Science.gov

Sample records for reaction rate uncertainties

  1. Correlated uncertainties in Monte Carlo reaction rate calculations

    NASA Astrophysics Data System (ADS)

    Longland, Richard

    2017-07-01

    Context. Monte Carlo methods have enabled nuclear reaction rates from uncertain inputs to be presented in a statistically meaningful manner. However, these uncertainties are currently computed assuming no correlations between the physical quantities that enter those calculations. This is not always an appropriate assumption. Astrophysically important reactions are often dominated by resonances, whose properties are normalized to a well-known reference resonance. This insight provides a basis from which to develop a flexible framework for including correlations in Monte Carlo reaction rate calculations. Aims: The aim of this work is to develop and test a method for including correlations in Monte Carlo reaction rate calculations when the input has been normalized to a common reference. Methods: A mathematical framework is developed for including correlations between input parameters in Monte Carlo reaction rate calculations. The magnitude of those correlations is calculated from the uncertainties typically reported in experimental papers, where full correlation information is not available. The method is applied to four illustrative examples: a fictional 3-resonance reaction, 27Al(p, γ)28Si, 23Na(p, α)20Ne, and 23Na(α, p)26Mg. Results: Reaction rates at low temperatures that are dominated by a few isolated resonances are found to minimally impacted by correlation effects. However, reaction rates determined from many overlapping resonances can be significantly affected. Uncertainties in the 23Na(α, p)26Mg reaction, for example, increase by up to a factor of 5. This highlights the need to take correlation effects into account in reaction rate calculations, and provides insight into which cases are expected to be most affected by them. The impact of correlation effects on nucleosynthesis is also investigated.

  2. Monte Carlo analysis of uncertainty propagation in a stratospheric model. 2: Uncertainties due to reaction rates

    NASA Technical Reports Server (NTRS)

    Stolarski, R. S.; Butler, D. M.; Rundel, R. D.

    1977-01-01

    A concise stratospheric model was used in a Monte-Carlo analysis of the propagation of reaction rate uncertainties through the calculation of an ozone perturbation due to the addition of chlorine. Two thousand Monte-Carlo cases were run with 55 reaction rates being varied. Excellent convergence was obtained in the output distributions because the model is sensitive to the uncertainties in only about 10 reactions. For a 1 ppby chlorine perturbation added to a 1.5 ppby chlorine background, the resultant 1 sigma uncertainty on the ozone perturbation is a factor of 1.69 on the high side and 1.80 on the low side. The corresponding 2 sigma factors are 2.86 and 3.23. Results are also given for the uncertainties, due to reaction rates, in the ambient concentrations of stratospheric species.

  3. 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.

  4. Probabilistic models and uncertainty quantification for the ionization reaction rate of atomic Nitrogen

    NASA Astrophysics Data System (ADS)

    Miki, K.; Panesi, M.; Prudencio, E. E.; Prudhomme, S.

    2012-05-01

    The objective in this paper is to analyze some stochastic models for estimating the ionization reaction rate constant of atomic Nitrogen (N + e- → N+ + 2e-). Parameters of the models are identified by means of Bayesian inference using spatially resolved absolute radiance data obtained from the Electric Arc Shock Tube (EAST) wind-tunnel. The proposed methodology accounts for uncertainties in the model parameters as well as physical model inadequacies, providing estimates of the rate constant that reflect both types of uncertainties. We present four different probabilistic models by varying the error structure (either additive or multiplicative) and by choosing different descriptions of the statistical correlation among data points. In order to assess the validity of our methodology, we first present some calibration results obtained with manufactured data and then proceed by using experimental data collected at EAST experimental facility. In order to simulate the radiative signature emitted in the shock-heated air plasma, we use a one-dimensional flow solver with Park's two-temperature model that simulates non-equilibrium effects. We also discuss the implications of the choice of the stochastic model on the estimation of the reaction rate and its uncertainties. Our analysis shows that the stochastic models based on correlated multiplicative errors are the most plausible models among the four models proposed in this study. The rate of the atomic Nitrogen ionization is found to be (6.2 ± 3.3) × 1011 cm3 mol-1 s-1 at 10,000 K.

  5. Nuclear reaction rate uncertainties and the 22Ne( p,gamma)23Na reaction: Classical novae and globular clusters

    NASA Astrophysics Data System (ADS)

    Kelly, Keegan John

    The overall theme of this thesis is the advancement of nuclear astrophysics via the analysis of stellar processes in the presence of varying levels of precision in the available nuclear data. With regard to classical novae, the level of mixing that occurs between the outer layers of the white dwarf core and the solar accreted material in oxygen-neon novae is presently undetermined by stellar models, but the nuclear data relevant to these explosive phenomena are fairly precise. This precision allowed for the identification of a series of elemental ratios indicative of the level of mixing occurring in novae. Direct comparisons of the modelled elemental ratios to observations showed that there is likely to be much less of this mixing than was previously assumed. Thus, our understanding of classical novae was altered via the investigation of the nuclear reactions relevant to this phenomenon. However, this level of experimental precision is rare and large nuclear reaction uncertainties can hinder our understanding of certain astrophysical phenomena. For example, it is commonly believed that uncertainties in the 22Ne(p,g)23Na reaction rate at temperatures relevant to thermally-pulsing asymptotic giant branch stars are largely responsible for our inability to explain the observed sodium-oxygen anti-correlation in globular clusters. With this motivation, resonances in the 22Ne(p,g) 23Na reaction at E_{c.m.} = 458, 417, 178, and 151 keV were measured. The direct-capture contribution was also measured at E_{lab} = 425 keV. It was determined that the 22Ne(p,g)23Na reaction rate in the astrophysically relevant temperature range is dominated by the resonances at 178 and 151 keV and that the total reaction rate is greater than the previously assumed rate by a factor of approximately ˜40 at 0.15 GK. This increased reaction rate impacts the expected nucleosynthesis that occurs in these stars and will shed light onto the origin of this anti-correlation as it is incorporated into

  6. 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…

  7. Uncertainty Quantification for Nonlinear Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Srinivasan, G.; Robinson, B. A.; Aceves, A. B.; Tartakovsky, D. M.

    2006-12-01

    Systems of coupled chemical reactions are greatly affected by the inherent uncertainties in natural phenomena. These uncertainties can be parametric in nature due to measurement errors or insufficient data. Modeling uncertainties also arise at the molecular level when determining what fraction of the population of each chemical species participates in a chemical reaction at any given time. We present different methods used to quantify both modeling and parametric uncertainties. The application we focus on is that of chemical reactions in the subsurface that greatly affect the transport of contaminants in groundwater. The example considered here is the sorption of Neptunium Np-237 through a competitive ion exchange process. Np-237 is a key radio-nuclide of concern for the Yucca Mountain High Level Waste storage site due to its relatively long half-life, high solubility and low sorption properties. By quantifying the effects of modeling and parametric uncertainties, we can estimate the error associated with Np-237 sorptivity and hence its transport.

  8. Formal modeling of a system of chemical reactions under uncertainty.

    PubMed

    Ghosh, Krishnendu; Schlipf, John

    2014-10-01

    We describe a novel formalism representing a system of chemical reactions, with imprecise rates of reactions and concentrations of chemicals, and describe a model reduction method, pruning, based on the chemical properties. We present two algorithms, midpoint approximation and interval approximation, for construction of efficient model abstractions with uncertainty in data. We evaluate computational feasibility by posing queries in computation tree logic (CTL) on a prototype of extracellular-signal-regulated kinase (ERK) pathway.

  9. Uncertainty Analysis for Photovoltaic Degradation Rates (Poster)

    SciTech Connect

    Jordan, D.; Kurtz, S.; Hansen, C.

    2014-04-01

    Dependable and predictable energy production is the key to the long-term success of the PV industry. PV systems show over the lifetime of their exposure a gradual decline that depends on many different factors such as module technology, module type, mounting configuration, climate etc. When degradation rates are determined from continuous data the statistical uncertainty is easily calculated from the regression coefficients. However, total uncertainty that includes measurement uncertainty and instrumentation drift is far more difficult to determine. A Monte Carlo simulation approach was chosen to investigate a comprehensive uncertainty analysis. The most important effect for degradation rates is to avoid instrumentation that changes over time in the field. For instance, a drifting irradiance sensor, which can be achieved through regular calibration, can lead to a substantially erroneous degradation rates. However, the accuracy of the irradiance sensor has negligible impact on degradation rate uncertainty emphasizing that precision (relative accuracy) is more important than absolute accuracy.

  10. Uncertainty quantification for quantum chemical models of complex reaction networks.

    PubMed

    Proppe, Jonny; Husch, Tamara; Simm, Gregor N; Reiher, Markus

    2016-12-22

    For the quantitative understanding of complex chemical reaction mechanisms, it is, in general, necessary to accurately determine the corresponding free energy surface and to solve the resulting continuous-time reaction rate equations for a continuous state space. For a general (complex) reaction network, it is computationally hard to fulfill these two requirements. However, it is possible to approximately address these challenges in a physically consistent way. On the one hand, it may be sufficient to consider approximate free energies if a reliable uncertainty measure can be provided. On the other hand, a highly resolved time evolution may not be necessary to still determine quantitative fluxes in a reaction network if one is interested in specific time scales. In this paper, we present discrete-time kinetic simulations in discrete state space taking free energy uncertainties into account. The method builds upon thermo-chemical data obtained from electronic structure calculations in a condensed-phase model. Our kinetic approach supports the analysis of general reaction networks spanning multiple time scales, which is here demonstrated for the example of the formose reaction. An important application of our approach is the detection of regions in a reaction network which require further investigation, given the uncertainties introduced by both approximate electronic structure methods and kinetic models. Such cases can then be studied in greater detail with more sophisticated first-principles calculations and kinetic simulations.

  11. Uncertainty propagation in a stratospheric model. I - Development of a concise stratospheric model. II - Monte Carlo analysis of imprecisions due to reaction rates. [for ozone depletion prediction

    NASA Technical Reports Server (NTRS)

    Rundel, R. D.; Butler, D. M.; Stolarski, R. S.

    1978-01-01

    The paper discusses the development of a concise stratospheric model which uses iteration to obtain coupling between interacting species. The one-dimensional, steady-state, diurnally-averaged model generates diffusion equations with appropriate sources and sinks for species odd oxygen, H2O, H2, CO, N2O, odd nitrogen, CH4, CH3Cl, CCl4, CF2Cl2, CFCl3, and odd chlorine. The model evaluates steady-state perturbations caused by injections of chlorine and NO(x) and may be used to predict ozone depletion. The model is used in a Monte Carlo study of the propagation of reaction-rate imprecisions by calculating an ozone perturbation caused by the addition of chlorine. Since the model is sensitive to only 10 of the more than 50 reaction rates considered, only about 1000 Monte Carlo cases are required to span the space of possible results.

  12. Uncertainties in Astrophysical β-decay Rates from the FRDM

    SciTech Connect

    Bertolli, M.G.; Möller, P.; Jones, S.

    2014-06-15

    β{sup −}-decay rates are of crucial importance in stellar evolution and nucleosynthesis, as they are a key component in stellar processes. Tabulated values of the decay rates as functions of both temperature T and density ρ are necessary input to stellar evolution codes such as MESA, or largescale nucleosynthesis simulations such as those performed by the NuGrid collaboration. Therefore, it is interesting to know the uncertainties in these rates and the effects of these uncertainties on stellar structure and isotopic yields. We have calculated β-strength functions and reaction rates for nuclei ranging from {sup 16}O to {sup 339}136, extending from the proton drip line to the neutron drip line based on a quasi-particle random-phase approximation (QRPA) in a deformed folded-Yukawa single-particle model. Q values are determined from the finite-range droplet mass model (FRDM). We have investigated the effect of model uncertainty on astrophysical β{sup −}-decay rates calculated by the FRDM. The sources of uncertainty considered are Q values and deformation. The rates and their uncertainties are generated for a variety of temperature and density ranges, corresponding to key stellar processes. We demonstrate the effects of these rate uncertainties on isotopic abundances using the NuGrid network calculations.

  13. 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.

  14. Cosmological Implications of the Uncertainty in Astrochemical Rate Coefficients

    NASA Technical Reports Server (NTRS)

    Glover, S. C. O.; Savin, D. W.; Jappsen, A.-K.

    2006-01-01

    The cooling of neutral gas of primordial composition, or with very low levels of metal enrichment, depends crucially on the formation of molecular coolants, such as H2 and HD within the gas. Although the chemical reactions involved in the formation and destruction of these molecules are well known, the same cannot be said for the rate coefficients of these reactions, some of which are uncertain by an order of magnitude. Here we discuss two reactions for which large uncertainties exist the formation of H2 by associative detachment of H- with H and the destruction of H- by mutual neutralization with protons. We show that these uncertainties can have a dramatic impact on the effectiveness of cooling during protogalactic collapse.

  15. Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics

    NASA Technical Reports Server (NTRS)

    Kawa, S. Randolph; Stolarksi, Richard S.; Douglass, Anne R.; Newman, Paul A.

    2008-01-01

    Several recent observational and laboratory studies of processes involved in polar stratospheric ozone loss have prompted a reexamination of aspects of our understanding for this key indicator of global change. To a large extent, our confidence in understanding and projecting changes in polar and global ozone is based on our ability to simulate these processes in numerical models of chemistry and transport. The fidelity of the models is assessed in comparison with a wide range of observations. These models depend on laboratory-measured kinetic reaction rates and photolysis cross sections to simulate molecular interactions. A typical stratospheric chemistry mechanism has on the order of 50- 100 species undergoing over a hundred intermolecular reactions and several tens of photolysis reactions. The rates of all of these reactions are subject to uncertainty, some substantial. Given the complexity of the models, however, it is difficult to quantify uncertainties in many aspects of system. In this study we use a simple box-model scenario for Antarctic ozone to estimate the uncertainty in loss attributable to known reaction kinetic uncertainties. Following the method of earlier work, rates and uncertainties from the latest laboratory evaluations are applied in random combinations. We determine the key reactions and rates contributing the largest potential errors and compare the results to observations to evaluate which combinations are consistent with atmospheric data. Implications for our theoretical and practical understanding of polar ozone loss will be assessed.

