium. 2. The rate equation for this model is shown to be v = d[P]/dt = (kcat.[E]T[S]o/A)/[(KmBC/DA) + [S]o], where Km is the usual assembly of rate constants around EHS and A-D are functions of the form (1 + [H]/K1 + K2/[H]), in which K1 and K2 are: in A, the molecular ionization constants of ES; in B, the analogous constants of E; in C and D, apparent ionization constants composed of molecular ionization constants (of E or ES) and assemblies of rate constants. 3. As in earlier treatments of this type of reaction which involve either the assumption that the reactants and intermediate are in equilibrium or the assumption of Peller & Alberty [(1959) J. Am. Chem. Soc. 81, 5907-5914] that only EH and EHS interconvert directly, the pH-dependence of kcat. is determined only by A. 4. The pH-dependence of Km is determined in general by B-C/A-D, but when reactants and intermediate are in equilibrium, C identical to D and this expression simplifies to B/A. 5. The pH-dependence of kcat./Km, i.e. of the rate when [S]o less than Km, is not necessarily a simple bell-shaped curve characterized only by the ionization constants of B, but is a complex curve characterized by D/B-C. 6. Various situations are discussed in which the pH-dependence of kcat./Km is determined by assemblies simpler than D/B-C. The special situation in which a kcat./Km-pH profile provides the molecular pKa values of

  19. A new rating scale for negative symptoms: the Motor-Affective-Social Scale.

    PubMed

    Trémeau, Fabien; Goggin, Michelle; Antonius, Daniel; Czobor, Pàl; Hill, Vera; Citrome, Leslie

    2008-09-30

    The commonly used rating scales for negative symptoms in schizophrenia have shown good reliability, but disagreement persists regarding both the content definition and the validity of several items. Instead, authors have recommended rating the specific behaviors that are defined as negative symptoms. To surmount these shortcomings, we developed a new rating scale for negative symptoms: the Motor-Affective-Social Scale (MASS). During a 5-minute structured interview, hand coverbal gestures, spontaneous smiles, voluntary smiling, and questions asked by the interviewer were counted and rated on 101 inpatients with a diagnosis of schizophrenia or schizoaffective disorder. Information on social behavior was obtained from nursing staff. The scale consisted of a total of eight items. The MASS showed high internal consistency (Cronbach alpha coefficient=0.81), inter-rater reliability, and test-retest reliability (intra-class correlation coefficient=0.81). Convergent validity analyses showed high correlations between MASS scores and scores on the Scale for the Assessment of Negative Symptom (SANS), and the negative symptoms subscale of the Positive and Negative Syndrome Scale (PANSS). The MASS showed excellent psychometric properties, practicality, and subject tolerability. Future research that includes the use of the MASS with other patient populations and that investigates the scale's sensitivity during clinical trials should be performed. PMID:18722021

  20. Scanning electrochemical microscopy of metallic biomaterials: reaction rate and ion release imaging modes.

    PubMed

    Gilbert, J L; Smith, S M; Lautenschlager, E P

    1993-11-01

    The Scanning Electrochemical Microscope (SECM) is a nonoptical scanning microscopic instrument capable of imaging highly localized electrical currents associated with charge transfer reactions on metallic biomaterials surfaces. The SECM operates as an aqueous electrochemical cell under bipotentiostatic control with a microelectrode and sample independently biased as working electrodes. Microelectrode current and position is recorded as it is scanned very near a metallurgically polished planar sample surface. To date, the SECM has imaged metallic biomaterials surfaces in oxygen reaction rate imaging (ORRI) and ion release and deposition imaging (IRDI) modes. In ORRI, sample and microelectrode are biased at sufficiently negative potentials to reduce absorbed oxygen. As the microelectrode scans areas of active oxygen reduction, localized diffusion fields with decreased oxygen solution concentrations are encountered and resultant decrements in microelectrode current are observed. In IRDI mode the sample is positively biased and the microelectrode is negatively biased. The microelectrode detects anodic dissolution products with highest currents being observed over the most active areas. Performance of the SECM has been evaluated on Ni minigrids, gamma-1 Hg-Ag dental amalgam crystals, and sintered beads of Co-Cr-Mo alloy which represent significantly different geometries and corrosion processes to help demonstrate the potential of this instrument. The SECM is a valuable tool for imaging microelectrochemical processes on the surfaces of metallurgically polished metallic biomaterials samples and a wide variety of other surfaces of biological interest where charge transfer reactions occur. The SECM allows selective biasing of metallic biomaterials surfaces and Faradaic reactions can be selectively imaged while the surface is in the active, passive, or transpassive state. PMID:8262998

  1. Reaction Rate Theory of Radiation Exposure and Scaling Hypothesis in Mutation Frequency

    NASA Astrophysics Data System (ADS)

    Manabe, Yuichiro; Nakamura, Issei; Bando, Masako

    2014-11-01

    We have developed a kinetic reaction model for cells with irradiated DNA molecules due to ionizing radiation exposure. Our theory simultaneously accounts for the time-dependent reactions of DNA damage, DNA mutation and DNA repair, and the proliferation and apoptosis of cells in a tissue with a minimal set of model parameters. In contrast to existing theories of radiation exposition, we do not assume the relationships between the total dose and the induced mutation frequency. Our theory provides a universal scaling function that reasonably explains the mega-mouse experiments by Russell and Kelly [Proc. Natl. Acad. Sci. U.S.A. 79, 542 (1982)] with different dose rates. Furthermore, we have estimated the effective dose rate, which is biologically equivalent to the ionizing effects other than those caused by artificial irradiation. This value is 1.11 × 10-3 Gy/h, which is significantly larger than the effect caused by natural background radiation.

  2. The application of the Reaction Rate Analyser LKB 8600 as an automatic coagulometer.

    PubMed

    Andersen, I; Thorsen, S

    1977-02-01

    The application of the Reaction Rate Analyser LKB 8600 (RRA) as an automatic coagulometer is described. The RRA was slightly modified without interfering with its function as an enzyme reaction rate analyser. The endpoint of coagulation was recorded when the increase in absorbance exceeded 0.047 at lambda = 340 nm. The coagulation time was monitored by a counter with automatic print-out or by a recorder. The analytical dispersion, s(x)x, ranged between 0.01 and 0.05. Results (x, y) of the determination of the quantity of plasma coagulation factors (II + VII + X) by RRA and manually by visual recording could be expressed by y = 0.93x + 0.04, r = 0.96, n = 66 (method of Owren & Aas) or by y = 1.00x + 0.02, r = 0.98, n = 49 (Normotest). Similarly, plasma activated partial thromboplastin time (Activated Thrombofax) could be expressed by y = 0.99x + 5.00, r = 0.99, n = 23. PMID:616030

  3. Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR.

    PubMed

    Balzan, Riccardo; Fernandes, Laetitia; Comment, Arnaud; Pidial, Laetitia; Tavitian, Bertrand; Vasos, Paul R

    2016-01-01

    The main limitation of NMR-based investigations is low sensitivity. This prompts for long acquisition times, thus preventing real-time NMR measurements of metabolic transformations. Hyperpolarization via dissolution DNP circumvents part of the sensitivity issues thanks to the large out-of-equilibrium nuclear magnetization stemming from the electron-to-nucleus spin polarization transfer. The high NMR signal obtained can be used to monitor chemical reactions in real time. The downside of hyperpolarized NMR resides in the limited time window available for signal acquisition, which is usually on the order of the nuclear spin longitudinal relaxation time constant, T1, or, in favorable cases, on the order of the relaxation time constant associated with the singlet-state of coupled nuclei, TLLS. Cellular uptake of endogenous molecules and metabolic rates can provide essential information on tumor development and drug response. Numerous previous hyperpolarized NMR studies have demonstrated the relevancy of pyruvate as a metabolic substrate for monitoring enzymatic activity in vivo. This work provides a detailed description of the experimental setup and methods required for the study of enzymatic reactions, in particular the pyruvate-to-lactate conversion rate in presence of lactate dehydrogenase (LDH), by hyperpolarized NMR. PMID:26967906

  4. Reaction Rate Measurement at the Californium User Facility (CUF) for unfolding the neutron spectrum

    NASA Astrophysics Data System (ADS)

    Hannan, Mohammad; Ortega, Ruben

    2011-03-01

    Neutron Activation Analysis was used to determine Reaction Rate measurement of several activation detectors at the ORNL Californium User Facility (CUF). The irradiations were performed with 34 mg Cf 252 neutron source strength.. Ten source capsules > 34 mgwerepositionedconcentricallyaroundasamplecavity . Wehavedeterminedabsoluteactivityperatomof 9 detectors : Au 197 (n , γ) Au 198 , Al 27 (n , α) Na 24 , Al 27 (n , p) Mg 27 , Fe 56 (n , p) Mn 5 , Fe 54 (n , p) Mn 54 , In 115 (n , γ) In 116 , Ti 46 (n , p) Sc 46 , Ni 60 (n , p) Co 60 , Fe 58 (n , γ) Fe 59 . Theerrorsarewithin 1.5 - 8 60 and Fe 58 have errors of 46% and 32 %. These high errors may be attributed to the counting statistics. These reaction rate values will be used to unfold the neutron spectrum of the CUF using the MAXED 2000, a computer code for the de convolution of multi sphere neutron spectrometer data and the results are discussed. The authors acknowledge help, advise, and using facility at ORNL-CUF to Dr. Rodger martin and Mr. David C. Galsgow.

  5. Individual variation affects departure rate from the natal pond in an ephemeral pond-breeding anuran

    USGS Publications Warehouse

    Chelgren, N.D.; Rosenberg, D.K.; Heppell, S.S.; Gitelman, A.I.