  16. Effect of Uncertainty on the Reaction Response in Fencing

    ERIC Educational Resources Information Center

    Gutierrez-Davila, Marcos; Rojas, F. Javier; Antonio, Raquel; Navarro, Enrique

    2013-01-01

    Purpose: The objective was to determine the way in which the level of uncertainty produced during the execution of a lunge attack with target change (two or four possible responses) affects reaction-response time parameters and kinematic factors involved in the technical coordination of the attack. Method: Seventeen fencers from the Spanish…

  17. Effect of Uncertainty on the Reaction Response in Fencing

    ERIC Educational Resources Information Center

    Gutierrez-Davila, Marcos; Rojas, F. Javier; Antonio, Raquel; Navarro, Enrique

    2013-01-01

    Purpose: The objective was to determine the way in which the level of uncertainty produced during the execution of a lunge attack with target change (two or four possible responses) affects reaction-response time parameters and kinematic factors involved in the technical coordination of the attack. Method: Seventeen fencers from the Spanish…

  18. Propagation of rating curve uncertainty in design flood estimation

    NASA Astrophysics Data System (ADS)

    Steinbakk, G. H.; Thorarinsdottir, T. L.; Reitan, T.; Schlichting, L.; Hølleland, S.; Engeland, K.

    2016-09-01

    Statistical flood frequency analysis is commonly performed based on a set of annual maximum discharge values which are derived from stage measurements via a stage-discharge rating curve model. Such design flood estimation techniques often ignore the uncertainty in the underlying rating curve model. Using data from eight gauging stations in Norway, we investigate the effect of curve and sample uncertainty on design flood estimation by combining results from a Bayesian multisegment rating curve model and a Bayesian flood frequency analysis. We find that sample uncertainty is the main contributor to the design flood estimation uncertainty. However, under extrapolation of the rating curve, the uncertainty bounds for both the rating curve model and the flood frequency analysis are highly skewed and ignoring these features may underestimate the potential risk of flooding. We expect this effect to be even more pronounced in arid and semiarid climates with a higher variability in floods.

  19. Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

    SciTech Connect

    Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.; Zhang, Guannan

    2014-01-01

    A multi-rate expression for uranyl [U(VI)] surface complexation reactions has been proposed to describe diffusion-limited U(VI) sorption/desorption in heterogeneous subsurface sediments. An important assumption in the rate expression is that its rate constants follow a certain type probability distribution. In this paper, a Bayes-based, Differential Evolution Markov Chain method was used to assess the distribution assumption and to analyze parameter and model structure uncertainties. U(VI) desorption from a contaminated sediment at the US Hanford 300 Area, Washington was used as an example for detail analysis. The results indicated that: 1) the rate constants in the multi-rate expression contain uneven uncertainties with slower rate constants having relative larger uncertainties; 2) the lognormal distribution is an effective assumption for the rate constants in the multi-rate model to simualte U(VI) desorption; 3) however, long-term prediction and its uncertainty may be significantly biased by the lognormal assumption for the smaller rate constants; and 4) both parameter and model structure uncertainties can affect the extrapolation of the multi-rate model with a larger uncertainty from the model structure. The results provide important insights into the factors contributing to the uncertainties of the multi-rate expression commonly used to describe the diffusion or mixing-limited sorption/desorption of both organic and inorganic contaminants in subsurface sediments.

  20. Bayesian Estimation of Thermonuclear Reaction Rates

    NASA Astrophysics Data System (ADS)

    Iliadis, C.; Anderson, K. S.; Coc, A.; Timmes, F. X.; Starrfield, S.

    2016-11-01

    The problem of estimating non-resonant astrophysical S-factors and thermonuclear reaction rates, based on measured nuclear cross sections, is of major interest for nuclear energy generation, neutrino physics, and element synthesis. Many different methods have been applied to this problem in the past, almost all of them based on traditional statistics. Bayesian methods, on the other hand, are now in widespread use in the physical sciences. In astronomy, for example, Bayesian statistics is applied to the observation of extrasolar planets, gravitational waves, and Type Ia supernovae. However, nuclear physics, in particular, has been slow to adopt Bayesian methods. We present astrophysical S-factors and reaction rates based on Bayesian statistics. We develop a framework that incorporates robust parameter estimation, systematic effects, and non-Gaussian uncertainties in a consistent manner. The method is applied to the reactions d(p,γ)3He, 3He(3He,2p)4He, and 3He(α,γ)7Be, important for deuterium burning, solar neutrinos, and Big Bang nucleosynthesis.

  1. Rating curve uncertainty: A comparison of estimation methods

    USGS Publications Warehouse

    Mason, Jr., Robert R.; Kiang, Julie E.; Cohn, Timothy A.; Constantinescu, George; Garcia, Marcelo H.; Hanes, Dan

    2016-01-01

    The USGS is engaged in both internal development and collaborative efforts to evaluate existing methods for characterizing the uncertainty of streamflow measurements (gaugings), stage-discharge relations (ratings), and, ultimately, the streamflow records derived from them. This paper provides a brief overview of two candidate methods that may be used to characterize the uncertainty of ratings, and illustrates the results of their application to the ratings of the two USGS streamgages.

  2. Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.; Zhang, Guannan

    2014-01-01

    Multi-rate surface complexation models have been proposed to describe the kinetics of uranyl (U(VI) surface complexation reactions (SCR) rate-limited by diffusive mass transfer to and from intragranular sorption sites in subsurface sediments. In this study, a Bayesian-based, Differential Evolution Markov Chain method was used to assess the uncertainty and to identify factors controlling the uncertainties of the multi-rate SCR model. The rate constants in the multi-rate SCR were estimated with and without assumption of a specified lognormal distribution to test the lognormal assumption typically used to minimize the number of the rate constants in the multi-rate model. U(VI) desorption under variable chemical conditions from a contaminated sediment at US Hanford 300 Area, Washington was used as an example. The results indicated that the estimated rate constants without a specified lognormal assumption approximately followed a lognormal distribution, indicating that the lognormal is an effective assumption for the rate constants in the multi-rate SCR model. However, those rate constants with their corresponding half-lives longer than the experimental durations for model characterization had larger uncertainties and could not be reliably estimated. The uncertainty analysis revealed that the time-scale of the experiments for calibrating the multi-rate SCR model, the assumption for the rate constant distribution, the geochemical conditions involved in predicting U(VI) desorption, and equilibrium U(VI) speciation reaction constants were the major factors contributing to the extrapolation uncertainties of the multi-rate SCR model. Overall, the results from this study demonstrated that the multi-rate SCR model with a lognormal distribution of its rate constants is an effective approach for describing rate-limited U(VI) desorption; however, the model contains uncertainties, especially for those smaller rate constants, that require careful consideration for predicting U

  3. Uncertainty quantification: Making predictions of complex reaction systems reliable

    NASA Astrophysics Data System (ADS)

    Russi, Trent; Packard, Andy; Frenklach, Michael

    2010-10-01

    There is increasing need to make chemical reaction models and modeling more predictive. We examine the modeling methodology from the perspective of propagation of uncertainties, those in assumed model parameters along with those in experimental observations. Accepting the length of the uncertainty interval in the predicted property as a measure of model predictiveness, we examine methodological factors affecting it. Employing the recently introduced technique of Data Collaboration, we show that even 'harmless' assumptions, invoked explicitly or implicitly to alleviate a burden of numerical procedures, could lead to substantial differences in model predictiveness. We also demonstrate that the direct, one-step methodology, such as Data Collaboration, necessarily makes modeling more predictive and thus more reliable than a two-step approach typical of most current methods.

  4. Uncertainties in the calculation of solar-neutrino capture rates

    SciTech Connect

    Filippone, B.W.

    1981-01-01

    A detailed estimate is presented of the possible uncertainty range for the neutrino flux from a standard solar model. Using present estimated errors in the key input parameters, detailed solar models are calculated to give an uncertainty in the theoretical nu/sub e/ capture rate in both the on-going /sup 37/Cl experiment and the proposed experiment using /sup 71/Ga. The uncertainty in capture rate is investigated by considering individual parameter variations about a mean model, by simultaneously varying several key parameters to yield upper and lower limits, and by a Monte Carlo method.

  5. 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)

  6. Effects of rating-curve uncertainty on probabilistic flood mapping

    NASA Astrophysics Data System (ADS)

    Domeneghetti, A.; Vorogushyn, S.; Castellarin, A.; Merz, B.; Brath, A.

    2012-08-01

    Comprehensive flood risk assessment studies should quantify the global uncertainty in flood hazard estimation, for instance by mapping inundation extents together with their confidence intervals. This appears of particular importance in case of flood hazard assessments along dike-protected reaches where the possibility of occurrence of dike failures may considerably enhance the uncertainty. We present a methodology to derive probabilistic flood maps in dike-protected flood prone areas, where several sources of uncertainty are taken into account. In particular, this paper focuses on a 50 km reach of River Po (Italy) and three major sources of uncertainty in hydraulic modelling and flood mapping: uncertainties in the (i) upstream and (ii) downstream boundary conditions, and (iii) uncertainties in dike failures. Uncertainties in the definition of upstream boundary conditions (i.e. design-hydrographs) are assessed by applying different bivariate copula families to model the frequency regime of flood peaks and volumes. Uncertainties in the definition of downstream boundary conditions are characterised by associating the rating-curve used as downstream boundary condition with confidence intervals which reflect discharge measurements errors and interpolation errors. The effects of uncertainties in boundary conditions and randomness of dike failures are assessed by means of the Inundation Hazard Assessment Model (IHAM), a recently proposed hybrid probabilistic-deterministic model that considers three different failure mechanisms: overtopping, piping and micro-instability due to seepage. The results of the study show that the IHAM-based analysis enables probabilistic flood hazard mapping and provides decision makers with a fundamental piece of information for devising and implementing flood risk mitigation strategies in the presence of various sources of uncertainty.

  7. Geodetic slip rate estimates in California, and their uncertainties

    NASA Astrophysics Data System (ADS)

    Evans, E. L.

    2016-12-01

    Current understanding of the seismic potential of faults in California is limited in part by our ability to resolve spatial and temporal changes in fault slip rates across the Pacific-North American plate boundary, and quantify their uncertainties. Fault slip rate can be estimated by modeling fault systems, based on space geodetic measurements of surface ground displacement (GPS and InSAR). However, models that include elastic deformation due to locked faults require fault geometries to be prescribed, and geodetic slip rate estimates may vary widely due to measurement and epistemic (model) uncertainties. To examine published geodetic slip rate estimates in California and quantify variability among models, we compile 31 published geodetic slip rate studies in California and Nevada. Because deformation models may vary in the number of faults represented and the precise location of faults, we combine published geodetic slip rate estimates on a georeferenced grid and compare models spatially. Within each grid cell, a number of metrics are considered based on the suite of fault slip rates in the cell. These metrics include geometric moment (potency), strain and rotation, and variation among models. This approach assumes that all published geodetic slip rate estimates are equally valid, and therefore this variability among models serves as a proxy for epistemic uncertainties in geodetic slip rates: we find an average standard deviation in potency rate of 1.5×106 m3/yr for cells of 725 km2 (1,365 cells), which corresponds to 2 mm/yr of model uncertainty on a given slip rate. These uncertainties may be incorporated into hazard estimates, enable rigorous comparison with geologic slip rates, and used to systematically identify regions that may require more careful consideration in terms of modeling available geologic and geodetic data.

  8. Science Based Stockpile Stewardship, Uncertainty Quantification, and Surrogate Reactions

    SciTech Connect

    Stoyer, M A; McNabb, D P; Burke, J T; Bernstein, L A

    2009-08-06

    Stewardship of this nation's nuclear weapons is predicated on developing a fundamental scientific understanding of the physics and chemistry required to describe weapon performance without the need to resort to underground nuclear testing and to predict expected future performance as a result of intended or unintended modifications. In order to construct more reliable models, underground nuclear test data is being reanalyzed in novel ways. To improve the interpretation of these experiments with quantified uncertainties, improved nuclear data is required. As an example, the thermonuclear yield of a device was often inferred through the use of radiochemical detectors. Conversion of the detector activations observed to thermonuclear yield was accomplished through explosion code calculations (models) and a good set of nuclear reaction cross-sections. Because of the unique high-fluence environment of an exploding nuclear weapon, many reactions occurred on radioactive nuclides, for which only theoretically calculated cross-sections are available. Surrogate nuclear reactions at STARS/LIBERACE offer the opportunity to measure cross-sections on unstable nuclei and thus improve the quality of the nuclear reaction cross-section sets. One radiochemical detector that was loaded in devices was mono-isotopic yttrium ({sup 89}Y). Nuclear reactions produced {sup 87}Y and {sup 88}Y which could be quantified post-shot as a ratio of {sup 87}Y/{sup 88}Y. The yttrium cross-section set from 1988 is shown in Figure 1(a) and contains approximately 62 cross-sections interconnecting the yttrium nuclides. The 6 experimentally measured cross-sections are shown in Figure 1(b). Any measurement of cross-sections on {sup 87}Y or {sup 88}Y would improve the quality of the cross-section set. A recent re-evaluation of the yttrium cross-section set was performed with many more calculated reaction cross-sections included.

  9. A New Look at Reaction Rates

    NASA Astrophysics Data System (ADS)

    Cvitas, Tomislav

    1999-11-01

    Both rates of radioactive decays and rates of chemical reactions can be thought of as numbers of transformations per time. The rate of reaction, as an intensive quantity characteristic of the process, is obtained by dividing the amount of chemical transformations per time by the volume of the reaction system. The practical definition of the reaction rate found in the literature can then be derived by defining the stoichiometric numbers as changes in the number of specific molecules taking part in the reaction per chemical transformation. The name concentration of chemical transformations is introduced for what was previously called reaction variable. It is suggested that the conceptual definition of the advancement of reaction and reaction rate be introduced in general chemistry courses.

  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. 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.

  12. Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics

    NASA Technical Reports Server (NTRS)

    Kawa, S. Randolph; Stolarski, Richard S.; Douglass, Anne R.; Newman, Paul A.

    2008-01-01

    Several recent observational and laboratory studies of processes involved in polar stratospheric ozone loss have prompted a reexamination of aspect of out understanding for this key indicator of global change. To a large extent, our confidence in understanding and projecting changes in polar and global ozone is based on our ability to to simulate these process in numerical models of chemistry and transport. These models depend on laboratory-measured kinetic reaction rates and photlysis cross section to simulate molecular interactions. In this study we use a simple box-model scenario for Antarctic ozone to estimate the uncertainty in loss attributable to known reaction kinetic uncertainties. Following the method of earlier work, rates and uncertainties from the latest laboratory evaluation are applied in random combinations. We determine the key reaction and rates contributing the largest potential errors and compare the results to observations to evaluate which combinations are consistent with atmospheric data. Implications for our theoretical and practical understanding of polar ozone loss will be assessed.

  13. Estimation of uncertainty for fatigue growth rate at cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Nyilas, Arman; Weiss, Klaus P.; Urbach, Elisabeth; Marcinek, Dawid J.

    2014-01-01

    Fatigue crack growth rate (FCGR) measurement data for high strength austenitic alloys at cryogenic environment suffer in general from a high degree of data scatter in particular at ΔK regime below 25 MPa√m. Using standard mathematical smoothing techniques forces ultimately a linear relationship at stage II regime (crack propagation rate versus ΔK) in a double log field called Paris law. However, the bandwidth of uncertainty relies somewhat arbitrary upon the researcher's interpretation. The present paper deals with the use of the uncertainty concept on FCGR data as given by GUM (Guidance of Uncertainty in Measurements), which since 1993 is a recommended procedure to avoid subjective estimation of error bands. Within this context, the lack of a true value addresses to evaluate the best estimate by a statistical method using the crack propagation law as a mathematical measurement model equation and identifying all input parameters. Each parameter necessary for the measurement technique was processed using the Gaussian distribution law by partial differentiation of the terms to estimate the sensitivity coefficients. The combined standard uncertainty determined for each term with its computed sensitivity coefficients finally resulted in measurement uncertainty of the FCGR test result. The described procedure of uncertainty has been applied within the framework of ITER on a recent FCGR measurement for high strength and high toughness Type 316LN material tested at 7 K using a standard ASTM proportional compact tension specimen. The determined values of Paris law constants such as C0 and the exponent m as best estimate along with the their uncertainty value may serve a realistic basis for the life expectancy of cyclic loaded members.

  14. Addressing uncertainty in fecal indicator bacteria dark inactivation rates.

    PubMed

    Gronewold, Andrew D; Myers, Luke; Swall, Jenise L; Noble, Rachel T

    2011-01-01

    Assessing the potential threat of fecal contamination in surface water often depends on model forecasts which assume that fecal indicator bacteria (FIB, a proxy for the concentration of pathogens found in fecal contamination from warm-blooded animals) are lost or removed from the water column at a certain rate (often referred to as an "inactivation" rate). In efforts to reduce human health risks in these water bodies, regulators enforce limits on easily-measured FIB concentrations, commonly reported as most probable number (MPN) and colony forming unit (CFU) values. Accurate assessment of the potential threat of fecal contamination, therefore, depends on propagating uncertainty surrounding "true" FIB concentrations into MPN and CFU values, inactivation rates, model forecasts, and management decisions. Here, we explore how empirical relationships between FIB inactivation rates and extrinsic factors might vary depending on how uncertainty in MPN values is expressed. Using water samples collected from the Neuse River Estuary (NRE) in eastern North Carolina, we compare Escherichia coli (EC) and Enterococcus (ENT) dark inactivation rates derived from two statistical models of first-order loss; a conventional model employing ordinary least-squares (OLS) regression with MPN values, and a novel Bayesian model utilizing the pattern of positive wells in an IDEXX Quanti-Tray®/2000 test. While our results suggest that EC dark inactivation rates tend to decrease as initial EC concentrations decrease and that ENT dark inactivation rates are relatively consistent across different ENT concentrations, we find these relationships depend upon model selection and model calibration procedures. We also find that our proposed Bayesian model provides a more defensible approach to quantifying uncertainty in microbiological assessments of water quality than the conventional MPN-based model, and that our proposed model represents a new strategy for developing robust relationships between

  15. 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…

  16. 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…

  17. Redox reaction rates using potentiostatic coulometry

    SciTech Connect

    Ramette, R.W.; Harris, R.Z.; Bengali, A.A.; Noll, R.J.

    1987-01-01

    A new method based on potentiostatic coulometry was used to study the kinetics of the aqueous redox reactions between the ions chlorate/iodide, bromate/iodide, and bromate/bromide. The halogen product was continuously and rapidly reduced back to halide at a large platinum gauze cathode, the current being a direct measure of reaction rate and the accumulated charge serving to measure the extent of reaction. The reactions were studied at several temperatures, and activation entropies and enthalpies were calculated.

  18. Reaction rates for reaction-diffusion kinetics on unstructured meshes

    NASA Astrophysics Data System (ADS)

    Hellander, Stefan; Petzold, Linda

    2017-02-01

    The reaction-diffusion master equation is a stochastic model often utilized in the study of biochemical reaction networks in living cells. It is applied when the spatial distribution of molecules is important to the dynamics of the system. A viable approach to resolve the complex geometry of cells accurately is to discretize space with an unstructured mesh. Diffusion is modeled as discrete jumps between nodes on the mesh, and the diffusion jump rates can be obtained through a discretization of the diffusion equation on the mesh. Reactions can occur when molecules occupy the same voxel. In this paper, we develop a method for computing accurate reaction rates between molecules occupying the same voxel in an unstructured mesh. For large voxels, these rates are known to be well approximated by the reaction rates derived by Collins and Kimball, but as the mesh is refined, no analytical expression for the rates exists. We reduce the problem of computing accurate reaction rates to a pure preprocessing step, depending only on the mesh and not on the model parameters, and we devise an efficient numerical scheme to estimate them to high accuracy. We show in several numerical examples that as we refine the mesh, the results obtained with the reaction-diffusion master equation approach those of a more fine-grained Smoluchowski particle-tracking model.

  19. 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…

  20. 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…

  1. 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%.

  2. Effective reaction rates for diffusion-limited reaction cycles.

    PubMed

    Nałęcz-Jawecki, Paweł; Szymańska, Paulina; Kochańczyk, Marek; Miękisz, Jacek; Lipniacki, Tomasz

    2015-12-07

    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%.

  3. Systematic Uncertainties in High-Rate Germanium Data

    SciTech Connect

    Gilbert, Andrew J.; Fast, James E.; Fulsom, Bryan G.; Pitts, William K.; VanDevender, Brent A.; Wood, Lynn S.

    2016-10-06

    For many nuclear material safeguards inspections, spectroscopic gamma detectors are required which can achieve high event rates (in excess of 10^6 s^-1) while maintaining very good energy resolution for discrimination of neighboring gamma signatures in complex backgrounds. Such spectra can be useful for non-destructive assay (NDA) of spent nuclear fuel with long cooling times, which contains many potentially useful low-rate gamma lines, e.g., Cs-134, in the presence of a few dominating gamma lines, such as Cs-137. Detectors in use typically sacrifice energy resolution for count rate, e.g., LaBr3, or visa versa, e.g., CdZnTe. In contrast, we anticipate that beginning with a detector with high energy resolution, e.g., high-purity germanium (HPGe), and adapting the data acquisition for high throughput will be able to achieve the goals of the ideal detector. In this work, we present quantification of Cs-134 and Cs-137 activities, useful for fuel burn-up quantification, in fuel that has been cooling for 22.3 years. A segmented, planar HPGe detector is used for this inspection, which has been adapted for a high-rate throughput in excess of 500k counts/s. Using a very-high-statistic spectrum of 2.4*10^11 counts, isotope activities can be determined with very low statistical uncertainty. However, it is determined that systematic uncertainties dominate in such a data set, e.g., the uncertainty in the pulse line shape. This spectrum offers a unique opportunity to quantify this uncertainty and subsequently determine required counting times for given precision on values of interest.

  4. 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.

  5. 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)

  6. Nuclear reaction uncertainties, massive gravitino decays and the cosmological lithium problem

    SciTech Connect

    Cyburt, Richard H.; Ellis, John; Fields, Brian D.; Luo, Feng; Olive, Keith A.; Spanos, Vassilis C. E-mail: john.ellis@cern.ch E-mail: fluo@physics.umn.edu E-mail: spanos@physics.umn.edu

    2010-10-01

    We consider the effects of uncertainties in nuclear reaction rates on the cosmological constraints on the decays of unstable particles during or after Big-Bang nucleosynthesis (BBN). We identify the nuclear reactions due to non-thermal hadrons that are the most important in perturbing standard BBN, then quantify the uncertainties in these reactions and in the resulting light-element abundances. These results also indicate the key nuclear processes for which improved cross section data would allow different light-element abundances to be determined more accurately, thereby making possible more precise probes of BBN and evaluations of the cosmological constraints on unstable particles. Applying this analysis to models with unstable gravitinos decaying into neutralinos, we calculate the likelihood function for the light-element abundances measured currently, taking into account the current experimental errors in the determinations of the relevant nuclear reaction rates. We find a region of the gravitino mass and abundance in which the abundances of deuterium, {sup 4}He and {sup 7}Li may be fit with χ{sup 2} = 5.5, compared with χ{sup 2} = 31.7 if the effects of gravitino decays are unimportant. The best-fit solution is improved to χ{sup 2} ∼ 2.0 when the lithium abundance is taken from globular cluster data. Some such re-evaluation of the observed light-element abundances and/or nuclear reaction rates would be needed if this region of gravitino parameters is to provide a complete solution to the cosmological {sup 7}Li problem.

  7. Calibrating reaction rates for the CREST model

    NASA Astrophysics Data System (ADS)

    Handley, Caroline A.; Christie, Michael A.

    2017-01-01

    The CREST reactive-burn model uses entropy-dependent reaction rates that, until now, have been manually tuned to fit shock-initiation and detonation data in hydrocode simulations. This paper describes the initial development of an automatic method for calibrating CREST reaction-rate coefficients, using particle swarm optimisation. The automatic method is applied to EDC32, to help develop the first CREST model for this conventional high explosive.

  8. Rate constant for the Cl + Chloroform reaction

    SciTech Connect

    Brahan, K.M.; Hewitt, A.D.; Boone, G.D.

    1995-12-01

    The rate constant for the reaction of Cl with chloroform has been measured relative to the reaction of Cl with methane, methyl chloride, and carbon monoxide using long path FTIR spectroscopy. Our measured rate constant at 298 K and 1 atm of (1.2{plus_minus}0.1)x10{sup -13} cm{sup 3}molecule{sup -1}sec{sup -1} is 50% higher than that recommended for stratospheric modeling; however, it is within experimental error of the values measured by Clyne and Walker and by Watson. The implications of this reaction on the budgets of chloroform and phosgene in the troposphere will be discussed.

  9. 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.

  10. Data Filtering Impact on PV Degradation Rates and Uncertainty (Poster)

    SciTech Connect

    Jordan, D. C.; Kurtz, S. R.

    2012-03-01

    To sustain the commercial success of photovoltaics (PV) it becomes vital to know how power output decreases with time. In order to predict power delivery, degradation rates must be determined accurately. Data filtering, any data treatment assessment of long-term field behavior, is discussed as part of a more comprehensive uncertainty analysis and can be one of the greatest sources of uncertainty in long-term performance studies. Several distinct filtering methods such as outlier removal and inclusion of only sunny days on several different metrics such as PVUSA, performance ratio, DC power to plane-of-array irradiance ratio, uncorrected, and temperature-corrected were examined. PVUSA showed the highest sensitivity while temperature-corrected power over irradiance ratio was found to be the least sensitive to data filtering conditions. Using this ratio it is demonstrated that quantification of degradation rates with a statistical accuracy of +/- 0.2%/year within 4 years of field data is possible on two crystalline silicon and two thin-film systems.

  11. Reaction rates for mesoscopic reaction-diffusion kinetics

    DOE PAGES

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-23

    The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In thismore » paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. Finally, we show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.« less

  12. Reaction rates for mesoscopic reaction-diffusion kinetics

    SciTech Connect

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-23

    The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. Finally, we show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.

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

    DOE PAGES

    Hellander, Stefan; Petzold, Linda

    2016-01-19

    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 inmore » 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.« less

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

    PubMed

    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.

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

    SciTech Connect

    Hellander, Stefan; Petzold, Linda

    2016-01-19

    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.

  16. Thermonuclear Reaction Rate Parameterization for Nuclear Astrophysics

    NASA Astrophysics Data System (ADS)

    Sharp, Jacob; Kozub, Raymond L.; Smith, Michael S.; Scott, Jason; Lingerfelt, Eric

    2004-10-01

    The knowledge of thermonuclear reaction rates is vital to simulate novae, supernovae, X-ray bursts, and other astrophysical events. To facilitate dissemination of this knowledge, a set of tools has been created for managing reaction rates, located at www.nucastrodata.org. One tool is a rate parameterizer, which provides a parameterization for nuclear reaction rate vs. temperature values in the most widely used functional form. Currently, the parameterizer uses the Levenberg-Marquardt method (LMM), which requires an initial estimate of the best-fit parameters. The initial estimate is currently provided randomly from a preselected pool. To improve the quality of fits, a new, active method of selecting parameters has been developed. The parameters of each set in the pool are altered for a few iterations to replicate the input data as closely as possible. Then, the set which most nearly matches the input data (based on chi squared) is used in the LMM as the initial estimate for the final fitting procedure. A description of the new, active algorithm and its performance will be presented. Supported by the U. S. Department of Energy.