    2008-01-01

    Frogs exhibit extreme plasticity and individual variation in growth and behavior during metamorphosis, driven by interactions of intrinsic state factors and extrinsic environmental factors. In northern red-legged frogs (Rana aurora Baird and Girard, 1852), we studied the timing of departure from the natal pond as it relates to date and size of individuals at metamorphosis in the context of environmental uncertainty. To affect body size at metamorphosis, we manipulated food availability during the larval stage for a sample (317) of 1045 uniquely marked individuals and released them at their natal ponds as newly metamorphosed frogs. We recaptured 34% of marked frogs in pitfall traps as they departed and related the timing of their initial terrestrial movements to individual properties using a time-to-event model. Median age at first capture was 4 and 9 days postmetamorphosis at two sites. The rate of departure was positively related to body size and to date of metamorphosis. Departure rate was strongly negatively related to time elapsed since rainfall, and this effect was diminished for smaller and later metamorphosing frogs. Individual variation in metamorphic traits thus affects individuals' responses to environmental variability, supporting a behavioral link with variation in survival associated with these same metamorphic traits. ?? 2008 NRC.

  6. Crack growth rates of irradiated austenitic stainless steel weld heat affected zone in BWR environments.

    SciTech Connect

    Chopra, O. K.; Alexandreanu, B.; Gruber, E. E.; Daum, R. S.; Shack, W. J.; Energy Technology

    2006-01-31

    Austenitic stainless steels (SSs) are used extensively as structural alloys in the internal components of reactor pressure vessels because of their superior fracture toughness. However, exposure to high levels of neutron irradiation for extended periods can exacerbate the corrosion fatigue and stress corrosion cracking (SCC) behavior of these steels by affecting the material microchemistry, material microstructure, and water chemistry. Experimental data are presented on crack growth rates of the heat affected zone (HAZ) in Types 304L and 304 SS weld specimens before and after they were irradiated to a fluence of 5.0 x 10{sup 20} n/cm{sup 2} (E > 1 MeV) ({approx} 0.75 dpa) at {approx}288 C. Crack growth tests were conducted under cycling loading and long hold time trapezoidal loading in simulated boiling water reactor environments on Type 304L SS HAZ of the H5 weld from the Grand Gulf reactor core shroud and on Type 304 SS HAZ of a laboratory-prepared weld. The effects of material composition, irradiation, and water chemistry on growth rates are discussed.

  7. Relationship between the surface coverage of spectator species and the rate of electrocatalytic reactions.

    SciTech Connect

    Strmcnik, D. S.; Rebec, P.; Gaberscek, M.; Tripkovic, D.; Stamenkovic, V.; Lucas, C.; Markovic, N. M.; Materials Science Division; Univ. of Chicago; National Inst. of Chemistry; Univ. of Liverpool

    2007-12-20

    Relationships between the surface coverage of spectator (blocking) species and the rate of the hydrogen oxidation reaction (HOR), the oxygen reduction reaction (ORR), and the bulk oxidation of dissolved CO on Pt(100) and Pt(111) single crystals in acidic electrolytes has been probed by cyclic voltammetry, in situ surface X-ray scattering (SXS), and ex situ scanning tunneling microscopy (STM) techniques. It is shown that the surface coverage by spectator species during the HOR and the ORR are the same as for the corresponding coverage obtained in the inert (Ar-saturated) environment. This observation is consistent with the proposition that the availability of active sites for H{sub 2} and O{sub 2} is determined almost entirely by the coverage of adsorbates from the supporting electrolyte and not by the active intermediates. Related electrochemical-SXS studies undertaken for bulk CO oxidation reveal that the maximum rate above the ignition potential is reached on a surface that is covered by {approx}90% of an ordered CO adlayer. The nature of the active sites in this case is determined by a combination of electrochemical and STM results. It is found that the active sites in this potential region are steps, which appear to be active sites for OH adsorption. To get insight into the relationship between the diffusion-limiting current and the surface coverage by the inactive CO adlayer, we introduce the concept of a partially blocked electrode surface with active and inactive areas. On the basis of the calculations and experimental results, it is proposed that the active sites for given electrochemical reactions on Pt electrodes are arrays of adsorbate-free nanoscale patches embedded in an inactive adlayer of nonreactive molecular species.

  8. Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study

    SciTech Connect

    Vasu, Subith; Huynh, Lam; Davidson, David F.; Hanson, Ronald K.; Golden, David

    2011-03-09

    Reactions of hydroxyl (OH) radicals with 1-butene (k1), trans-2-butene (k2), and cis-2-butene (k3) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH3)3-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C5 oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.

  9. Thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates of BTATz-CMDB propellant.

    PubMed

    Yi, Jian-Hua; Zhao, Feng-Qi; Wang, Bo-Zhou; Liu, Qian; Zhou, Cheng; Hu, Rong-Zu; Ren, Ying-Hui; Xu, Si-Yu; Xu, Kang-Zhen; Ren, Xiao-Ning

    2010-09-15

    The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f(alpha)=(1-alpha)(2), and the kinetic equations are dalpha/dt = 10(19.24)(1-alpha)(2)e(-2.32x10(4)/T) and dalpha/dt = 10(20.32)(1-alpha)(2)e(-2.32x10(4)/T). The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa. PMID:20542638

  10. Product distributions and rate constants for ion-molecule reactions in water, hydrogen sulfide, ammonia, and methane

    NASA Technical Reports Server (NTRS)

    Huntress, W. T., Jr.; Pinizzotto, R. F., Jr.

    1973-01-01

    The thermal energy, bimolecular ion-molecule reactions occurring in gaseous water, hydrogen sulfide, ammonia, and methane have been identified and their rate constants determined using ion cyclotron resonance methods. Absolute rate constants were determined for the disappearance of the primary ions by using the trapped ion method, and product distributions were determined for these reactions by using the cyclotron ejection method. Previous measurements are reviewed and compared with the results using the present methods. The relative rate constants for hydrogen-atom abstraction, proton transfer, and charge transfer are also determined for reactions of the parent ions.

  11. Mechanisms linking affective reactions to competition-related and competition-extraneous concerns in male martial artists

    PubMed Central

    Cerin, E; Barnett, A

    2011-01-01

    The main aim of this study was to examine affective linkages between competition-related and competition-extraneous concern domains. A secondary purpose was to establish the contributions of pre-competition affects to post-competition performance appraisals, independent of pre-competition performance expectations. Thirty-nine highly skilled male martial artists were assessed at five random times a day for a week and 1 h before a major competition on affective states and sources of concern. They also reported their performance expectations and post-competition performance appraisals. Affective states triggered by competition-related and competition-extraneous concerns persisted in time. Carry-over effects were stronger after reports of competition-related concerns, emphasizing the subjective importance of the competitive event. Although positive (enjoyment and surprise) and negative (sadness and guilt) affective spill-over was observed from competition-extraneous to competition-related concerns, the reverse held true only for disgust. These findings may be due to the athletes' ability to regulate affective reactions within a sporting setting, in particular. Spill-over from competition-extraneous to competition-related concerns is indicative of a lesser degree of control over work/study and family life. Given that average weekly negative affects and anger/disgust were independent predictors of post-competition performance appraisals, the phenomenon of spill-over and other affective linkage mechanisms in sport warrant further investigation. PMID:21917020

  12. Ground reaction forces and loading rates associated with parkour and traditional drop landing techniques.

    PubMed

    Puddle, Damien L; Maulder, Peter S

    2013-01-01

    Due to the relative infancy of Parkour there is currently a lack of empirical evidence on which to base specific technique instruction upon. The purpose of this study was to compare the ground reaction forces and loading rates involved in two Parkour landing techniques encouraged by local Parkour instructors and a traditional landing technique recommended in the literature. Ten male participants performed three different drop landing techniques (Parkour precision, Parkour roll, and traditional) onto a force plate. Compared to the traditional technique the Parkour precision technique demonstrated significantly less maximal vertical landing force (38%, p < 0.01, ES = 1.76) and landing loading rate (54%, p < 0.01, ES = 1.22). Similarly, less maximal vertical landing force (43%, p < 0.01, ES = 2.04) and landing loading rate (63%, p < 0.01, ES = 1.54) were observed in the Parkour roll technique compared to the traditional technique. It is unclear whether or not the Parkour precision technique produced lower landing forces and loading rates than the Parkour roll technique as no significant differences were found. The landing techniques encouraged by local Parkour instructors such as the precision and roll appear to be more appropriate for Parkour practitioners to perform than a traditional landing technique due to the lower landing forces and loading rates experienced. Key pointsParkour precision and Parkour roll landings were found to be safer than a traditional landing technique, resulting in lower maximal vertical forces, slower times to maximal vertical force and ultimately lesser loading rates.Parkour roll may be more appropriate (safer) to utilize than the Parkour precision during Parkour landing scenarios.The Parkour landing techniques investigated n this study may be beneficial for landing by non-Parkour practitioners in everyday life. PMID:24149735

  13. Ground Reaction Forces and Loading Rates Associated with Parkour and Traditional Drop Landing Techniques

    PubMed Central

    Puddle, Damien L.; Maulder, Peter S.