  17. Influence of rating-curve uncertainty on discharge signatures for 43 UK basins

    NASA Astrophysics Data System (ADS)

    Westerberg, Ida; Coxon, Gemma; Wagener, Thorsten; McMillan, Hilary; Freer, Jim

    2015-04-01

    Understanding rating-curve uncertainty is fundamental to understanding the information content of discharge data for hydrological analyses and modelling. Many studies have investigated discharge uncertainty and its effects at individual sites, but there is a need to estimate and compare uncertainty magnitudes across larger sets of catchments. This would enable a better understanding of the factors that control the discharge uncertainty magnitudes. In this study we investigated how rating-curve uncertainties propagate to uncertainty in hydrological signatures (derived as index values from the discharge time series) across a UK dataset. Such signature indices are used for a wide variety of purposes including model calibration, regionalisation, change detection, and eco-hydrological studies. The study was made using a diverse dataset of 43 catchments in the UK, incorporating gauging (stage-discharge) data and water level time series data from all the discharge stations. The signature uncertainties were assessed within a Monte Carlo framework, where rating-curve uncertainty was estimated using the "Voting Point" likelihood method that incorporated aleatory gauging uncertainty as well as epistemic uncertainty in the rating-curve approximation of the true stage-discharge relation. The rating-curve uncertainty estimation method worked well across the whole range of gauging stations in the dataset, incorporating different causes of epistemic uncertainty (e.g. weed growth, backwater) and different numbers of sections in the power-law rating curves. The discharge uncertainty was found to have a highly place-specific variability with flow range that propagated to the signature uncertainties. The signature uncertainty resulted from the conditions at the gauging station in combination with the flow series variability. The results show that discharge signature uncertainty can be large, with different factors controlling the uncertainty in different signatures, and that place

  18. Two-temperature reaction and relaxation rates

    NASA Astrophysics Data System (ADS)

    Kolesnichenko, E.; Gorbachev, Yu.

    2017-05-01

    Within the method of solving the kinetic equations for gas mixtures with internal degrees of freedom developed by the authors and based on the approximate summational invariants (ASI) concept, gas-dynamic equations for a multi-temperature model for the spatially inhomogeneous case are derived. For the two-temperature case, the expressions for the non-equilibrium reaction and relaxation rates are obtained. Special attention is drawn to corresponding thermodynamic equations. Different possibilities of introducing the gas-dynamic variables related to the internal degrees of freedom are considered. One is based on the choice of quantum numbers as the ASI, while the other is based on the choice of internal (vibrational) energy as the ASI. Limits to a one-temperature situation are considered in all the cases. For the cutoff harmonic oscillator model, explicit expressions for the reaction and relaxation rates are derived.

  19. 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.

  20. Quantum theory of chemical reaction rates

    SciTech Connect

    Miller, W.H. |

    1994-10-01

    If one wishes to describe a chemical reaction at the most detailed level possible, i.e., its state-to-state differential scattering cross section, then it is necessary to solve the Schroedinger equation to obtain the S-matrix as a function of total energy E and total angular momentum J, in terms of which the cross sections can be calculated as given by equation (1) in the paper. All other physically observable attributes of the reaction can be derived from the cross sections. Often, in fact, one is primarily interested in the least detailed quantity which characterizes the reaction, namely its thermal rate constant, which is obtained by integrating Eq. (1) over all scattering angles, summing over all product quantum states, and Boltzmann-averaging over all initial quantum states of reactants. With the proper weighting factors, all of these averages are conveniently contained in the cumulative reaction probability (CRP), which is defined by equation (2) and in terms of which the thermal rate constant is given by equation (3). Thus, having carried out a full state-to-state scattering calculation to obtain the S-matrix, one can obtain the CRP from Eq. (2), and then rate constant from Eq. (3), but this seems like ``overkill``; i.e., if one only wants the rate constant, it would clearly be desirable to have a theory that allows one to calculate it, or the CRP, more directly than via Eq. (2), yet also correctly, i.e., without inherent approximations. Such a theory is the subject of this paper.

  1. 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.

  2. 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.

  3. Reaction Rate Parameterization for Nuclear Astrophysics Research

    NASA Astrophysics Data System (ADS)

    Scott, J. P.; Lingerfelt, E. J.; Smith, M. S.; Hix, W. R.; Bardayan, D. W.; Sharp, J. E.; Kozub, R. L.; Meyer, R. A.

    2004-11-01

    Libraries of thermonuclear reaction rates are used in element synthesis models of a wide variety of astrophysical phenomena, such as exploding stars and the inner workings of our sun. These computationally demanding models are more efficient when libraries, which may contain over 60000 rates and vary by 20 orders of magnitude, have a uniform parameterization for all rates. We have developed an on-line tool, hosted at www.nucastrodata.org, to obtain REACLIB parameters (F.-K. Thielemann et al., Adv. Nucl. Astrophysics 525, 1 (1987)) that represent reaction rates as a function of temperature. This helps to rapidly incorporate the latest nuclear physics results in astrophysics models. The tool uses numerous techniques and algorithms in a modular fashion to improve the quality of the fits to the rates. Features, modules, and additional applications of this tool will be discussed. * Managed by UT-Battelle, LLC, for the U.S. D.O.E. under contract DE-AC05-00OR22725 + Supported by U.S. D.O.E. under Grant No. DE-FG02-96ER40955

  4. 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.

  5. Uncertainty

    USGS Publications Warehouse

    Hunt, Randall J.

    2012-01-01

    Management decisions will often be directly informed by model predictions. However, we now know there can be no expectation of a single ‘true’ model; thus, model results are uncertain. Understandable reporting of underlying uncertainty provides necessary context to decision-makers, as model results are used for management decisions. This, in turn, forms a mechanism by which groundwater models inform a risk-management framework because uncertainty around a prediction provides the basis for estimating the probability or likelihood of some event occurring. Given that the consequences of management decisions vary, it follows that the extent of and resources devoted to an uncertainty analysis may depend on the consequences. For events with low impact, a qualitative, limited uncertainty analysis may be sufficient for informing a decision. For events with a high impact, on the other hand, the risks might be better assessed and associated decisions made using a more robust and comprehensive uncertainty analysis. The purpose of this chapter is to provide guidance on uncertainty analysis through discussion of concepts and approaches, which can vary from heuristic (i.e. the modeller’s assessment of prediction uncertainty based on trial and error and experience) to a comprehensive, sophisticated, statistics-based uncertainty analysis. Most of the material presented here is taken from Doherty et al. (2010) if not otherwise cited. Although the treatment here is necessarily brief, the reader can find citations for the source material and additional references within this chapter.

  6. Chlorination of Amino Acids: Reaction Pathways and Reaction Rates.

    PubMed

    How, Zuo Tong; Linge, Kathryn L; Busetti, Francesco; Joll, Cynthia A

    2017-05-02

    Chlorination of amino acids can result in the formation of organic monochloramines or organic dichloramines, depending on the chlorine to amino acid ratio (Cl:AA). After formation, organic chloramines degrade into aldehydes, nitriles and N-chloraldimines. In this paper, the formation of organic chloramines from chlorination of lysine, tyrosine and valine were investigated. Chlorination of tyrosine and lysine demonstrated that the presence of a reactive secondary group can increase the Cl:AA ratio required for the formation of N,N-dichloramines, and potentially alter the reaction pathways between chlorine and amino acids, resulting in the formation of unexpected byproducts. In a detailed investigation, we report rate constants for all reactions in the chlorination of valine, for the first time, using experimental results and modeling. At Cl:AA = 2.8, the chlorine was found to first react quickly with valine (5.4 × 10(4) M(-1) s(-1)) to form N-monochlorovaline, with a slower subsequent reaction with N-monochlorovaline to form N,N-dichlorovaline (4.9 × 10(2) M(-1) s(-1)), although some N-monochlorovaline degraded into isobutyraldehyde (1.0 × 10(-4) s(-1)). The N,N-dichlorovaline then competitively degraded into isobutyronitrile (1.3 × 10(-4) s(-1)) and N-chloroisobutyraldimine (1.2 × 10(-4) s(-1)). In conventional drinking water disinfection, N-chloroisobutyraldimine can potentially be formed in concentrations higher than its odor threshold concentration, resulting in aesthetic challenges and an unknown health risk.

  7. 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.

  8. STARLIB: A NEXT-GENERATION REACTION-RATE LIBRARY FOR NUCLEAR ASTROPHYSICS

    SciTech Connect

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

    2013-07-15

    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, {gamma}), (p, {alpha}), ({alpha}, 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.

  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. Synthesis of superheavy elements: Uncertainty analysis to improve the predictive power of reaction models

    NASA Astrophysics Data System (ADS)

    Lü, Hongliang; Boilley, David; Abe, Yasuhisa; Shen, Caiwan

    2016-09-01

    Background: Synthesis of superheavy elements is performed by heavy-ion fusion-evaporation reactions. However, fusion is known to be hindered with respect to what can be observed with lighter ions. Thus some delicate ambiguities remain on the fusion mechanism that eventually lead to severe discrepancies in the calculated formation probabilities coming from different fusion models. Purpose: In the present work, we propose a general framework based upon uncertainty analysis in the hope of constraining fusion models. Method: To quantify uncertainty associated with the formation probability, we propose to propagate uncertainties in data and parameters using the Monte Carlo method in combination with a cascade code called kewpie2, with the aim of determining the associated uncertainty, namely the 95 % confidence interval. We also investigate the impact of different models or options, which cannot be modeled by continuous probability distributions, on the final results. An illustrative example is presented in detail and then a systematic study is carried out for a selected set of cold-fusion reactions. Results: It is rigorously shown that, at the 95 % confidence level, the total uncertainty of the empirical formation probability appears comparable to the discrepancy between calculated values. Conclusions: The results obtained from the present study provide direct evidence for predictive limitations of the existing fusion-evaporation models. It is thus necessary to find other ways to assess such models for the purpose of establishing a more reliable reaction theory, which is expected to guide future experiments on the production of superheavy elements.

  11. A simple reaction-rate model for turbulent diffusion flames

    NASA Technical Reports Server (NTRS)

    Bangert, L. H.

    1975-01-01

    A simple reaction rate model is proposed for turbulent diffusion flames in which the reaction rate is proportional to the turbulence mixing rate. The reaction rate is also dependent on the mean mass fraction and the mean square fluctuation of mass fraction of each reactant. Calculations are compared with experimental data and are generally successful in predicting the measured quantities.

  12. 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.

  13. Reduced Uncertainties in the Supernova Production of the Gamma Emitting Nuclei 26Al, 44Ti, and 60Fe Using Effective Helium Burning Rates

    NASA Astrophysics Data System (ADS)

    Austin, Sam M.; West, Christopher; Heger, Alexander

    2016-09-01

    Uncertainties in the helium burning reaction rates caused large uncertainties in previous predictions of the production of the gamma emitting nuclei 26Al and (especially) 60Fe in core collapse supernovae. This precluded a meaningful comparison of the predictions with observed gamma ray intensities. We present results using a newly developed effective reaction rate (ERR) for the helium burning reactions to predict the yields of 26Al, 44Ti, and 60Fe. The resulting yield uncertainties using the ERR are much smaller than obtained previously, and smaller than other uncertainties. The yield ratio, 60Fe/26Al, had variations of less than 20 percent and appears to be the most robust observable related to the production of these nuclei. We also estimated the effects of failed supernovae on the yields by using a compactness filter. This substantially reduced the three yields but the ratio, 60Fe/26Al, was little affected. Research supported by US NSF and DOE, and by ARC.

  14. 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…

  15. 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…

  16. Empirical rate formula for ion-dipolar molecule reactions

    NASA Astrophysics Data System (ADS)

    Sato, Shin

    2017-04-01

    New empirical rate formula for the low temperature reactions is proposed. The formula proposed previously has been simplified by using incomplete gamma function. A few examples of temperature dependence of rate constants for the reactions of ions with dipolar molecules and that for the reaction F +H2 →HF +H are demonstrated by using new rate formula.

  17. Effects of Upstream Turbulence on Measurement Uncertainty of Flow Rate by Venturi

    NASA Astrophysics Data System (ADS)

    Lee, Jungho; Yoon, Seok Ho; Yu, Cheong-Hwan; Park, Sang-Jin; Chung, Chang-Hwan

    2010-06-01

    Venturi has been widely used for measuring flow rate in a variety of engineering applications since pressure loss is relatively small compared with other measuring method. The current study focuses on making detailed estimation of measured uncertainties as the upstream turbulence affects uncertainty levels of the water flows in the closed-loop testing. Upstream turbulences can be controlled by selecting 9 different swirl generators. Measurement uncertainty of flow rate has been estimated by a quantitative uncertainty analysis which is based on the ANSI/ASME PTC 19.1-2005 standard. The best way to reduce error in measuring flow rate was investigated for evaluating its measurement uncertainty. The results of flow rate uncertainty analysis show that the case with systematic error has higher than that without systematic error. Especially the result with systematic error exhibits that the uncertainty of flow rate was gradually increased by upstream turbulence. Uncertainty of flow rate measurement can be mainly affected by differential pressure and discharge coefficient. Flow disturbance can be also reduced by increasing of the upstream straight length of Venturi.

  18. In-cell reaction rate distributions and cell-average reaction rates in fast critical assemblies

    SciTech Connect

    Brumbach, S.B.; Gasidlo, J.M.