    2013-01-01

    Due to the relative infancy of Parkour there is currently a lack of empirical evidence on which to base specific technique instruction upon. The purpose of this study was to compare the ground reaction forces and loading rates involved in two Parkour landing techniques encouraged by local Parkour instructors and a traditional landing technique recommended in the literature. Ten male participants performed three different drop landing techniques (Parkour precision, Parkour roll, and traditional) onto a force plate. Compared to the traditional technique the Parkour precision technique demonstrated significantly less maximal vertical landing force (38%, p < 0.01, ES = 1.76) and landing loading rate (54%, p < 0.01, ES = 1.22). Similarly, less maximal vertical landing force (43%, p < 0.01, ES = 2.04) and landing loading rate (63%, p < 0.01, ES = 1.54) were observed in the Parkour roll technique compared to the traditional technique. It is unclear whether or not the Parkour precision technique produced lower landing forces and loading rates than the Parkour roll technique as no significant differences were found. The landing techniques encouraged by local Parkour instructors such as the precision and roll appear to be more appropriate for Parkour practitioners to perform than a traditional landing technique due to the lower landing forces and loading rates experienced. Key points Parkour precision and Parkour roll landings were found to be safer than a traditional landing technique, resulting in lower maximal vertical forces, slower times to maximal vertical force and ultimately lesser loading rates. Parkour roll may be more appropriate (safer) to utilize than the Parkour precision during Parkour landing scenarios. The Parkour landing techniques investigated n this study may be beneficial for landing by non-Parkour practitioners in everyday life. PMID:24149735

  14. Blastocyst rate of in vitro embryo production in sheep is affected by season.

    PubMed

    Mara, L; Sanna, D; Casu, S; Dattena, M; Muñoz, I M Mayorga

    2014-08-01

    It has been reported that the number and quality of in vitro produced embryos is season related. This study was conducted to assess the effect of season on cleavage, blastocyst and lambing rates of in vitro produced ovine embryos during 3 years of collection data. Ovaries of Sarda sheep were collected from a slaughterhouse. In total, 5035 oocytes were recovered and matured in TCM-199 with 4 mg/ml bovine serum albumin (BSA), 100 μM cysteamine, 0.3 mM Na pyruvate, 0.1 UI/ml recombinant follicle-stimulating hormone (r-FSH), 0.1 UI/ml recombinant luteinising hormone (r-LH), and 1 μg/ml estradiol-17β. Matured oocytes were fertilized with fresh semen in synthetic oviductal fluid (SOF) with 20% heat inactivated estrous sheep serum. The presumptive zygotes were cultured for 6-7 days (blastocyst stage) in SOF medium supplemented with 1% Basel Medium Eagle (BME), 1% Minimum Essential Medium, 1 mM glutamine and 8 mg/ml fatty acid-free BSA. The embryos produced were vitrified and a total of 165 blastocysts (80 from the breeding season and 85 from the anoestrous season) were transferred in pairs into recipient ewes during the reproductive period. There were no significant differences in cleavage rates between seasons in any of the 3 years examined (84% versus 83%, 81% versus 80% and 80% versus 79%, respectively). The blastocyst rate varied significantly between seasons in 2005 and 2007 (P < 0.05), and in 2006 (P < 0.001). There were no differences in pregnancy and lambing rates between embryos during anoestrous versus during the breeding season. In conclusion, only the blastocyst rate appeared to have been affected by season, possibly due to variation in the number of developmentally competent oocytes. PMID:23458093

  15. Alcohol-to-acid ratio and substrate concentration affect product structure in chain elongation reactions initiated by unacclimatized inoculum.

    PubMed

    Liu, Yuhao; Lü, Fan; Shao, Liming; He, Pinjing

    2016-10-01

    The objective of the study was to investigate whether the ratio of ethanol to acetate affects yield and product structure in chain elongation initiated by unacclimatized mixed cultures. The effect of varying the substrate concentration, while maintaining the same ratio of alcohol to acid, was also investigated. With a high substrate concentration, an alcohol to acid ratio >2:1 provided sufficient electron donor capacity for the chain elongation reaction. With an ethanol to acetate ratio of 3:1 (300mM total carbon), the highest n-caproate concentration (3033±98mg/L) was achieved during the stable phase of the reaction. A lower substrate concentration (150mM total carbon) gave a lower yield of products and led to reduced carbon transformation efficiency compared with other reaction conditions. The use of unacclimatized inoculum in chain elongation can produce significant amounts of odd-carbon-number carboxylates as a result of protein hydrolysis. PMID:27469095

  16. Rate and reaction probability of the surface reaction between ozone and dihydromyrcenol measured in a bench scale reactor and a room-sized chamber

    NASA Astrophysics Data System (ADS)

    Shu, Shi; Morrison, Glenn C.

    2012-02-01

    Low volatility terpenoids emitted from consumer products can react with ozone on surfaces and may significantly alter concentrations of ozone, terpenoids and reaction products in indoor air. We measured the reaction probability and a second-order surface-specific reaction rate for the ozonation of dihydromyrcenol, a representative indoor terpenoid, adsorbed onto polyvinylchloride (PVC), glass, and latex paint coated spheres. The reaction probability ranged from (0.06-8.97) × 10 -5 and was very sensitive to humidity, substrate and mass adsorbed. The average surface reaction probability is about 10 times greater than that for the gas-phase reaction. The second-order surface-specific rate coefficient ranged from (0.32-7.05) × 10 -15 cm 4 s -1 molecule -1and was much less sensitive to humidity, substrate, or mass adsorbed. We also measured the ozone deposition velocity due to adsorbed dihydromyrcenol on painted drywall in a room-sized chamber, Based on that, we calculated the rate coefficient ((0.42-1.6) × 10 -15 cm 4 molecule -1 s -1), which was consistent with that derived from bench-scale experiments for the latex paint under similar conditions. We predict that more than 95% of dihydromyrcenol oxidation takes place on indoor surfaces, rather than in building air.

  17. Attachment Status Affects Heart Rate Responses to Experimental Ostracism in Inpatients with Depression.

    PubMed

    De Rubeis, Jannika; Sütterlin, Stefan; Lange, Diane; Pawelzik, Markus; van Randenborgh, Annette; Victor, Daniela; Vögele, Claus

    2016-01-01

    Depression is assumed to be both a risk factor for rejection and a result of it, and as such constitutes an important factor in rejection research. Attachment theory has been applied to understand psychological disorders, such as depression, and can explain individual differences in responses to rejection. Research on autonomic nervous system activity to rejection experiences has been contradictory, with opposing strings of argumentation (activating vs. numbing). We investigated autonomic nervous system-mediated peripheral physiological responses (heart rate) to experimentally manipulated ostracism (Cyberball) in 97 depressed patients with organized (n = 52) and disorganized attachment status (n = 45). Controlling for baseline mean heart rate levels, depressed patients with disorganized attachment status responded to ostracism with significantly higher increases in heart rate than depressed patients with organized attachment status (p = .029; ηp2 = .051). These results suggest that attachment status may be a useful indicator of autonomic responses to perceived social threat, which in turn may affect the therapeutic process and the patient-therapist relationship. PMID:26943924

  18. The impact of social content and negative symptoms on affective ratings in schizophrenia

    PubMed Central

    Bodapati, Anjuli Singh; Herbener, Ellen

    2014-01-01

    The anhedonia paradox has been a topic of ongoing study in schizophrenia. Previous research has found that schizophrenia patients report less enjoyment from various activities when compared to their healthy counterparts; however, the two groups appear to have similar in-the-moment emotional ratings of these events (Gard et al., 2007; Herbener et al., 2007; Horan et al., 2006). This study examined these in-the-moment experiences further, by assessing whether they differed between social and non-social experiences. The data were collected from 38 individuals with schizophrenia and 53 matched healthy controls in the greater Chicago area. In-the-moment emotional experience was measured by self-reported arousal and valence ratings for social and non-social stimuli taken from the International Affective Picture System (IAPS). Clinical ratings for patients were gathered by the Positive and Negative Syndrome Scale. A series of ANOVAs revealed that controls were more aroused by the social than nonsocial unpleasant stimuli, whereas patients did not show this distinction. Further, regression analyses revealed that negative symptom severity uniquely predicted lower arousal responses to unpleasant social, but not nonsocial, stimuli. Our results indicate that both subject and stimulus factors appear to contribute to differences in emotional responses in individuals with schizophrenia. PMID:24745467

  19. Does Acellular Dermal Matrix Thickness Affect Complication Rate in Tissue Expander Based Breast Reconstruction?

    PubMed Central

    2016-01-01

    Background. While the benefits of using acellular dermal matrices (ADMs) in breast reconstruction are well described, their use has been associated with additional complications. The purpose of this study was to determine if ADM thickness affects complications in breast reconstruction. Methods. A retrospective chart review was performed including all tissue expander based breast reconstructions with AlloDerm (LifeCell, Branchburg, NJ) over 4 years. We evaluated preoperative characteristics and assessed postoperative complications including seroma, hematoma, infection, skin necrosis, and need for reintervention. We reviewed ADM thickness and time to Jackson-Pratt (JP) drain removal. Results. Fifty-five patients underwent 77 ADM-associated tissue expander based breast reconstructions, with average age of 48.1 years and average BMI of 25.9. Average ADM thickness was 1.21 mm. We found higher complication rates in the thick ADM group. Significant associations were found between smokers and skin necrosis (p < 0.0001) and seroma and prolonged JP drainage (p = 0.0004); radiated reconstructed breasts were more likely to suffer infections (p = 0.0085), and elevated BMI is a significant predictor for increased infection rate (p = 0.0037). Conclusion. We found a trend toward increased complication rates with thicker ADMs. In the future, larger prospective studies evaluating thickness may provide more information.