    1985-08-01

    Measurements are described for determining average values of fission rates in /sup 235/U, /sup 238/U and /sup 239/Pu and capture rates in /sup 238/U for heterogeneous cells used to construct fast critical assemblies. The measurements are based on irradiations of foils of /sup 238/U, /sup 235/U and /sup 239/Pu with counting of fission and capture products using gamma-ray spectroscopy. Both plate and pin cells are considered. Procedures are described for inferring cell-average reaction rate values from a single foil location based on a cell using a quantity called a cell factor. Cell factors are determined from special measurements in which several foils are irradiated within a cell. Comparisons are presented between cell factors determined by measurements and by Monte Carlo calculations which lend credibility to the measurement procedures.

  19. The MapCHECK Measurement Uncertainty function and its effect on planar dose pass rates.

    PubMed

    Bailey, Daniel W; Spaans, Jason D; Kumaraswamy, Lalith K; Podgorsak, Matthew B

    2016-03-01

    Our study aimed to quantify the effect of the Measurement Uncertainty function on planar dosimetry pass rates, as measured and analyzed with the Sun Nuclear Corporation MapCHECK 2 array and its associated software. This optional function is toggled in the program preferences of the software (though turned on by default upon installation), and automatically increases the dose difference tolerance defined by the user for each planar dose comparison. Dose planes from 109 static-gantry IMRT fields and 40 VMAT arcs, of varying modulation complexity, were measured at 5 cm water-equivalent depth in the MapCHECK 2 diode array, and respective calculated dose planes were exported from a commercial treatment planning system. Planar dose comparison pass rates were calculated within the Sun Nuclear Corporation analytic software using a number of calculation parameters, including Measurement Uncertainty on and off. By varying the percent difference (%Diff) criterion for similar analyses performed with Measurement Uncertainty turned off, an effective %Diff criterion was defined for each field/arc corresponding to the pass rate achieved with Measurement Uncertainty turned on. On average, the Measurement Uncertainty function increases the user-defined %Diff criterion by 0.8%-1.1% for 3%/3 mm analysis, depending on plan type and calculation technique (corresponding to an average change in pass rate of 1.0%-3.5%, and a maximum change of 8.7%). At the 2%/2 mm level, the Measurement Uncertainty function increases the user-defined %Diff criterion by 0.7%-1.2% on average, again depending on plan type and calculation technique (corresponding to an average change in pass rate of 3.5%-8.1%, and a maximum change of 14.2%). The largest increases in pass rate due to the Measurement Uncertainty function are generally seen with poorly matched planar dose comparisons, while the function has a notably smaller effect as pass rates approach 100%. The Measurement Uncertainty function, then, may

  20. The MapCHECK Measurement Uncertainty function and its effect on planar dose pass rates.

    PubMed

    Bailey, Daniel W; Spaans, Jason D; Kumaraswamy, Lalith K; Podgorsak, Matthew B

    2016-03-08

    Our study aimed to quantify the effect of the Measurement Uncertainty function on planar dosimetry pass rates, as measured and analyzed with the Sun Nuclear Corporation MapCHECK 2 array and its associated software. This optional function is toggled in the program preferences of the software (though turned on by default upon installation), and automatically increases the dose difference tolerance defined by the user for each planar dose comparison. Dose planes from 109 static-gantry IMRT fields and 40 VMAT arcs, of varying modulation complexity, were measured at 5 cm water-equivalent depth in the MapCHECK 2 diode array, and respective calculated dose planes were exported from a commercial treatment planning system. Planar dose comparison pass rates were calculated within the Sun Nuclear Corporation analytic software using a number of calculation parameters, including Measurement Uncertainty on and off. By varying the percent difference (%Diff) criterion for similar analyses performed with Measurement Uncertainty turned off, an effective %Diff criterion was defined for each field/arc corresponding to the pass rate achieved with Measurement Uncertainty turned on. On average, the Measurement Uncertainty function increases the user-defined %Diff criterion by 0.8%-1.1% for 3%/3 mm analysis, depending on plan type and calculation technique (corresponding to an average change in pass rate of 1.0%-3.5%, and a maximum change of 8.7%). At the 2%/2 mm level, the Measurement Uncertainty function increases the user-defined %Diff criterion by 0.7%-1.2% on average, again depending on plan type and calculation technique (corresponding to an average change in pass rate of 3.5%-8.1%, and a maximum change of 14.2%). The largest increases in pass rate due to the Measurement Uncertainty function are generally seen with poorly matched planar dose comparisons, while the function has a notably smaller effect as pass rates approach 100%. The Measurement Uncertainty function, then, may

  1. Measurement uncertainty analysis of low-dose-rate prostate seed brachytherapy: post-implant dosimetry.

    PubMed

    Gregory, Kent J; Pattison, John E; Bibbo, Giovanni

    2015-03-01

    The minimal dose covering 90 % of the prostate volume--D 90--is arguably the most important dosimetric parameter in low-dose-rate prostate seed brachytherapy. In this study an analysis of the measurement uncertainties in D 90 from low-dose-rate prostate seed brachytherapy was conducted for two common treatment procedures with two different post-implant dosimetry methods. The analysis was undertaken in order to determine the magnitude of D 90 uncertainty, how the magnitude of the uncertainty varied when D 90 was calculated using different dosimetry methods, and which factors were the major contributors to the uncertainty. The analysis considered the prostate as being homogeneous and tissue equivalent and made use of published data, as well as original data collected specifically for this analysis, and was performed according to the Guide to the expression of uncertainty in measurement (GUM). It was found that when prostate imaging and seed implantation were conducted in two separate sessions using only CT images for post-implant analysis, the expanded uncertainty in D 90 values were about 25 % at the 95 % confidence interval. When prostate imaging and seed implantation were conducted during a single session using CT and ultrasound images for post-implant analysis, the expanded uncertainty in D 90 values were about 33 %. Methods for reducing these uncertainty levels are discussed. It was found that variations in contouring the target tissue made the largest contribution to D 90 uncertainty, while the uncertainty in seed source strength made only a small contribution. It is important that clinicians appreciate the overall magnitude of D 90 uncertainty and understand the factors that affect it so that clinical decisions are soundly based, and resources are appropriately allocated.

  2. Harnessing the uncertainty monster: Putting quantitative constraints on the intergenerational social discount rate

    NASA Astrophysics Data System (ADS)

    Lewandowsky, Stephan; Freeman, Mark C.; Mann, Michael E.

    2017-09-01

    There is broad consensus among economists that unmitigated climate change will ultimately have adverse global economic consequences, that the costs of inaction will likely outweigh the cost of taking action, and that social planners should therefore put a price on carbon. However, there is considerable debate and uncertainty about the appropriate value of the social discount rate, that is the extent to which future damages should be discounted relative to mitigation costs incurred now. We briefly review the ethical issues surrounding the social discount rate and then report a simulation experiment that constrains the value of the discount rate by considering 4 sources of uncertainty and ambiguity: Scientific uncertainty about the extent of future warming, social uncertainty about future population and future economic development, political uncertainty about future mitigation trajectories, and ethical ambiguity about how much the welfare of future generations should be valued today. We compute a certainty-equivalent declining discount rate that accommodates all those sources of uncertainty and ambiguity. The forward (instantaneous) discount rate converges to a value near 0% by century's end and the spot (horizon) discount rate drops below 2% by 2100 and drops below previous estimates by 2070.

  3. NACRE: A European Compilation of Reaction Rates for Astrophysics

    SciTech Connect

    Carmen Angulo

    1999-12-31

    We report on the program and results of the NACRE network (Nuclear Astrophysics Compilation of Reaction rates). We have compiled low-energy cross section data for 86 charged-particle induced reactions involving light (1 {<=} Z {<=} 14) nuclei. The corresponding Maxwellian-averaged thermonuclear reactions rates are calculated in the temperature range from 10{sup 6} K to 10{sup 10} K. The web site, http://pntpm.ulb.ac.be/nacre.htm, including the cross section data base and the reaction rates, allows users to browse electronically all the information on the reactions studied in this compilation.

  4. NACRE: A European Compilation of Reaction rates for Astrophysics

    SciTech Connect

    Angulo, Carmen

    1999-11-16

    We report on the program and results of the NACRE network (Nuclear Astrophysics Compilation of REaction rates). We have compiled low-energy cross section data for 86 charged-particle induced reactions involving light (1{<=}Z{<=}14) nuclei. The corresponding Maxwellian-averaged thermonuclear reactions rates are calculated in the temperature range from 10{sup 6} K to 10{sup 10} K. The web site http://pntpm.ulb.ac.be/nacre.htm, including the cross section data base and the reaction rates, allows users to browse electronically all the information on the reactions studied in this compilation.

  5. Subterranean production of neutrons, 39Ar and 21Ne: Rates and uncertainties

    NASA Astrophysics Data System (ADS)

    Šrámek, Ondřej; Stevens, Lauren; McDonough, William F.; Mukhopadhyay, Sujoy; Peterson, R. J.

    2017-01-01

    Accurate understanding of the subsurface production rate of the radionuclide 39Ar is necessary for argon dating techniques and noble gas geochemistry of the shallow and the deep Earth, and is also of interest to the WIMP dark matter experimental particle physics community. Our new calculations of subsurface production of neutrons, 21Ne , and 39Ar take advantage of the state-of-the-art reliable tools of nuclear physics to obtain reaction cross sections and spectra (TALYS) and to evaluate neutron propagation in rock (MCNP6). We discuss our method and results in relation to previous studies and show the relative importance of various neutron, 21Ne , and 39Ar nucleogenic production channels. Uncertainty in nuclear reaction cross sections, which is the major contributor to overall calculation uncertainty, is estimated from variability in existing experimental and library data. Depending on selected rock composition, on the order of 107-1010 α particles are produced in one kilogram of rock per year (order of 1-103 kg-1 s-1); the number of produced neutrons is lower by ∼ 6 orders of magnitude, 21Ne production rate drops by an additional factor of 15-20, and another one order of magnitude or more is dropped in production of 39Ar. Our calculation yields a nucleogenic 21Ne /4He production ratio of (4.6 ± 0.6) ×10-8 in Continental Crust and (4.2 ± 0.5) ×10-8 in Oceanic Crust and Depleted Mantle. Calculated 39Ar production rates span a great range from 29 ± 9 atoms kg-rock-1 yr-1 in the K-Th-U-enriched Upper Continental Crust to (2.6 ± 0.8) × 10-4 atoms kg-rock-1 yr-1 in Depleted Upper Mantle. Nucleogenic 39Ar production exceeds the cosmogenic production below ∼700 m depth and thus, affects radiometric ages of groundwater. The 39Ar chronometer, which fills in a gap between 3H and 14C , is particularly important given the need to tap deep reservoirs of ancient drinking water.

  6. Sensitivity of p-Nuclei to (n,g) Reaction Rates

    NASA Astrophysics Data System (ADS)

    Scriven, Dustin; Naqvi, Farheen; Spyrou, Artemis; Simon, Anna; Mayer, Brad

    2015-10-01

    The astrophysical p-process, which is responsible for the creation of the proton-rich p-nuclei, is still not well understood. A sensitivity study of p-nuclei abundances to (n, γ) and (γ,n) reaction rates was conducted at the National Superconducting Cyclotron Laboratory using a nuclear reaction network created at Clemson University. This network simulates the explosive shock front of a Type II supernova passing through the oxygen/neon layer of a 25 M⊙ star. Reaction rates of many (n, γ) reactions and their inverses were increased and decreased by a factor of 3 and the effects were observed. Probing the sensitivity of p-nuclei abundances aids in pointing out reactions important to the p-process. In turn, this information can be used as a tool to drive experimental research, helping to decrease uncertainties and increase the robustness of p-process and other stellar models.

  7. Multidimensional reaction rate theory with anisotropic diffusion.

    PubMed

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

    2014-11-28

    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.

  8. Can hydraulic-modelled rating curves reduce uncertainty in high flow data?

    NASA Astrophysics Data System (ADS)

    Westerberg, Ida; Lam, Norris; Lyon, Steve W.

    2017-04-01

    Flood risk assessments rely on accurate discharge data records. Establishing a reliable rating curve for calculating discharge from stage at a gauging station normally takes years of data collection efforts. Estimation of high flows is particularly difficult as high flows occur rarely and are often practically difficult to gauge. Hydraulically-modelled rating curves can be derived based on as few as two concurrent stage-discharge and water-surface slope measurements at different flow conditions. This means that a reliable rating curve can, potentially, be derived much faster than a traditional rating curve based on numerous stage-discharge gaugings. In this study we compared the uncertainty in discharge data that resulted from these two rating curve modelling approaches. We applied both methods to a Swedish catchment, accounting for uncertainties in the stage-discharge gauging and water-surface slope data for the hydraulic model and in the stage-discharge gauging data and rating-curve parameters for the traditional method. We focused our analyses on high-flow uncertainty and the factors that could reduce this uncertainty. In particular, we investigated which data uncertainties were most important, and at what flow conditions the gaugings should preferably be taken. First results show that the hydraulically-modelled rating curves were more sensitive to uncertainties in the calibration measurements of discharge than water surface slope. The uncertainty of the hydraulically-modelled rating curves were lowest within the range of the three calibration stage-discharge gaugings (i.e. between median and two-times median flow) whereas uncertainties were higher outside of this range. For instance, at the highest observed stage of the 24-year stage record, the 90% uncertainty band was -15% to +40% of the official rating curve. Additional gaugings at high flows (i.e. four to five times median flow) would likely substantially reduce those uncertainties. These first results show

  9. 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.

  10. Uncertainty in Population Growth Rates: Determining Confidence Intervals from Point Estimates of Parameters

    PubMed Central

    Devenish Nelson, Eleanor S.; Harris, Stephen; Soulsbury, Carl D.; Richards, Shane A.; Stephens, Philip A.

    2010-01-01

    Background Demographic models are widely used in conservation and management, and their parameterisation often relies on data collected for other purposes. When underlying data lack clear indications of associated uncertainty, modellers often fail to account for that uncertainty in model outputs, such as estimates of population growth. Methodology/Principal Findings We applied a likelihood approach to infer uncertainty retrospectively from point estimates of vital rates. Combining this with resampling techniques and projection modelling, we show that confidence intervals for population growth estimates are easy to derive. We used similar techniques to examine the effects of sample size on uncertainty. Our approach is illustrated using data on the red fox, Vulpes vulpes, a predator of ecological and cultural importance, and the most widespread extant terrestrial mammal. We show that uncertainty surrounding estimated population growth rates can be high, even for relatively well-studied populations. Halving that uncertainty typically requires a quadrupling of sampling effort. Conclusions/Significance Our results compel caution when comparing demographic trends between populations without accounting for uncertainty. Our methods will be widely applicable to demographic studies of many species. PMID:21049049

  11. Estimating trends in the total fertility rate with uncertainty using imperfect data: Examples from West Africa

    PubMed Central

    Alkema, Leontine; Raftery, Adrian E.; Gerland, Patrick; Clark, Samuel J.; Pelletier, François

    2013-01-01

    Background Estimating the total fertility rate is challenging for many developing countries because of limited data and varying data quality. A standardized, reproducible approach to produce estimates that include an uncertainty assessment is desired. Methods We develop a method to estimate and assess uncertainty in the total fertility rate over time, based on multiple imperfect observations from different data sources, including surveys and censuses. We take account of measurement error in observations by decomposing it into bias and variance, and assess both by linear regression on a variety of data quality covariates. We estimate the total fertility rate using a local smoother, and assess uncertainty using the weighted likelihood bootstrap. Results We apply our method to data from seven countries in West Africa and construct estimates and uncertainty intervals for the total fertility rate. Based on cross-validation exercises, we find that accounting for differences in data quality between observations gives better calibrated confidence intervals and reduces bias. Conclusions When working with multiple imperfect observations from different data sources to estimate the total fertility rate, or demographic indicators in general, potential biases and differences in error variance should be taken into account to improve the estimates and their uncertainty assessment. PMID:24273449

  12. 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.

  13. Imaginary-time formalism for triple-α reaction rates

    NASA Astrophysics Data System (ADS)

    Akahori, T.; Funaki, Y.; Yabana, K.

    2015-08-01

    Using imaginary-time formalism, it is shown that the triple-α reaction rate can be reliably calculated without the need to solve scattering problems involving three charged particles. The calculated reaction rate is found to agree well with the empirical NACRE rate, which is widely adopted in stellar evolution calculations. The reason for this is explained using R -matrix theory. Extremely slow convergence is found to occur when a coupled-channel expansion is introduced, which helps to explain the very different reaction rates obtained using a coupled-channel approach.

  14. Non-resonant Triple- α Reaction Rate at Low Temperature

    NASA Astrophysics Data System (ADS)

    Tamii, A.; Aoi, N.; Fujita, H.; Fujita, Y.; Hatanaka, K.; Hashimoto, T.; Kawabata, T.; Miki, K.; Itoh, M.; Itoh, T.; Kamimura, M.; Ogata, K.; Ong, H. J.; Sakaguchi, H.; Shima, T.; Suzuki, T.; Yamamoto, T.

    2013-08-01

    The triple α reaction rate in stars is quite important in many astrophysical scenarios including the stellar evolution and carbon synthesis in stars. Recently the non-resonant triple α reaction rate has been reevaluated using a calculation with the continuum-discretized coupled-channels (CDCC) method, which dramatically increased the rate at low temperature compared to the widely-used NACRE compilation. Since the enhancement influences strongly on astrophysical model simulations, we have planned an experiment for drawing conclusion on the non-resonant triple α reaction rate at low temperature by measuring the three- α continuum state in 12C. We report the present situation of the experiment.

  15. Influence of autoregressive model parameter uncertainty on spectral estimates of heart rate dynamics.

    PubMed

    Christini, D J; Kulkarni, A; Rao, S; Stutman, E R; Bennett, F M; Hausdorff, J M; Oriol, N; Lutchen, K R

    1995-01-01

    Linear autoregressive (AR) model-based heart rate (HR) spectral analysis has been widely used to study HR dynamics. Owing to system and measurement noise, the parameters of an AR model have intrinsic statistical uncertainty. In this study, we evaluate how this AR parameter uncertainty can translate to uncertainty in HR power spectra. HR time series, obtained from seven subjects in supine and standing positions, were fitted to AR models by least squares minimization via singular value decomposition. Spectral uncertainty due to inexact parameter estimation was assessed through a Monte Carlo study in which the AR model parameters were varied randomly according to their Gaussian distributions. Histogram techniques were used to evaluate the distribution of 50,000 AR spectral estimates of each HR time series. These Monte Carlo uncertainties were found to exceed those predicted by previous theoretical approximations. It was determined that the uncertainty of AR HR spectral estimates, particularly the locations and magnitudes of spectral peaks, can often be large. The same Monte Carlo analysis was applied to synthetic AR time series and found levels of spectral uncertainty similar to that of the HR data, thus suggesting that the results of this study are not specific to experimental HR data. Therefore, AR spectra may be unreliable, and one must be careful in assigning pathophysiological origins to specific spectral features of any one spectrum.

  16. 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.

  17. Blaming for a better future: future orientation and associated intolerance of personal uncertainty lead to harsher reactions toward innocent victims.

    PubMed

    Bal, Michèlle; van den Bos, Kees

    2012-07-01

    People are often encouraged to focus on the future and strive for long-term goals. This noted, the authors argue that this future orientation is associated with intolerance of personal uncertainty, as people usually cannot be certain that their efforts will pay off. To be able to tolerate personal uncertainty, people adhere strongly to the belief in a just world, paradoxically resulting in harsher reactions toward innocent victims. In three experiments, the authors show that a future orientation indeed leads to more negative evaluations of an innocent victim (Study 1), enhances intolerance of personal uncertainty (Study 2), and that experiencing personal uncertainty leads to more negative evaluations of a victim (Study 3). So, while a future orientation enables people to strive for long-term goals, it also leads them to be harsher toward innocent victims. One underlying mechanism causing these reactions is intolerance of personal uncertainty, associated with a future orientation.

  18. Propagation of neutron-reaction uncertainties through multi-physics models of novel LWR's

    NASA Astrophysics Data System (ADS)

    Hernandez-Solis, Augusto; Sjöstrand, Henrik; Helgesson, Petter

    2017-09-01

    The novel design of the renewable boiling water reactor (RBWR) allows a breeding ratio greater than unity and thus, it aims at providing for a self-sustained fuel cycle. The neutron reactions that compose the different microscopic cross-sections and angular distributions are uncertain, so when they are employed in the determination of the spatial distribution of the neutron flux in a nuclear reactor, a methodology should be employed to account for these associated uncertainties. In this work, the Total Monte Carlo (TMC) method is used to propagate the different neutron-reactions (as well as angular distributions) covariances that are part of the TENDL-2014 nuclear data (ND) library. The main objective is to propagate them through coupled neutronic and thermal-hydraulic models in order to assess the uncertainty of important safety parameters related to multi-physics, such as peak cladding temperature along the axial direction of an RBWR fuel assembly. The objective of this study is to quantify the impact that ND covariances of important nuclides such as U-235, U-238, Pu-239 and the thermal scattering of hydrogen in H2O have in the deterministic safety analysis of novel nuclear reactors designs.

  19. The Multi-Step CADIS method for shutdown dose rate calculations and uncertainty propagation

    SciTech Connect

    Ibrahim, Ahmad M.; Peplow, Douglas E.; Grove, Robert E.; Peterson, Joshua L.; Johnson, Seth R.

    2015-12-01

    Shutdown dose rate (SDDR) analysis requires (a) a neutron transport calculation to estimate neutron flux fields, (b) an activation calculation to compute radionuclide inventories and associated photon sources, and (c) a photon transport calculation to estimate final SDDR. In some applications, accurate full-scale Monte Carlo (MC) SDDR simulations are needed for very large systems with massive amounts of shielding materials. However, these simulations are impractical because calculation of space- and energy-dependent neutron fluxes throughout the structural materials is needed to estimate distribution of radioisotopes causing the SDDR. Biasing the neutron MC calculation using an importance function is not simple because it is difficult to explicitly express the response function, which depends on subsequent computational steps. Furthermore, the typical SDDR calculations do not consider how uncertainties in MC neutron calculation impact SDDR uncertainty, even though MC neutron calculation uncertainties usually dominate SDDR uncertainty.

  20. The Multi-Step CADIS method for shutdown dose rate calculations and uncertainty propagation

    DOE PAGES

    Ibrahim, Ahmad M.; Peplow, Douglas E.; Grove, Robert E.; ...

    2015-12-01

    Shutdown dose rate (SDDR) analysis requires (a) a neutron transport calculation to estimate neutron flux fields, (b) an activation calculation to compute radionuclide inventories and associated photon sources, and (c) a photon transport calculation to estimate final SDDR. In some applications, accurate full-scale Monte Carlo (MC) SDDR simulations are needed for very large systems with massive amounts of shielding materials. However, these simulations are impractical because calculation of space- and energy-dependent neutron fluxes throughout the structural materials is needed to estimate distribution of radioisotopes causing the SDDR. Biasing the neutron MC calculation using an importance function is not simple becausemore » it is difficult to explicitly express the response function, which depends on subsequent computational steps. Furthermore, the typical SDDR calculations do not consider how uncertainties in MC neutron calculation impact SDDR uncertainty, even though MC neutron calculation uncertainties usually dominate SDDR uncertainty.« less

  1. Rate constant for reaction of atomic hydrogen with germane

    NASA Technical Reports Server (NTRS)

    Nava, David F.; Payne, Walter A.; Marston, George; Stief, Louis J.

    1990-01-01

    Due to the interest in the chemistry of germane in the atmospheres of Jupiter and Saturn, and because previously reported kinetic reaction rate studies at 298 K gave results differing by a factor of 200, laboratory measurements were performed to determine the reaction rate constant for H + GeH4. Results of the study at 298 K, obtained via the direct technique of flash photolysis-resonance fluorescence, yield the reaction rate constant, k = (4.08 + or - 0.22) x 10(exp -12) cu cm/s.

  2. Development of an Uncertainty Quantification Predictive Chemical Reaction Model for Syngas Combustion

    DOE PAGES

    Slavinskaya, N. A.; Abbasi, M.; Starcke, J. H.; ...

    2017-01-24

    An automated data-centric infrastructure, Process Informatics Model (PrIMe), was applied to validation and optimization of a syngas combustion model. The Bound-to-Bound Data Collaboration (B2BDC) module of PrIMe was employed to discover the limits of parameter modifications based on uncertainty quantification (UQ) and consistency analysis of the model–data system and experimental data, including shock-tube ignition delay times and laminar flame speeds. Existing syngas reaction models are reviewed, and the selected kinetic data are described in detail. Empirical rules were developed and applied to evaluate the uncertainty bounds of the literature experimental data. Here, the initial H2/CO reaction model, assembled from 73more » reactions and 17 species, was subjected to a B2BDC analysis. For this purpose, a dataset was constructed that included a total of 167 experimental targets and 55 active model parameters. Consistency analysis of the composed dataset revealed disagreement between models and data. Further analysis suggested that removing 45 experimental targets, 8 of which were self-inconsistent, would lead to a consistent dataset. This dataset was subjected to a correlation analysis, which highlights possible directions for parameter modification and model improvement. Additionally, several methods of parameter optimization were applied, some of them unique to the B2BDC framework. The optimized models demonstrated improved agreement with experiments compared to the initially assembled model, and their predictions for experiments not included in the initial dataset (i.e., a blind prediction) were investigated. The results demonstrate benefits of applying the B2BDC methodology for developing predictive kinetic models.« less

  3. On the Initial Rate of Fluid-Solid Reactions

    NASA Astrophysics Data System (ADS)

    Sohn, Hong Yong; Fan, De-Qiu

    2017-02-01

    It is argued in this paper that the initial rate should not be used for the measurement or analysis the kinetics of a fluid-solid reaction, especially for a reaction in which the effect of pore diffusion starts appearing even moderately as the reaction proceeds. Even in the absence of external mass transfer effects, it is shown in this work by rigorous mathematical analysis that the range of conditions where the initial rate represents the intrinsic kinetics is very narrow. For an initially non-porous solid in the absence of external mass transfer effects, the very initial rate should mathematically be the intrinsic rate even when pore diffusion becomes important as the reaction proceeds. However, even in this case, the range of conditions for this statement is very limited. For the reaction of an initially porous solid, the rate at time zero is already affected by pore diffusion unless its effect is negligible over the entire range of conversion. Furthermore, the initial reaction rates of porous solids reacting under large values of k/D e ratio (chemical reactivity is much greater than the capacity for pore diffusion) have an apparent rate constant of √ {k \\cdot D_{e} } and thus pore diffusion alone does not control the initial rate no matter how large the effect of pore diffusion is overall.

  4. The affects on Titan atmospheric modeling by variable molecular reaction rates

    NASA Astrophysics Data System (ADS)

    Hamel, Mark D.

    The main effort of this thesis is to study the production and loss of molecular ions in the ionosphere of Saturn's largest moon Titan. Titan's atmosphere is subject to complex photochemical processes that can lead to the production of higher order hydrocarbons and nitriles. Ion-molecule chemistry plays an important role in this process but remains poorly understood. In particular, current models that simulate the photochemistry of Titan's atmosphere overpredict the abundance of the ionosphere's main ions suggesting a flaw in the modeling process. The objective of this thesis is to determine which reactions are most important for production and loss of the two primary ions, C2H5+ and HCNH+, and what is the impact of uncertainty in the reaction rates on the production and loss of these ions. In reviewing the literature, there is a contention about what reactions are really necessary to illuminate what is occurring in the atmosphere. Approximately seven hundred reactions are included in the model used in this discussion (INT16). This paper studies what reactions are fundamental to the atmospheric processes in Titan's upper atmosphere, and also to the reactions that occur in the lower bounds of the ionosphere which are used to set a baseline molecular density for all species, and reflects what is expected at those altitudes on Titan. This research was conducted through evaluating reaction rates and cross sections available in the scientific literature and through conducting model simulations of the photochemistry in Titan's atmosphere under a range of conditions constrained by the literature source. The objective of this study is to determine the dependence of ion densities of C2H5+ and HCNH+ on the uncertainty in the reaction rates that involve these two ions in Titan's atmosphere.