  20. Does Acellular Dermal Matrix Thickness Affect Complication Rate in Tissue Expander Based Breast Reconstruction?

    PubMed

    Rose, Jessica F; Zafar, Sarosh N; Ellsworth Iv, Warren A

    2016-01-01

    Background. While the benefits of using acellular dermal matrices (ADMs) in breast reconstruction are well described, their use has been associated with additional complications. The purpose of this study was to determine if ADM thickness affects complications in breast reconstruction. Methods. A retrospective chart review was performed including all tissue expander based breast reconstructions with AlloDerm (LifeCell, Branchburg, NJ) over 4 years. We evaluated preoperative characteristics and assessed postoperative complications including seroma, hematoma, infection, skin necrosis, and need for reintervention. We reviewed ADM thickness and time to Jackson-Pratt (JP) drain removal. Results. Fifty-five patients underwent 77 ADM-associated tissue expander based breast reconstructions, with average age of 48.1 years and average BMI of 25.9. Average ADM thickness was 1.21 mm. We found higher complication rates in the thick ADM group. Significant associations were found between smokers and skin necrosis (p < 0.0001) and seroma and prolonged JP drainage (p = 0.0004); radiated reconstructed breasts were more likely to suffer infections (p = 0.0085), and elevated BMI is a significant predictor for increased infection rate (p = 0.0037). Conclusion. We found a trend toward increased complication rates with thicker ADMs. In the future, larger prospective studies evaluating thickness may provide more information. PMID:27190645

  1. Attachment Status Affects Heart Rate Responses to Experimental Ostracism in Inpatients with Depression

    PubMed Central

    De Rubeis, Jannika; Sütterlin, Stefan; Lange, Diane; Pawelzik, Markus; van Randenborgh, Annette; Victor, Daniela; Vögele, Claus

    2016-01-01

    Depression is assumed to be both a risk factor for rejection and a result of it, and as such constitutes an important factor in rejection research. Attachment theory has been applied to understand psychological disorders, such as depression, and can explain individual differences in responses to rejection. Research on autonomic nervous system activity to rejection experiences has been contradictory, with opposing strings of argumentation (activating vs. numbing). We investigated autonomic nervous system-mediated peripheral physiological responses (heart rate) to experimentally manipulated ostracism (Cyberball) in 97 depressed patients with organized (n = 52) and disorganized attachment status (n = 45). Controlling for baseline mean heart rate levels, depressed patients with disorganized attachment status responded to ostracism with significantly higher increases in heart rate than depressed patients with organized attachment status (p = .029; ηp2 = .051). These results suggest that attachment status may be a useful indicator of autonomic responses to perceived social threat, which in turn may affect the therapeutic process and the patient-therapist relationship. PMID:26943924

  2. The Rate of Change of Vergence-Accommodation Conflict Affects Visual Discomfort

    PubMed Central

    Kane, David; Banks, Martin S.

    2014-01-01

    Stereoscopic (S3D) displays create conflicts between the distance to which the eyes must converge and the distance to which the eyes must accommodate. Such conflicts require the viewer to overcome the normal coupling between vergence and accommodation, and this effort appears to cause viewer discomfort. Vergence-accommodation coupling is driven by the phasic components of the underlying control systems, and those components respond to relatively fast changes in vergence and accommodative stimuli. Given the relationship between phasic changes and vergence-accommodation coupling, we examined how the rate of change in the vergence-accommodation conflict affects viewer discomfort. We used a stereoscopic display that allows independent manipulation of the stimuli to vergence and accommodation. We presented stimuli that simulate natural viewing (i.e., vergence and accommodative stimuli changed together) and stimuli that simulate S3D viewing (i.e., vergence stimulus changes but accommodative stimulus remains fixed). The changes occurred at 0.01, 0.05, or 0.25Hz. The lowest rate is too slow to stimulate the phasic components while the highest rate is well within the phasic range. The results were consistent with our expectation: somewhat greater discomfort was experienced when stimulus distance changed rapidly, particularly in S3D viewing when the vergence stimulus changed but the accommodative stimulus did not. These results may help in the generation of guidelines for the creation and viewing of stereo content with acceptable viewer comfort. PMID:25448713

  3. Conflicts during Response Selection Affect Response Programming: Reactions toward the Source of Stimulation

    ERIC Educational Resources Information Center

    Buetti, Simona; Kerzel, Dirk

    2009-01-01

    In the Simon effect, participants make a left or right keypress in response to a nonspatial attribute (e.g., color) that is presented on the left or right. Reaction times (RTs) increase when the response activated by the irrelevant stimulus location and the response retrieved by instruction are in conflict. The authors measured RTs and movement…

  4. Risk factors affecting the survival rate in patients with symptomatic pericardial effusion undergoing surgical intervention

    PubMed Central

    Mirhosseini, Seyed Mohsen; Fakhri, Mohammad; Mozaffary, Amirhossein; Lotfaliany, Mojtaba; Behzadnia, Neda; Ansari Aval, Zahra; Ghiasi, Seyed Mohammad Saeed; Boloursaz, Mohammad Reza; Masjedi, Mohammad Reza

    2013-01-01

    OBJECTIVES The optimal management and treatment of pericardial effusion are still controversial. There is limited data related to the risk factors affecting survival in these patients. The aim of this study was to determine the risk factors affecting the survival rate of patients with symptomatic pericardial effusion who underwent surgical interventions. METHODS From 2004 to 2011, we retrospectively analysed 153 patients who underwent subxiphoid pericardial window as their surgical intervention to drain pericardial effusions at the National Research Institute of Tuberculosis and Lung diseases (NRITLD). To determine the effects of risk factors on survival rate, demographic data, clinical records, echocardiographic data, computed tomographic and cytopathological findings and also operative information of patients were recorded. Patients were followed annually until the last clinical follow-up (August 2011). To determine the prognostic factors affecting survival, both univariate analysis and multivariate Cox proportional hazards model were utilized. RESULTS There were 89 men and 64 women with a mean age of 50.3 ± 15.5 years. The most prevalent symptom was dyspnoea. Concurrent malignancies were present in 66 patients. Lungs were the most prevalent primary site for malignancy. The median duration of follow-up was 15 (range 1–85 months). Six-month, 1-year and 18-month survival rates were 85.6, 61.4 and 36.6%, respectively. In a multivariate analysis, positive history of lung cancer (hazard ratio [HR] 2.894, 95% confidence interval [CI] 1.362–6.147, P = 0.006) or other organ cancers (HR 2.315, 95% CI 1.009–50311, P = 0.048), presence of a mass in the computed tomography (HR 1.985, 95% CI 1.100–3.581, P = 0.023), and echocardiographic findings compatible with tamponade (HR 1.745, 95% CI 1.048–2.90 P = 0.032) were the three independent predictors of postoperative death. CONCLUSIONS In the surgical management of pericardial effusion, patients with underlying

  5. Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1974-01-01

    Rate constants of two elementary bimolecular reactions involved in the oxidation of methane have been determined by monitoring the exponential growth of CO flame band emission behind incident shocks in three suitably chosen gas mixtures. The data do not support a mechanism which invokes the four center process CH3 + O2 yields CH2O + OH for the reaction of methyl with oxygen.

  6. Stress-associated cardiovascular reaction masks heart rate dependence on physical load in mice.

    PubMed

    Andreev-Andrievskiy, A A; Popova, A S; Borovik, A S; Dolgov, O N; Tsvirkun, D V; Custaud, M; Vinogradova, O L

    2014-06-10

    When tested on the treadmill mice do not display a graded increase of heart rate (HR), but rather a sharp shift of cardiovascular indices to high levels at the onset of locomotion. We hypothesized that under test conditions cardiovascular reaction to physical load in mice is masked with stress-associated HR increase. To test this hypothesis we monitored mean arterial pressure (MAP) and heart rate in C57BL/6 mice after exposure to stressful stimuli, during spontaneous locomotion in the open-field test, treadmill running or running in a wheel installed in the home cage. Mice were treated with β1-adrenoblocker atenolol (2mg/kg ip, A), cholinolytic ipratropium bromide (2mg/kg ip, I), combination of blockers (A+I), anxiolytic diazepam (5mg/kg ip, D) or saline (control trials, SAL). MAP and HR in mice increased sharply after handling, despite 3weeks of habituation to the procedure. Under stressful conditions of open field test cardiovascular parameters in mice were elevated and did not depend on movement speed. HR values did not differ in I and SAL groups and were reduced with A or A+I. HR was lower at rest in D pretreated mice. In the treadmill test HR increase over speeds of 6, 12 and 18m/min was roughly 1/7-1/10 of HR increase observed after placing the mice on the treadmill. HR could not be increased with cholinolytic (I), but was reduced after sympatholytic (A) or A+I treatment. Anxiolytic (D) reduced heart rate at lower speeds of movement and its overall effect was to unmask the dependency of HR on running speed. During voluntary running in non-stressful conditions of the home cage HR in mice linearly increased with increasing running speeds. We conclude that in test situations cardiovascular reactions in mice are governed predominantly by stress-associated sympathetic activation, rendering efforts to evaluate HR and MAP reactions to workload unreliable. PMID:24802359

  7. The role of advanced reactive surface area characterization in improving predictions of mineral reaction rates

    NASA Astrophysics Data System (ADS)

    Beckingham, L. E.; Zhang, S.; Mitnick, E.; Cole, D. R.; Yang, L.; Anovitz, L. M.; Sheets, J.; Swift, A.; Kneafsey, T. J.; Landrot, G.; Mito, S.; Xue, Z.; Steefel, C. I.; DePaolo, D. J.; Ajo Franklin, J. B.

    2014-12-01

    Geologic sequestration of CO2 in deep sedimentary formations is a promising means of mitigating carbon emissions from coal-fired power plants but the long-term fate of injected CO2 is challenging to predict. Reactive transport models are used to gain insight over long times but rely on laboratory determined mineral reaction rates that have been difficult to extrapolate to field systems. This, in part, is due to a lack of understanding of mineral reactive surface area. Many models use an arbitrary approximation of reactive surface area, applying orders of magnitude scaling factors to measured BET or geometric surface areas. Recently, a few more sophisticated approaches have used 2D and 3D image analyses to determine mineral-specific reactive surface areas that account for the accessibility of minerals. However, the ability of these advanced surface area estimates to improve predictions of mineral reaction rates has yet to be determined. In this study, we fuse X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB analysis to determine mineral-specific accessible reactive surface areas for a core sample from the Nagaoka pilot CO2 injection site (Japan). This sample is primarily quartz, plagioclase, smectite, K-feldspar, and pyroxene. SEM imaging shows abundant smectite cement and grain coatings that decrease the fluid accessibility of other minerals. However, analysis of FIB-SEM images reveals that smectite nano-pores are well connected such that access to underlying minerals is not occluded by smectite coatings. Mineral-specific accessible surfaces are determined, accounting for the connectivity of the pore space with and without connected smectite nano-pores. The large-scale impact of variations in accessibility and dissolution rates are then determined through continuum scale modeling using grid-cell specific information on accessible surface areas. This approach will be compared with a traditional continuum scale model using mineral abundances and common surface area

  8. Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes

    SciTech Connect

    Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang

    2014-05-07

    We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula.

  9. Mixed quantum classical calculation of proton transfer reaction rates: from deep tunneling to over the barrier regimes.

    PubMed

    Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang

    2014-05-01

    We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula. PMID:24811623

  10. The interplay between transport and reaction rates as controls on nitrate attenuation in permeable, streambed sediments

    NASA Astrophysics Data System (ADS)

    Lansdown, K.; Heppell, C. M.; Trimmer, M.; Binley, A.; Heathwaite, A. L.; Byrne, P.; Zhang, H.

    2015-06-01

    Anthropogenic nitrogen fixation and subsequent use of this nitrogen as fertilizer have greatly disturbed the global nitrogen cycle. Rivers are recognized hot spots of nitrogen removal in the landscape as interaction between surface water and sediments creates heterogeneous redox environments conducive for nitrogen transformations. Our understanding of riverbed nitrogen dynamics to date comes mainly from shallow sediments or hyporheic exchange flow pathways with comparatively little attention paid to groundwater-fed, gaining reaches. We have used 15N techniques to quantify in situ rates of nitrate removal to 1 m depth within a groundwater-fed riverbed where subsurface hydrology ranged from strong upwelling to predominantly horizontal water fluxes. We combine these rates with detailed hydrologic measurements to investigate the interplay between biogeochemical activity and water transport in controlling nitrogen attenuation along upwelling flow pathways. Nitrate attenuation occurred via denitrification rather than dissimilatory nitrate reduction to ammonium or anammox (range = 12 to >17,000 nmol 15N L-1 h-1). Overall, nitrate removal within the upwelling groundwater was controlled by water flux rather than reaction rate (i.e., Damköhler numbers <1) with the exception of two hot spots of biogeochemical activity. Deep sediments were as important a nitrate sink as shallow sediments with fast rates of denitrification and short water residence time close to the riverbed surface balanced by slower rates of denitrification and water flux at depth. Within this permeable riverbed >80% of nitrate removal occurs within sediments not exposed to hyporheic exchange flows under base flow conditions, illustrating the importance of deep sediments as nitrate sinks in upwelling systems.

  11. Shock tube measurements of specific reaction rates in branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1974-01-01

    Rate constants of two elementary bimolecular reactions involved in the oxidation of methane were determined by monitoring the exponential growth of CO flame band emission behind incident shocks in three suitably chosen gas mixtures.

  12. A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

    NASA Technical Reports Server (NTRS)

    Chinitz, W.; Foy, E.; Rowan, G.; Goldstein, D.

    1982-01-01

    The use of probability theory to determine the effects of turbulent fluctuations on reaction rates in turbulent combustion systems is briefly reviewed. Results are presented for the effect of species fluctuations in particular. It is found that turbulent fluctuations of species act to reduce the reaction rates, in contrast with the temperature fluctuations previously determined to increase Arrhenius reaction rate constants. For the temperature fluctuations, a criterion is set forth for determining if, in a given region of a turbulent flow field, the temperature can be expected to exhibit ramp like fluctuations. Using the above results, along with results previously obtained, a model is described for testing the effects of turbulent fluctuations of temperature and species on reaction rates in computer programs dealing with turbulent reacting flows. An alternative model which employs three variable probability density functions (temperature and two species) and is currently being formulated is discussed as well.

  13. Revised Production Rates for Na-22 and Mn-54 in Meteorites Using Cross Sections Measured for Neutron-induced Reactions

    NASA Technical Reports Server (NTRS)

    Sisterson, J. M.; Kim, K. J.; Reedy, R. C.

    2004-01-01

    The interactions of galactic cosmic rays (GCR) with extraterrestrial bodies produce small amounts of radionuclides and stable isotopes. The production rates of many relatively short-lived radionuclides, including 2.6-year Na-22 and 312-day Mn-54, have been measured in several meteorites collected very soon after they fell. Theoretical models used to calculate production rates for comparison with the measured values rely on input data containing good cross section measurements for all relevant reactions. Most GCR particles are protons, but secondary neutrons make most cosmogenic nuclides. Calculated production rates using only cross sections for proton-induced reactions do not agree well with measurements. One possible explanation is that the contribution to the production rate from reactions initiated by secondary neutrons produced in primary GCR interactions should be included explicitly. This, however, is difficult to do because so few of the relevant cross sections for neutron-induced reactions have been measured.

  14. Analysis of turbulent free jet hydrogen-air diffusion flames with finite chemical reaction rates

    NASA Technical Reports Server (NTRS)

    Sislian, J. P.

    1978-01-01

    The nonequilibrium flow field resulting from the turbulent mixing and combustion of a supersonic axisymmetric hydrogen jet in a supersonic parallel coflowing air stream is analyzed. Effective turbulent transport properties are determined using the (K-epsilon) model. The finite-rate chemistry model considers eight reactions between six chemical species, H, O, H2O, OH, O2, and H2. The governing set of nonlinear partial differential equations is solved by an implicit finite-difference procedure. Radial distributions are obtained at two downstream locations of variables such as turbulent kinetic energy, turbulent dissipation rate, turbulent scale length, and viscosity. The results show that these variables attain peak values at the axis of symmetry. Computed distributions of velocity, temperature, and mass fraction are also given. A direct analytical approach to account for the effect of species concentration fluctuations on the mean production rate of species (the phenomenon of unmixedness) is also presented. However, the use of the method does not seem justified in view of the excessive computer time required to solve the resulting system of equations.

  15. Muscular contraction mode differently affects autonomic control during heart rate matched exercise

    PubMed Central

    Weippert, Matthias; Behrens, Martin; Gonschorek, Ray; Bruhn, Sven; Behrens, Kristin

    2015-01-01

    The precise contributions of afferent feedback to cardiovascular and respiratory responses to exercise are still unclear. The aim of this crossover study was to assess whether and how autonomic cardiovascular and respiratory control differed in response to dynamic (DYN) and isometric contractions (ISO) at a similar, low heart rate (HR) level. Therefore, 22 healthy males (26.7 ± 3.6 yrs) performed two kinds of voluntary exercises at similar HR: ISO and DYN of the right quadriceps femoris muscle. Although HR was eqivalent (82 ± 8 bpm for DYN and ISO, respectively), rating of exertion, blood pressures, and rate pressure product were higher, whereas breathing frequency, minute ventilation, oxygen uptake and carbon dioxide output were significantly lower during ISO. Tidal volume, end-tidal partial pressures of O2 and CO2, respiratory exchange ratio and capillary blood lactate concentration were comparable between both contraction modes. Heart rate variability (HRV) indicators, SDNN, HF-Power and LF-Power, representing both vagal and sympathetic influences, were significantly higher during ISO. Sample entropy, a non-linear measure of HRV was also significantly affected by contraction mode. It can be concluded that, despite the same net effect on HR, the quality of cardiovascular control during low intensity exercise is significantly different between DYN and ISO. HRV analysis indicated a sympatho-vagal coactivation during ISO. Whether mechanoreceptor feedback alone, a change in central command, or the interaction of both mechanisms is the main contributor of the distinct autonomic responses to the different exercise modes remains to be elucidated. PMID:26042047

  16. Evaluating recipient and embryo factors that affect pregnancy rates of embryo transfer in beef cattle.

    PubMed

    Spell, A R; Beal, W E; Corah, L R; Lamb, G C

    2001-07-15

    The objectives of this experiment were to determine the effects of corpus luteum characteristics, progesterone concentration, donor-recipient synchrony, embryo quality, type, and developmental stage on pregnancy rates after embryo transfer. We synchronized 763 potential recipients for estrus using one of two synchronization protocols: two doses of PGF2alpha (25 mg i.m.) given 11 d apart (Location 1); and, a single norgestomet implant for 7 d with one dose of PGF2alpha (25 mg i.m.) 24 h before implant removal (Location 2). At embryo transfer, ovaries were examined by rectal palpation and ultrasonography. Of the 526 recipients presented for embryo transfer, 122 received a fresh embryo and 326 received a frozen embryo. Pregnancy rates were greater (P < 0.05) with fresh embryos (83%) than frozen-thawed embryos (69%). Pregnancy rates were not affected by embryo grade, embryo stage, donor-recipient synchrony, or the palpated integrity of the CL. Corpus luteum diameter and luteal tissue volume increased as days post-estrus for the recipients increased. However, pregnancy rates did not differ among recipients receiving embryos 6.5 to 8.5 days after estrus (P > 0.1). There was a significant, positive simple correlation between CL diameter or luteal tissue volume and plasma progesterone concentration (r = 0.15, P < 0.01 and r = 0.18, P < 0.01, respectively). There were no significant differences in mean CL diameter, luteal volume or plasma progesterone concentration among recipients that did or did not become pregnant after embryo transfer. We conclude that suitability of a potential embryo transfer recipient is determined by observed estrus and a palpable corpus luteum, regardless of size or quality. PMID:11480620