  5. Calibrating a hydrological model in stage space to account for rating curve uncertainties: general framework and key challenges

    NASA Astrophysics Data System (ADS)

    Sikorska, Anna E.; Renard, Benjamin

    2017-07-01

    Hydrological models are typically calibrated with discharge time series derived from a rating curve, which is subject to parametric and structural uncertainties that are usually neglected. In this work, we develop a Bayesian approach to probabilistically represent parametric and structural rating curve errors in the calibration of hydrological models. To achieve this, we couple the hydrological model with the inverse rating curve yielding the rainfall-stage model that is calibrated in stage space. Acknowledging uncertainties of the hydrological and the rating curve models allows assessing their contribution to total uncertainties of stages and discharges. Our results from a case study in France indicate that (a) ignoring rating curve uncertainty leads to changes in hydrological parameters, and (b) structural uncertainty of hydrological model dominates other uncertainty sources. The paper ends with discussing key challenges that remain to be addressed to achieve a meaningful quantification of various uncertainty sources that affect hydrological model, as including input errors.

  6. Reaction sintering of zinc ferrite during constant rates of heating

    SciTech Connect

    Rahaman, M.N. . Ceramic Engineering Dept.); De Jonghe, L.C. . Lawrence Berkeley Lab.)

    1993-07-01

    The reaction sintering of equimolar quantities of zinc oxide and ferric oxide was investigated under conditions of constant rates of heating and the data were compared with those for a calcined, single-phase zinc ferrite powder. For the heating rate of 1C/min, the densifications of the reaction-sintered sample and the calcined sample were approximately the same. However, as the heating rate increased, the density at any temperature increased slightly for the reaction-sintered sample but decreased slightly for the calcined powder. The factors responsible for this slight difference in sintering between the reaction-sintered sample and the calcined sample are discussed. For the constant heating rates used, the reaction was completed prior to any significant densification. Relative densities of >95% were obtained for both the reaction-sintered sample and the calcined sample under identical sintering conditions (1-10C/min to 1350C). Reaction sintering in a steep temperature gradient produced a nearly fully dense body prior to complete reaction; a composite microstructure consisting of fine zinc oxide grains in matrix of zinc ferrite was obtained.

  7. 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.

  8. 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.

  9. 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.

  10. Characterising the sources and impacts of rating curve uncertainty across the United Kingdom gauging network

    NASA Astrophysics Data System (ADS)

    Coxon, Gemma; Westerberg, Ida; Freer, Jim; Wagener, Thorsten

    2015-04-01

    Knowledge of hydrological systems is largely derived from observed streamflow. Such data is often obtained from multiple different sources and providers that are regionally managed, and equally, all gauges are unique in their characteristics and their resultant uncertainties. Hydrologists are increasingly interrogating and using streamflow time series from ever increasing numbers of gauging stations. Therefore, to ensure that robust conclusions can be drawn from these datasets, it is important to assess their quality and quantify their uncertainties prior to any modelling. This is particularly important as observational data can be subject to significant sources of uncertainty that can vary across the flow range, between gauging stations and have non-stationary properties. In this study, we contribute to the hydrological community's understanding and awareness of discharge uncertainty by analysing a dataset of rating curves and stage-discharge measurements from 1192 gauging stations in the United Kingdom. The objectives of the study are to, a) demonstrate the different uncertainty sources that impact the modelling of the stage-discharge relationship across the UK, and b) quantify their impact on uncertainty in modelled rating curves and the discharge time series derived from them. To do this, we first reviewed the dataset on a national scale. Different aspects of the stage-discharge relationship were quantified including the number of stage-discharge measurements and historical rating curves, and the amount of time flow is extrapolated at low and high flows. We identified regional differences in the uncertainty sources that affect the modelling of the stage-discharge relationship and were able to draw links between these and differences in the gauging station network, regional hydrometric priorities and catchment characteristics. For the second part of the study, we drew upon a set of case studies where the rating curves and stage-discharge measurements are

  11. 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.

  12. 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.

  13. 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.

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

    PubMed Central

    Motagamwala, Ali Hussain; Dumesic, James A.

    2016-01-01

    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. PMID:27162366

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

    DOE PAGES

    Motagamwala, Ali Hussain; Dumesic, James A.

    2016-05-09

    In this paper, 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 themore » 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. Finally, 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.« less

  16. Diversity dynamics in Nymphalidae butterflies: effect of phylogenetic uncertainty on diversification rate shift estimates.

    PubMed

    Peña, Carlos; Espeland, Marianne

    2015-01-01

    The species rich butterfly family Nymphalidae has been used to study evolutionary interactions between plants and insects. Theories of insect-hostplant dynamics predict accelerated diversification due to key innovations. In evolutionary biology, analysis of maximum credibility trees in the software MEDUSA (modelling evolutionary diversity using stepwise AIC) is a popular method for estimation of shifts in diversification rates. We investigated whether phylogenetic uncertainty can produce different results by extending the method across a random sample of trees from the posterior distribution of a Bayesian run. Using the MultiMEDUSA approach, we found that phylogenetic uncertainty greatly affects diversification rate estimates. Different trees produced diversification rates ranging from high values to almost zero for the same clade, and both significant rate increase and decrease in some clades. Only four out of 18 significant shifts found on the maximum clade credibility tree were consistent across most of the sampled trees. Among these, we found accelerated diversification for Ithomiini butterflies. We used the binary speciation and extinction model (BiSSE) and found that a hostplant shift to Solanaceae is correlated with increased net diversification rates in Ithomiini, congruent with the diffuse cospeciation hypothesis. Our results show that taking phylogenetic uncertainty into account when estimating net diversification rate shifts is of great importance, as very different results can be obtained when using the maximum clade credibility tree and other trees from the posterior distribution.

  17. Diversity Dynamics in Nymphalidae Butterflies: Effect of Phylogenetic Uncertainty on Diversification Rate Shift Estimates

    PubMed Central

    Peña, Carlos; Espeland, Marianne

    2015-01-01

    The species rich butterfly family Nymphalidae has been used to study evolutionary interactions between plants and insects. Theories of insect-hostplant dynamics predict accelerated diversification due to key innovations. In evolutionary biology, analysis of maximum credibility trees in the software MEDUSA (modelling evolutionary diversity using stepwise AIC) is a popular method for estimation of shifts in diversification rates. We investigated whether phylogenetic uncertainty can produce different results by extending the method across a random sample of trees from the posterior distribution of a Bayesian run. Using the MultiMEDUSA approach, we found that phylogenetic uncertainty greatly affects diversification rate estimates. Different trees produced diversification rates ranging from high values to almost zero for the same clade, and both significant rate increase and decrease in some clades. Only four out of 18 significant shifts found on the maximum clade credibility tree were consistent across most of the sampled trees. Among these, we found accelerated diversification for Ithomiini butterflies. We used the binary speciation and extinction model (BiSSE) and found that a hostplant shift to Solanaceae is correlated with increased net diversification rates in Ithomiini, congruent with the diffuse cospeciation hypothesis. Our results show that taking phylogenetic uncertainty into account when estimating net diversification rate shifts is of great importance, as very different results can be obtained when using the maximum clade credibility tree and other trees from the posterior distribution. PMID:25830910

  18. New Astrophysical Reaction Rate for the 12C(α, γ)16O Reaction

    NASA Astrophysics Data System (ADS)

    An, Zhen-Dong; Ma, Yu-Gang; Fan, Gong-Tao; Li, Yong-Jiang; Chen, Zhen-Peng; Sun, Ye-Ying

    2016-01-01

    A new astrophysical reaction rate for 12C(α, γ)16O has been evaluated on the basis of a global R-matrix fitting to the available experimental data. The reaction rates of 12C(α, γ)16O for stellar temperatures between 0.04 ≤ T9 ≤ 10 are provided in a tabular form and by an analytical fitting expression. At T9 = 0.2, the reaction rate is (7.83 ± 0.35) × 1015 cm3 mol-1 s-1, where stellar helium burning occurs.

  19. On reaction rate constants IO+NO, IO+CO

    NASA Astrophysics Data System (ADS)

    Larin, Igor; Spasskiy, Alexandr; Trofimova, Elen

    2013-04-01

    A method, allowing to define, whether an investigated chemical reaction in a gas phase or on a surface of a reactor for those cases when dependence of the reaction rate on concentration of reagents for heterogeneous and for homogeneous reaction are identical, has been suggested. The method has been used for investigation of reactions of IO with nitric oxide and carbon monoxide. Experiments have been run in the flow reactor with using a method of resonance fluorescence to record atoms of iodine. It has been proved that the reaction of radical IO with nitric oxide proceeds in the gas phase, whereas the reaction of radical IO with carbon monoxide proceeds on the surface of the reactor. It has been obtained that reaction rate constant of IO with nitrogen monoxide in the temperature range 298-353 K is kNO(T)=(1,01±0,2)•10^-11•exp((210±80)/T) cm3*molecule*s-1 and the same for reaction of IO with carbon monoxide is kCO(T)=(1,14±0,64)•10^-14•exp((612±41)/T) cm3*molecule*s-1.

  20. From cutting-edge pointwise cross-section to groupwise reaction rate: A primer

    NASA Astrophysics Data System (ADS)

    Sublet, Jean-Christophe; Fleming, Michael; Gilbert, Mark R.

    2017-09-01

    The nuclear research and development community has a history of using both integral and differential experiments to support accurate lattice-reactor, nuclear reactor criticality and shielding simulations, as well as verification and validation efforts of cross sections and emitted particle spectra. An important aspect to this type of analysis is the proper consideration of the contribution of the neutron spectrum in its entirety, with correct propagation of uncertainties and standard deviations derived from Monte Carlo simulations, to the local and total uncertainty in the simulated reactions rates (RRs), which usually only apply to one application at a time. This paper identifies deficiencies in the traditional treatment, and discusses correct handling of the RR uncertainty quantification and propagation, including details of the cross section components in the RR uncertainty estimates, which are verified for relevant applications. The methodology that rigorously captures the spectral shift and cross section contributions to the uncertainty in the RR are discussed with quantified examples that demonstrate the importance of the proper treatment of the spectrum profile and cross section contributions to the uncertainty in the RR and subsequent response functions. The recently developed inventory code FISPACT-II, when connected to the processed nuclear data libraries TENDL-2015, ENDF/B-VII.1, JENDL-4.0u or JEFF-3.2, forms an enhanced multi-physics platform providing a wide variety of advanced simulation methods for modelling activation, transmutation, burnup protocols and simulating radiation damage sources terms. The system has extended cutting-edge nuclear data forms, uncertainty quantification and propagation methods, which have been the subject of recent integral and differential, fission, fusion and accelerators validation efforts. The simulation system is used to accurately and predictively probe, understand and underpin a modern and sustainable understanding

  1. Space Shuttle Orbiter flight heating rate measurement sensitivity to thermal protection system uncertainties

    NASA Technical Reports Server (NTRS)

    Bradley, P. F.; Throckmorton, D. A.

    1981-01-01

    A study was completed to determine the sensitivity of computed convective heating rates to uncertainties in the thermal protection system thermal model. Those parameters considered were: density, thermal conductivity, and specific heat of both the reusable surface insulation and its coating; coating thickness and emittance; and temperature measurement uncertainty. The assessment used a modified version of the computer program to calculate heating rates from temperature time histories. The original version of the program solves the direct one dimensional heating problem and this modified version of The program is set up to solve the inverse problem. The modified program was used in thermocouple data reduction for shuttle flight data. Both nominal thermal models and altered thermal models were used to determine the necessity for accurate knowledge of thermal protection system's material thermal properties. For many thermal properties, the sensitivity (inaccuracies created in the calculation of convective heating rate by an altered property) was very low.

  2. 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.

  3. Generalized rate equation for single-substrate enzyme catalyzed reactions.

    PubMed

    Kargi, Fikret

    2009-04-24

    The most widely used rate expression for single-substrate enzyme catalyzed reactions, namely the Michaelis-Menten kinetics is based upon the assumption that enzyme concentration is in excess of the substrate in the medium and the rate is mainly limited by the substrate concentration according to saturation kinetics. However, this is only a special case and the actual rate expression varies depending on the initial enzyme/substrate ratio (E(0)/S(0)). When the substrate concentration exceeds the enzyme concentration the limitation is due to low enzyme concentration and the rate increases with the enzyme concentration according to saturation kinetics. The maximum rate is obtained when the initial concentrations of the enzyme and the substrate are equal. A generalized rate equation was developed in this study and special cases were discussed for enzyme catalyzed reactions.

  4. SIFT and FALP determinations of ionic reactions rate coefficients

    NASA Astrophysics Data System (ADS)

    Smith, D.; Adams, N. G.

    1990-06-01

    A brief review is presented of some recent results of studies of ionic reactions at thermal energies using the selected ion flow tube (SIFT) and the flowing afterglow/Langmuir probe (FALP) techniques in our laboratory. From the SIFT results, we summarise the recent data on positive ion-molecule reactions, much of which relate to the synthesis of interstellar molecules. Thus, for example, data are discussed relating to the reactions of some hydrocarbon ions in the series CnHm+, and phosphorus-bearing ions in the series PHn+, which can lead to interstellar hydrocarbon and phosphorus-bearing molecules. From the FALP results, we summarise the data obtained on the rate coefficients for dissociative recombination, highlighting the recent work on the determination of the products of some dissociative recombination reactions, and discuss recent results on studies of dissociative electron attachment reactions. Reference is also made to our earlier studies of ion-ion mutual neutralization.