  17. Myasthenia gravis in patients with thymoma affects survival rate following extended thymectomy

    PubMed Central

    ZHANG, ZHEFENG; CUI, YOUBIN; JIA, RUI; XUE, LEI; LIANG, HUAGANG

    2016-01-01

    Thymomas are the most common adult tumors in the anterior mediastinal compartment, and a significant amount of thymomas are complicated by myasthenia gravis (MG). Extended thymectomy (ET) is the primary treatment method for thymomas and is used to completely resect possible ectopic thymus to avoid recurrence. Studies on the effect of MG in thymoma patients following ET are limited. The aim of the present study was to determine whether the presence of MG affects the prognosis of patients with thymoma. The present study consisted of 104 patients with thymoma that underwent ET; 61 men (58.7%) and 43 women (41.3%) (mean age, 54.6 years). In total, 38 patients had MG (36.5%). MG was most frequently observed in World Health Organization (WHO) classification type B2 thymoma compared with other types of thymoma. During the 5-year follow-up period, 11 patients succumbed to a recurrence of thymoma or respiratory failure due to MG. The overall 5-year survival rate in patients without MG or with MG was 89.1 and 76.0%, respectively. The overall survival (OS) rate in patients with Masaoka stages I + II and III + IV was 90.0 and 68.0%, respectively. The OS rate in patients with WHO type A + AB + B1 and type B2 + B3 was 96.9 and 76.8%, respectively. The patients with MG (P=0.026), Masaoka stages III + IV (P=0.008) and WHO type B2 + B3 (P=0.032) had a poorer prognosis compared with patients without these characteristics. Furthermore, multivariate analysis by Cox regression revealed that age [P=0.032; relative risk (RR)=1.097; 95% confidence interval (CI)=1.097–1.192] and MG (P=0.042; RR=0.167; 95% CI=0.037–0.940) significantly affected OS rate. In summary, ET is a reliable method for the treatment of thymoma. Long-term survival is expected for patients at early Masaoka stages, and for patients without MG. The prognosis of patients with thymomas with MG is poorer compared with patients without MG. The present findings provide useful information for the future management of

  18. Early diagenetic processes, fluxes, and reaction rates in sediments of the South Atlantic

    SciTech Connect

    Schulz, H.D.; Dahmke, A.; Schinzel, U.; Wallmann, K.; Zabel, M. )

    1994-05-01

    Porewaters recovered from sediment cores (gravity corers, box corers, and multicorers) from various subregions of the South Atlantic (Amazon River mouth, equatorial upwelling, Congo River mouth, Benguela coastal upwelling area, and Angola Basin) were investigated geochemically. Objectives included determination of Eh, pH, oxygen, nitrate, sulfate, alkalinity, phosphate, ammonium, fluoride, sulfide, Ca, Mg, Sr, Fe, Mn, and Si, in order to quantify organic matter diagenesis and related mineral precipitation and dissolution processes. Porewater profiles from the eastern upwelling areas of the South Atlantic suggest that sulfate reduction in the deeper parts of the sediment may be attributed mainly to methane oxidation, whereas organic matter degradation by sulfate reduction is restricted to the near-surface sediments. Further, a prominent concentration gradient change of sulfate and related mineralization products occurred typically in the upwelling sediments at a depth of 4 to 8 m, far below the zone of bioturbation or bioirrigation. Because other sedimentological reasons seem to fail as explanations, an early diagenetic sulfide oxidation to sulfate within the anoxic environment is discussed. Porewater profiles from the sediments of the Amazon fan area are mainly influenced by reactions with Fe(III)-phases. The remarkable linearity of the concentration gradients of sulfate supports the idea of distinct reaction layers in these sediments. In contrast to the upwelling sediments, the sulfate gradient develops from the sediment surface to a sulfate reduction zone at a depth of 5.3 m, probably because a reoxidation of sulfide is prevented by the reaction with iron oxides and the formation of iron sulfide minerals. A comparison of organic matter degradation rates from the different areas of the South Atlantic show the expected relationship to primary productivity.

  19. Actinometric measurement of solar ultraviolet and development of a weighted solar UV integral. [photochemical reaction rate determination

    NASA Technical Reports Server (NTRS)

    Gupta, A.; Coulbert, C.

    1978-01-01

    An actinometer has been developed to measure outdoor irradiance in the range 295-400 nm. Actinometric measurements of radiation are based on determination of photochemical reaction rates for reactions of known quantum efficiency. Actinometers have the advantage of providing irradiance data over surfaces of difficult accessibility; in addition, actinometrically determined irradiance data are wavelength weighted and therefore provide a useful means of assessing the degradation rates of polymers employed in solar energy systems.

  20. Laboratory Measurement of the Gas-Phase Rate Constant for Formation of Nitric Acid from the Reaction of OH and NO2

    NASA Astrophysics Data System (ADS)

    Mollner, A. K.; Feng, L.; Sprague, M. K.; Okumura, M.; Vallavudasan, S.; Sander, S. P.; Martien, P. T.; Harley, R. A.; McCoy, A. B.

    2007-12-01

    The rate constant for the reaction OH + NO2 + M → HONO2 + M is among the most influential parameters affecting air pollution levels. There remains significant uncertainty about this rate, due to lack of laboratory data at 1 atm and to the unknown yield of a secondary channel forming peroxynitrous acid (HOONO). New experimental measurements of both the kinetics and HOONO/HONO2 branching ratios at 760 Torr are presented. The results are compared with current recommendations; when incorporated in models, the new parameters lead to significantly higher modeled ozone levels and reduced formation of nitric acid.

  1. Analytical Solution of Steady State Equations for Chemical Reaction Networks with Bilinear Rate Laws

    PubMed Central

    Halász, Ádám M.; Lai, Hong-Jian; McCabe, Meghan M.; Radhakrishnan, Krishnan; Edwards, Jeremy S.

    2014-01-01

    True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher dimensional space. We show that the linearized version of the steady state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1. PMID:24334389

  2. Path-integral virial estimator for reaction rate calculation basedon the quantum instanton aproximation

    SciTech Connect

    Yang, Sandy; Yamamoto, Takeshi; Miller, William H.

    2005-11-28

    The quantum instanton approximation is a type of quantum transition state theory that calculates the chemical reaction rate using the reactive flux correlation function and its low order derivatives at time zero. Here we present several path-integral estimators for the latter quantities, which characterize the initial decay profile of the flux correlation function. As with the internal energy or heat capacity calculation, different estimators yield different variances (and therefore different convergence properties) in a Monte Carlo calculation. Here we obtain a virial(-type) estimator by using a coordinate scaling procedure rather than integration by parts, which allows more computational benefits. We also consider two different methods for treating the flux operator, i.e., local-path and global-path approaches, in which the latter achieves a smaller variance at the cost of using second-order potential derivatives. Numerical tests are performed for a one-dimensional Eckart barrier and a model proton transfer reaction in a polar solvent, which illustrates the reduced variance of the virial estimator over the corresponding thermodynamic estimator.

  3. Intraindividual reaction time variability affects P300 amplitude rather than latency

    PubMed Central

    Ramchurn, Anusha; de Fockert, Jan W.; Mason, Luke; Darling, Stephen; Bunce, David

    2014-01-01

    The neural correlates of intraindividual response variability were investigated in a serial choice reaction time (CRT) task. Reaction times (RTs) from the faster and slower portions of the RT distribution for the task were separately aggregated and associated P300 event-related potentials computed. Independent behavioral measures of executive function and IQ were also recorded. Across frontal, fronto-central, central, centro-parietal and parietal scalp regions, P300 amplitudes were significantly greater for faster relative to slower behavioral responses. However, P300 peak amplitude latencies did not differ according to the speed of the behavioral RT. Importantly, controlling for select independent measures of executive function attenuated shared variance in P300 amplitude for faster and slower trials. The findings suggest that P300 amplitude rather than latency is associated with the speed of behavioral RTs, and the possibility that fluctuations in executive control underlie variability in speeded responding. PMID:25120458

  4. Pressure dependence on the reaction propagation rate of PETN at high pressure

    SciTech Connect

    Foltz, M.F.

    1993-04-01

    The reaction propagation rate (RPR) of the sensitive high explosive pentaerythritol tetranitrate (PETN) was measured in a diamond anvil cell (DAC) over the pressure range of 2--20 GPa. The experimental technique used is the same as that previously reported. The RPR data shows that it burns one to two orders of magnitude faster in the DAC than 1,3,5,-triamino-2,4,6-trinitrobenzene (TATB) and nitromethane (CH{sub 3}NO{sub 2}) respectively. The PETN RPR curve did not show sample pressure-dependent behavior like that of nitromethane, but instead varied abruptly like the RPR curve of TATB. In order to interpret these changes, static-pressure DAC mid-IR FTIR spectra were taken of micro-pellets of PETN embedded in KBr. The relationship between changes in the spectra, the RPR curve, and published single crystal PETN wedge test data are discussed.

  5. Temperature dependence of the NO + O3 reaction rate from 195 to 369 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Allen, J. E., Jr.; Brobst, W. D.

    1981-01-01

    The temperature dependence of the NO + O3 reaction rate was examined by means of the fast flow technique. Several different experimental conditions and detection schemes were employed. With excess NO or excess O3, NO2 chemiluminescence was monitored. In addition, with excess O3, NO was followed by fluorescence induced by an NO microwave discharge lamp. The results of the three independent sets of data are compared and found to agree within experimental error, indicating the absence of secondary chemistry which might complicate the kinetics. The data exhibit curvature on an Arrhenius plot; however, the simple Arrhenius expression k = (2.6 + or - 0.8) x 10 to the -12th exp(-1435 + or - 64/T) cu cm/molecule s is an adequate description for T between 195 and 369 K. This result is compared to earlier determinations.

  6. Relative rate constants for the reactions of atomic oxygen with HO2 anad OH radicals

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1983-01-01

    Relative rate constants for the reactions O + HO2 - OH + O2 (1) and O + OH - H + O2 (2) were obtained by using the discharge-flow resonance fluorescence technique at 2 torr total pressure and 299 K. HO2 radicals were generated by reacting atomic hydrogen with an excess of O2. Quasi-steady-state concentrations of OH and HO2 were established in the presence of excess atomic oxygen. Observed concentration ratios, namely the ratio of the OH concentration to the HO2 concentration, resulted in a value of 1.7 + or 0.2 for k1/k2. The error limits are twice the standard deviation obtained from the data analysis. Overall experimental error is estimated to be + or - 25 percent. This result confirms earlier direct measurements of k1 and k2 which required knowledge of absolute radical or atomic oxygen concentrations.

  7. Partial reactions of the Na,K-ATPase: determination of rate constants

    PubMed Central

    1994-01-01

    Experiments were designed to characterize several partial reactions of the Na,K-ATPase and to demonstrate that a model can be defined that reproduces most of the transport features of the pump with a single set of kientic parameters. We used the fluorescence label 5- iodoacetamidofluorescein, which is thought to be sensitive to conformational changes, and the styryl dye RH 421, which can be applied to detect ion-binding and -release reactions. In addition transient electric currents were measured, which are associated mainly with the E1-->E2 conformational transition. Numerical simulations were performed on the basis of a reaction model, that has been developed from the Post- Albers cycle. Analysis of the experimental data allows the determination of several rate constants of the pump cycle. Our conclusions may be summarized as follows: (a) binding of one Na+ ion at the cytoplasmic face is electrogenic. This Na+ ion is specifically bound to a neutral binding site with an affinity of 8 mM in the presence of 10 mM Mg2+. In the absence of divalent cations, the intrinsic binding affinity was found to be 0.7 mM. (b) The analysis of fluorescence experiments with the cardiotonic steroid strophanthidin indicates that the 5-iodoacetamidofluorescein label monitors the conformational transition (Na3)E1-P-->P-E2(Na2), which is accompanied by the release of one Na+ ion. 5-IAF does not respond to the release of the subsequent two Na+ ions, which can be monitored by the RH 421 dye. These experiments indicate further that the conformational transition E1P-->P-E2 is the rate limiting process of the Na+ translocation. The corresponding rate constant was determined to be 22 s-1 at 20 degrees C. From competition experiments with cardiotonic steroids, we estimated that the remaining 2 Na+ ions are released subsequently with a rate constant of at least 5,000 s-1 from their negatively charged binding sites. (c) Comparing the fluorescence experiments with electric current transients

  8. An examination of factors that could affect choice reaction time in histology technicians

    SciTech Connect

    Kilburn, K.H.; Warshaw, R.; Thornton, J.C.; Husmark, I.

    1989-01-01

    Histology technicians exposed to formaldehyde and solvents have symptoms and objective evidence of neurobehavioral impairment of memory, judgment, and equilibrium. Because reaction time has been prolonged in many groups of workers exposed to toxicants, choice reaction time was measured in 385 female formaldehyde and solvent-exposed histology technicians, and 79 unexposed female laboratory workers. Choice reaction time to a visual stimulus (CRT) is defined, for the purpose of this study, as the time required for discriminated cancellation of two different letters on a microcomputer screen by pressing the matching keys. Initial analysis showed that increases in age, years of cigarette smoking, and hours per day of formaldehyde exposure significantly lengthened CRT, but xylene-toluene exposure had no effect. Since duration of smoking and length of daily formaldehyde exposure were age related, multiple linear regression analysis of CRT was performed using them as independent variables. Increasing age was the only significant factor in lengthening CRT. However, in these female histology technicians, the second measurement one year later was 44 msec faster (p less than .04). The reason for improved performance is unclear, but it may be an effect of training encompassing familiarity, improved attention, or learning.

  9. High-precision {sup 28}Si(p,t){sup 26}Si reaction to determine {sup 22}Mg({alpha},p){sup 25}Al reaction rates

    SciTech Connect

    Matic, A.; Berg, A. M. van den; Harakeh, M. N.; Woertche, H. J.; Beard, M.; Berg, G. P. A.; Goerres, J.; LeBlanc, P.; O'Brien, S.; Wiescher, M.; Fujita, K.; Hatanaka, K.; Sakemi, Y.; Shimizu, Y.; Tameshige, Y.; Tamii, A.; Yosoi, M.; Adachi, T.; Fujita, Y.; Shimbara, Y.

    2011-08-15

    The rise time of stellar x-ray bursts is a signature of thermonuclear runaway processes in the atmosphere of neutron stars and is highly sensitive to a series of ({alpha},p) reactions via high-lying resonances in sd-shell nuclei. Lacking data for the relevant resonance levels, the stellar reaction rates have been calculated using statistical, Hauser-Feshbach models, assuming a high-level density. This assumption may not be correct in view of the selectivity of the ({alpha},p) reaction to natural parity states. We measured the {sup 28}Si(p,t){sup 26}Si reaction with a high-resolution spectrometer to identify resonance levels in {sup 26}Si above the {alpha}-emission threshold at 9.164 MeV excitation energy. These resonance levels are used to calculate the stellar reaction rate of the {sup 22}Mg({alpha},p){sup 25}Al reaction and to test the validity of the statistical assumption.

  10. Factors affecting surgical site infection rate after elective gastric cancer surgery

    PubMed Central

    Özmen, Tolga; Javadov, Mirkhalig; Yeğen, Cumhur S.

    2016-01-01

    Objective Surgical site infection (SSI) is a common complication after surgery and is an indicator of quality of care. Risk factors for SSI are studied thoroughly for most types of gastrointestinal surgeries and especially colorectal surgeries, but accumulated data is still lacking for gastric surgeries. We studied the parameters affecting SSI rate after gastric cancer surgery. Material and Methods Consecutive patients, who underwent elective gastric cancer surgery between June and December 2013, were included. Descriptive parameters, laboratory values and past medical histories were recorded prospectively. All patients were followed for 1 month. Recorded parameters were compared between the SSI (+) and SSI (−) groups. Results Fifty-two patients (mean age: 58.87±9.25 [31–80]; 67% male) were included. SSI incidence was 19%. ASA score ≥3 (p<0.001), postoperative weight gain (p<0.001), smoking (p=0.014) and body mass index (BMI) ≥30 (p=0.025) were related with a higher SSI incidence. Also patients in the SSI (+) group had a higher preoperative serum C-reactive protein level (p=0.014). Conclusion We assume that decreasing BMI to <30, stopping smoking at least 3 weeks before the operation, and preventing postoperative weight gain by avoiding excessive intravenous hydration will all help decrease SSI rate after gastric surgery. PMID:27528811

  11. Season and application rates affect vaccine bait consumption by prairie dogs in Colorado and Utah, USA

    USGS Publications Warehouse

    Tripp, Daniel W.; Rocke, Tonie E.; Streich, Sean P.; Brown, Nathanael L.; Fernandez, Julia Rodriguez-Ramos; Miller, Michael W.

    2014-01-01

    Plague, a zoonotic disease caused by the bacterium Yersinia pestis, causes high rates of mortality in prairie dogs (Cynomys spp.). An oral vaccine against plague has been developed for prairie dogs along with a palatable bait to deliver vaccine and a biomarker to track bait consumption. We conducted field trials between September 2009 and September 2012 to develop recommendations for bait distribution to deliver plague vaccine to prairie dogs. The objectives were to evaluate the use of the biomarker, rhodamine B, in field settings to compare bait distribution strategies, to compare uptake of baits distributed at different densities, to assess seasonal effects on bait uptake, and to measure bait uptake by nontarget small mammal species. Rhodamine B effectively marked prairie dogs' whiskers during these field trials. To compare bait distribution strategies, we applied baits around active burrows or along transects at densities of 32, 65, and 130 baits/ha. Distributing baits at active burrows or by transect did not affect uptake by prairie dogs. Distributing baits at rates of ≥65/ha (or ≥1 bait/active burrow) produced optimal uptake, and bait uptake by prairie dogs in the autumn was superior to uptake in the spring. Six other species of small mammals consumed baits during these trials. All four species of tested prairie dogs readily consumed the baits, demonstrating that vaccine uptake will not be an obstacle to plague control via oral vaccination.

  12. Investigation of factors affecting terrestrial passive sampling device performance and uptake rates in laboratory chambers

    SciTech Connect

    Johnson, K.A.; Weisskopf, C.P.

    1995-12-31

    A rapid sampling method using passive sampling devices (PSDS) for soil contaminant characterization shows extreme promise. The use of PSDs increases ease and speed of analysis, decreases solvent usage and cost, and minimizes the transport of contaminated soils. Time and cost savings allow a high sampling frequency, providing a more thorough site characterization than traditional methods. The authors have conducted both laboratory and field studies with terrestrial PSDS. Laboratory studies demonstrated the concentration and moisture dependence of sampler uptake and provided an estimate of the optimal field sampling time for soils contaminated with polychlorinated biphenyls (PCBs). These PSDs were also used to accurately estimate PCB concentrations at hazardous waste site where concentrations ranged from 0.01 to 200 ug PCB/g soil. However, PSDs in the field had sampling rates approximately three times greater than in the laboratory. As a result several factors affecting PSD sampling rates and/or performance in laboratory chambers were evaluated. The parameters investigated were soil bulk density or compactness, chamber size and air flow. The chemicals used in these studies included two PCB congeners (52 and 153), three organochlorine pesticides (DDT, dieldrin and methoxychlor), three organophosphate pesticides (chlorpyrifos, diazinon and terbufos) and three herbicides (alachlor, atrazine and metolachlor).

  13. Does Mutual Interference Affect the Feeding Rate of Aphidophagous Coccinellids? A Modeling Perspective.

    PubMed

    Papanikolaou, Nikos E; Demiris, Nikos; Milonas, Panagiotis G; Preston, Simon; Kypraios, Theodore

    2016-01-01

    Mutual interference involves direct interactions between individuals of the same species that may alter their foraging success. Larvae of aphidophagous coccinellids typically stay within a patch during their lifetime, displaying remarkable aggregation to their prey. Thus, as larvae are exposed to each other, frequent encounters may affect their foraging success. A study was initiated in order to determine the effect of mutual interference in the coccinellids' feeding rate. One to four 4th larval instars of the fourteen-spotted ladybird beetle Propylea quatuordecimpunctata were exposed for 6 hours into plastic containers with different densities of the black bean aphid, Aphis fabae, on potted Vicia faba plants. The data were used to fit a purely prey-dependent Holling type II model and its alternatives which account for interference competition and have thus far been underutilized, i.e. the Beddington-DeAngelis, the Crowley-Martin and a modified Hassell-Varley model. The Crowley-Martin mechanistic model appeared to be slightly better among the competing models. The results showed that although the feeding rate became approximately independent of predator density at high prey density, some predator dependence in the coccinellid's functional response was observed at the low prey-high predator density combination. It appears that at low prey densities, digestion breaks are negligible so that the predators do waste time interfering with each other, whereas at high prey densities time loss during digestion breaks may fully accommodate the cost of interference, so that the time cost may be negligible. PMID:26756980

  14. Season and application rates affect vaccine bait consumption by prairie dogs in Colorado and Utah, USA.

    PubMed

    Tripp, Daniel W; Rocke, Tonie E; Streich, Sean P; Brown, Nathanael L; Fernandez, Julia Rodriguez-Ramos; Miller, Michael W

    2014-04-01

    Plague, a zoonotic disease caused by the bacterium Yersinia pestis, causes high rates of mortality in prairie dogs (Cynomys spp.). An oral vaccine against plague has been developed for prairie dogs along with a palatable bait to deliver vaccine and a biomarker to track bait consumption. We conducted field trials between September 2009 and September 2012 to develop recommendations for bait distribution to deliver plague vaccine to prairie dogs. The objectives were to evaluate the use of the biomarker, rhodamine B, in field settings to compare bait distribution strategies, to compare uptake of baits distributed at different densities, to assess seasonal effects on bait uptake, and to measure bait uptake by nontarget small mammal species. Rhodamine B effectively marked prairie dogs' whiskers during these field trials. To compare bait distribution strategies, we applied baits around active burrows or along transects at densities of 32, 65, and 130 baits/ha. Distributing baits at active burrows or by transect did not affect uptake by prairie dogs. Distributing baits at rates of ≥ 65/ha (or ≥ 1 bait/active burrow) produced optimal uptake, and bait uptake by prairie dogs in the autumn was superior to uptake in the spring. Six other species of small mammals consumed baits during these trials. All four species of tested prairie dogs readily consumed the baits, demonstrating that vaccine uptake will not be an obstacle to plague control via oral vaccination. PMID:24484490

  15. Helium effects on microstructural change in RAFM steel under irradiation: Reaction rate theory modeling

    NASA Astrophysics Data System (ADS)

    Watanabe, Y.; Morishita, K.; Nakasuji, T.; Ando, M.; Tanigawa, H.

    2015-06-01

    Reaction rate theory analysis has been conducted to investigate helium effects on the formation kinetics of interstitial type dislocation loops (I-loops) and helium bubbles in reduced-activation-ferritic/martensitic steel during irradiation, by focusing on the nucleation and growth processes of the defect clusters. The rate theory model employs the size and chemical composition dependence of thermal dissociation of point defects from defect clusters. In the calculations, the temperature and the production rate of Frenkel pairs are fixed to be T = 723 K and PV = 10-6 dpa/s, respectively. And then, only the production rate of helium atoms was changed into the following three cases: PHe = 0, 10-7 and 10-5 appm He/s. The calculation results show that helium effect on I-loop formation quite differs from that on bubble formation. As to I-loops, the loop formation hardly depends on the existence of helium, where the number density of I-loops is almost the same for the three cases of PHe. This is because helium atoms trapped in vacancies are easily emitted into the matrix due to the recombination between the vacancies and SIAs, which induces no pronounced increase or decrease of vacancies and SIAs in the matrix, leading to no remarkable impact on the I-loop nucleation. On the other hand, the bubble formation depends much on the existence of helium, in which the number density of bubbles for PHe = 10-7 and 10-5 appm He/s is much higher than that for PHe = 0. This is because helium atoms trapped in a bubble increase the vacancy binding energy, and suppress the vacancy dissociation from the bubble, resulting in a promotion of the bubble nucleation. And then, the helium effect on the promotion of bubble nucleation is very strong, even the number of helium atoms in a bubble is not so large.

  16. Reaction rates, depositional history and sources of indium in sediments from Appalachian and Canadian Shield lakes

    NASA Astrophysics Data System (ADS)

    Tessier, André; Gobeil, Charles; Laforte, Lucie

    2014-07-01

    Sediment cores were collected at the deepest site of twelve headwater lakes from the Province of Québec, Canada that receive contaminants only from atmospheric deposition, either directly to the lake surface or indirectly from the watershed. Several of the lakes are located within relatively short distance (<40 km) and others at more than 200 km from potential sources of contamination. The sediments were dated and analyzed for In and other elements including Fe, Mn, Al and organic C. Fe-rich authigenic material was collected on Teflon sheets inserted vertically into the sediments at the only study site whose hypolimnion remains perennially oxic. Porewater samples collected at the coring site of four of the lakes were also analyzed for In and other solutes including sulfide, sulfate, Fe, Mn, inorganic and organic C and major ions. The porewater In profiles display concentration gradients at or below the sediment-water interface. Modeling these profiles with a one-dimensional transport-reaction equation assuming steady state allows definition of depth intervals (zones) where In is either released to or removed from porewater and quantification of net In reactions rates in each zone. The position of the In consumption zones, the shape of the vertical profiles of dissolved In, sulfide and iron, as well as thermodynamic calculations of saturation states collectively suggest that In(OH)3(s) and In2S3(s) do not precipitate in the sediments and that adsorption of In onto sedimentary FeS(s) does not occur. However, similarities in the In and Fe porewater profiles, and the presence of In in the authigenic Fe-rich solids, reveal that part of the In becomes associated with authigenic Fe oxyhydroxides in the perennially oxic lake and is coupled to the Fe redox cycling. Comparison of the In/Corg and In/Fe molar ratios in the authigenic Fe-rich material and in surface sediments (0-0.5 cm) of this lake suggests that most non-lithogenic In was bound to humic substances. From the

  17. Upper bound and probable value of the rate constant of the reaction OH + HO2 yields H2O + O2

    NASA Technical Reports Server (NTRS)

    Chang, J. S.; Kaufman, F.

    1978-01-01

    Discharge-flow experiments at 295 K of the OH + HO2 reaction are described in which excess O3 is added to OH through a movable injector; OH concentration is measured downstream by resonance fluorescence with and without addition of excess NO just upstream of the detector so that both OH concentration and OH concentration + HO2 concentration are determined independently. The data are compared with a computer model involving 12 reaction steps. A simple sensitivity analysis is carried out to establish how errors in the other 'known' rate constants affect the data fit. Best agreement is obtained between computer calculations and experiments when k1 for the OH + HO2 reaction is in the range 2-3 x 10 to the -11th cu cm/s. Values above about 5 x 10 to the -11th are very unlikely whereas those below about 1 x 10 to the -11th are less strongly excluded.

  18. Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.

    PubMed

    Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua

    2016-03-01

    The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error. PMID:26484648

  19. Soil GHG emissions in a Miscanthus plantation as affected by increasing rates of biochar application.

    NASA Astrophysics Data System (ADS)

    Panzacchi, P.; Davies, C. A.; Ventura, M.; Michie, E. J.; Tonon, G.

    2012-04-01

    Biochar is defined as charcoal produced by pyrolysis with the aim to apply it to the soil in order to improve its fertility and carbon (C) storage capacity. Biochar physical and chemical properties can vary depending on the original biomass feedstock and pyrolysis conditions. The potential agricultural benefits and CO2 carbon sequestration from the application of biochar to soil, were assessed in field trials with well characterised biochar. In May 2010 we applied biochar from Miscanthus biomass produced at 450 °C at 3 different application rates: 10, 25 and 50 tons ha-1 to a 6 year old Miscanthus x giganteus plantation in Brattleby (Lincoln, UK) . Each treated 25 m2 plot had 4 replicates according to a randomised block experimental design. Biochar was incorporated to a depth of 10 cm in the soil between plant rhizomes after the harvest, through shallow tilling. CO2 emissions from biochar amended soil were monitored every two weeks by a portable infrared gas analyser (IRGA) with a closed dynamic chamber system, and continuously through 8 automated chambers (both systems from Li-COR, Lincoln, Nebraska). N2O fluxes were monitored using a closed static chamber technique with manual gas sampling and subsequent gas chromatography. Cation/anion exchange resin lysimeters were buried 20 cm deep in order to capture the leached nitrogen. Higher biochar applications led to a reduction of CO2 effluxes in the first 10 weeks of the experiment, after which no treatment effect was observed. The emission of N2O was significantly reduced in the 25 and 50 tons ha-1 application rates. Addition of biochar had no significant affect on the surface soil temperature, however the temperature sensitivity of soil respiration in the biochar treated plots decreased with increasing application rates

  20. Reactions to Stigmas among Canadian Students: Testing an Attribution-Affect-Help Judgment Model.

    ERIC Educational Resources Information Center

    Menec, Verena H.; Perry, Raymond P.

    1998-01-01

    Tests Weiner's (Bernard) attribution-affect-help judgment model in the context of nine stigmas and ascribed each to either a controllable or uncontrollable factor. Finds that higher controllability was linked to greater anger and less pity, greater pity was predictive of a greater willingness to help, and anger did not predict help judgments. (CMK)