  5. Inference of reaction rate parameters based on summary statistics from experiments

    DOE PAGES

    Khalil, Mohammad; Chowdhary, Kamaljit Singh; Safta, Cosmin; ...

    2016-10-15

    Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H2/O2-mechanism chain branching reaction H + O2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the given summary statistics, usingmore » Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto-ignition computations to illustrate

  6. Inference of reaction rate parameters based on summary statistics from experiments

    SciTech Connect

    Khalil, Mohammad; Chowdhary, Kamaljit Singh; Safta, Cosmin; Sargsyan, Khachik; Najm, Habib N.

    2016-10-15

    Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H2/O2-mechanism chain branching reaction H + O2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the given summary statistics, using Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto

  7. 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.

  8. 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.

  9. Uncertainty analysis of the Measured Performance Rating (MPR) method. Final report

    SciTech Connect

    Not Available

    1993-11-01

    A report was commissioned by the New York State Energy Research and Development Authority and the Electric Power Research Institute to evaluate the uncertainties in the energy monitoring method known as measured performance rating (MPR). The work is intended to help further development of the MPR system by quantitatively analyzing the uncertainties in estimates of the heat loss coefficients and heating system efficiencies. The analysis indicates that the MPR should detect as little as a 7 percent change in the heat loss coefficients and heating system efficiencies. The analysis indicate that the MPR should be able to detect as little as a 7 percent change in the heat loss coefficient at 95 percent confidence level. MPR appears sufficiently robust for characterizing common weatherization treatments; e.g., increasing attic insulation from R-7 to R-19 in a typical single-story, 1,100 sq. ft. house resulting in a 19 percent reduction in heat loss coefficient. Furnace efficiency uncertainties ranged up to three times those of the heat loss coefficients. Measurement uncertainties (at the 95 percent confidence level) were estimated to be from 1 to 5 percent for heat loss coefficients and 1.5 percent for a typical furnace efficiency. The analysis also shows a limitation in applying MPR to houses with heating ducts in slabs on grade and to those with very large thermal mass. Most of the uncertainties encountered in the study were due more to the methods of estimating the ``true`` heat loss coefficients, furnace efficiency, and furnace fuel consumption (by collecting fuel bills and simulating two actual houses) than to the MPR approach. These uncertainties in the true parameter values become evidence for arguments in favor of the need of empirical measures of heat loss coefficient and furnace efficiency, like the MPR method, rather than arguments against.

  10. Reaction rates between water and the Karl Fischer reagent.

    PubMed

    Cedergren, A

    1974-04-01

    Reaction rates between water and the Karl Fischer reagent have been determined by potentiometric measurement for various compositions of the Karl Fischer reagent. The study has been made with an iodine complex concentration of 0.3-1.2 mM and sulphur dioxide complex at 0.01-0.5M. The concentration of excess of pyridine had no measurable effect on the rate of the main reaction. The reaction was found to be first-order with respect to iodine complex, to sulphur dioxide complex, and to water. The rate constant was (1.2+/-0.2) x 10(3) 1(2). mole(-2). sec(-1). In an ordinary titration it is therefore essential to keep the sulphur dioxide concentration high for the reaction to go to completion within a reasonable time. The extent of side-reactions was found to be independent of the iodine concentration at low concentrations. The side-reactions increased somewhat with increasing sulphur dioxide pyridine concentrations and decreased to about 60% when the temperature was lowered from 24 degrees to 7 degrees.

  11. Uncertainties in corrosion rate measurements of fasteners exposed to treated wood at 100% relative humidity

    Treesearch

    Samuel L. Zelinka

    2007-01-01

    This paper evaluates the effect that uncertainties in measurements of time, weight, and surface area have on the determination of the corrosion rate of metal fasteners in contact with wood. Three different types of nails were driven into alkaline copper quaternary (ACQ)-treated wood and exposed to 26.7°C (80°C) at 100 % relative humidity environment for up to 1 year....

  12. The Role of Rating Curve Uncertainty in Real Time Flood Forecasting

    NASA Astrophysics Data System (ADS)

    Ocio, D.; Le Vine, N.; Westerberg, I.; Pappenberger, F.; Buytaert, W.

    2016-12-01

    Data assimilation (DA) techniques have been widely tested in flood forecasting, although their use in operational systems is mainly limited to a statistical error correction. The complexity of selecting a priori hypotheses about the nature of model and measurement errors can be behind this fact. Model error may result in large deviations between observed and predicted flows, but is difficult to quantify objectively. Measurement error is often used in DA to help represent the true discharge and to improve the forecast quality. It is possible to specify this error objectively, but this requires an analysis of the uncertainty in the underlying rating curve model.Recent advances in the definition of rating curve uncertainty, based on the available gaugings together with the results from hydraulic modelling, have opened new possibilities to establish an unbiased measurement error including both aleatory and epistemic uncertainties, instead of adopting a benchmark, albeit arbitrary, choice. We addressed this issue by constructing a comprehensive probabilistic framework where forcing data, model structure and observation uncertainties have all been considered to test the effect that the selection of the measurement error model may have on the performance of three common DA techniques: Autoregressive error correction, Ensemble Kalman Filter and Particle Filter. Results from gauging stations located in the flood-prone Oria catchment (Basque Country, northern Spain) serves to establish a general guidance for future applications. They point towards a modest impact on forecasting skills when the official rating curve is close to the median true flow, suggesting that a benchmark measurement error model can still be used operationally providing that the existing rating curve is properly defined.

  13. Reaction rates of atmospheric gases with lithium(silicon) alloy

    SciTech Connect

    Searcy, J Q; Reinhardt, F W

    1980-12-01

    Reaction rates of small pellets of Li(Si) alloy with atmospheric gases were studied as a prerequisite to specifying how this alloy should be handled during the production of thermal batteries. The results indicate that Li(Si) reacts with oxygen and nitrogen at ambient conditions too slowly to be of concern, but it reacts very rapidly with water vapor. Rate expressions and constants are developed that allow calculating the weight gain of Li(Si) after its reaction with water vapor, and calculated values are given for three water-vapor concentrations that typify those used in dry rooms where thermal batteries are produced.

  14. Rate coefficient for the OH radical reaction with HONO2 under UT/LS conditions

    NASA Astrophysics Data System (ADS)

    Winiberg, F.; Liu, Y.; Sander, S. P.

    2016-12-01

    Nitric acid (HONO2) is one of the most reactive nitrogen-containing species in our atmosphere and its oxidation chemistry plays an important role in controlling the O3 budget in the upper troposphere/lower stratosphere (UT/LS). The O3 budget in the UT/LS is largely controlled by the cycling of HOx (OH + HO2) and NOx (NO + NO2). The HONO2 reaction with OH is a net HOx radical sink and drives NOx/y partitioning chemistry by yielding NO3 radicals; therefore, understanding the rate coefficient of the OH + HONO2 reaction is critical for accurate prediction of the O3, HOx, and NOx budgets in the UT/LS. Previous studies have observed both negative temperature-dependent and pressure-dependent kinetics below, which results from the formation of a pre-reactive complex between OH and HONO2 ( 6 kcal mol-1). Currently, the JPL recommended uncertainty in kOH+HONO2 is 20% (±1σ) at STP, but under UT/LS conditions (low T and p), the uncertainty could increase to as much as ± 50%, which translates to 10 - 20% in model predictions of NOx/NOy partitioning. Previous groups have measured the concentration of HONO2 after or before the reaction cell but never in-situ, which could lead to greater uncertainties in the overall determination of the rate coefficient from heterogeneous uptake of the low volatility HONO2. Here, we present experimental results into the matrix of the temperature and pressure dependence of the OH + HONO2 rate coefficient. Specifically, our results represent the first determination of kOH+HONO2 using in-situ [HONO2] measurements coupled to a Light Induced Fluorescence (LIF) technique to probe OH radicals. Results and importance to UT/LS chemistry will be discussed. Copyright 2015, California Institute of Technology

  15. Dynamic rating curve assessment for hydrometric stations and computation of the associated uncertainties: Quality and station management indicators

    NASA Astrophysics Data System (ADS)

    Morlot, Thomas; Perret, Christian; Favre, Anne-Catherine; Jalbert, Jonathan

    2014-09-01

    A rating curve is used to indirectly estimate the discharge in rivers based on water level measurements. The discharge values obtained from a rating curve include uncertainties related to the direct stage-discharge measurements (gaugings) used to build the curves, the quality of fit of the curve to these measurements and the constant changes in the river bed morphology. Moreover, the uncertainty of discharges estimated from a rating curve increases with the “age” of the rating curve. The level of uncertainty at a given point in time is therefore particularly difficult to assess. A “dynamic” method has been developed to compute rating curves while calculating associated uncertainties, thus making it possible to regenerate streamflow data with uncertainty estimates. The method is based on historical gaugings at hydrometric stations. A rating curve is computed for each gauging and a model of the uncertainty is fitted for each of them. The model of uncertainty takes into account the uncertainties in the measurement of the water level, the quality of fit of the curve, the uncertainty of gaugings and the increase of the uncertainty of discharge estimates with the age of the rating curve computed with a variographic analysis (Jalbert et al., 2011). The presented dynamic method can answer important questions in the field of hydrometry such as “How many gaugings a year are required to produce streamflow data with an average uncertainty of X%?” and “When and in what range of water flow rates should these gaugings be carried out?”. The Rocherousse hydrometric station (France, Haute-Durance watershed, 946 [km2]) is used as an example throughout the paper. Others stations are used to illustrate certain points.

  16. An international comparison of physicians' judgments of outcome rates of cardiac procedures and attitudes toward risk, uncertainty, justifiability, and regret.

    PubMed

    Poses, R M; De Saintonge, D M; McClish, D K; Smith, W R; Huber, E C; Clemo, F L; Schmitt, B P; Alexander-Forti, D; Racht, E M; Colenda, C C; Centor, R M

    1998-01-01

    Compare U.K. and U.S. physicians' judgments of population probabilities of important outcomes of invasive cardiac procedures; and values held by them about risk, uncertainty, regret, and justifiability relevant to utilization of cardiac treatments. Cross-sectional study. University hospital and VA medical center in the United States; two teaching hospitals in the United Kingdom. 171 housestaff and attendings at U.S. teaching hospitals; 51 physician trainees and consultants at U.K. hospitals. Judgments of probabilities of severe complications and deaths due to Swan-Ganz catheterization, cardiac catheterization, percutaneous transluminal coronary angioplasty (PTCA), and coronary artery bypass grafting (CABG); judgments of malpractice risks for case vignettes; Nightingale's risk-aversion instrument; Gerrity's reaction-to-uncertainty instrument; questions about need to justify decisions; responses to case vignettes regarding regret. The U.S. physicians judged rates of two bad outcomes of cardiac procedures (complications due to cardiac catheterization; death due to CABG) to be significantly higher (p < or = 0.01) than did the U.K. physicians (U.S. medians, 5 and 3.5, respectively; U.K. medians 3 and 2). The median ratio of (risk of malpractice suit I error of omission)/(risk of suit I error of commission) judged by U.K. physicians, 3, was significantly (p=0.0006) higher than that judged by U.S. physicians, 1.5. The U.K. physicians were less often risk-seeking in the context of possible losses than the U.S. physicians (odds ratio for practicing in the U.K. as a predictor of risk seeking 0.3, p=0.003). The U.K. physicians had significantly more discomfort with uncertainty than did the U.S. physicians, as reflected by higher scores on the stress scale (U.K. median 48, U.S. 42, p=0.0001) and the reluctance-to-disclose-uncertainty scale (U.K. 40, U.S. 37, p < 0.0001) of the Gerrity instrument. There was no clear international difference in perceived need to justify

  17. 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.

  18. 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.

  19. 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.

  20. Reaction rates of graphite with ozone measured by etch decoration

    NASA Technical Reports Server (NTRS)

    Hennig, G. R.; Montet, G. L.

    1968-01-01

    Etch-decoration technique of detecting vacancies in graphite has been used to determine the reaction rates of graphite with ozone in the directions parallel and perpendicular to the layer planes. It consists essentially of peeling single atom layers off graphite crystals without affecting the remainder of the crystal.

  1. 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.

  2. Renormalized reaction and relaxation rates for harmonic oscillator model

    NASA Astrophysics Data System (ADS)

    Gorbachev, Yuriy E.

    2017-07-01

    The thermal dissociation process is considered within the method of solving the kinetic equations for spatially inhomogeneous reactive gas mixtures developed in the previous papers. For harmonic oscillator model explicit expressions for reaction and relaxation rates in the renormalized form are derived.

  3. Rates of membrane-associated reactions: reduction of dimensionality revisited

    PubMed Central

    1986-01-01

    The hypothesis that reactions associated with intracellular membranes enjoy a kinetic advantage from a reduced dimensionality for diffusion is inconsistent with available data on lateral diffusion rates, membrane-substrate affinities, and endogenous concentrations of enzymes and their aqueous substrates. PMID:3001105

  4. Noise slows the rate of Michaelis-Menten reactions.

    PubMed

    Van Dyken, J David

    2017-10-07

    Microscopic randomness and the small volumes of living cells combine to generate random fluctuations in molecule concentrations called "noise". Here I investigate the effect of noise on biochemical reactions obeying Michaelis-Menten kinetics, concluding that substrate noise causes these reactions to slow. I derive a general expression for the time evolution of the joint probability density of chemical species in arbitrarily connected networks of non-linear chemical reactions in small volumes. This equation is a generalization of the chemical master equation (CME), a common tool for investigating stochastic chemical kinetics, extended to reaction networks occurring in small volumes, such as living cells. I apply this equation to a generalized Michaelis-Menten reaction in an open system, deriving the following general result: 〈p〉≤p¯ and 〈s〉≥s¯, where s¯ and p¯ denote the deterministic steady-state concentration of reactant and product species, respectively, and 〈s〉 and 〈p〉 denote the steady-state ensemble average over independent realizations of a stochastic reaction. Under biologically realistic conditions, namely when substrate is degraded or diluted by cell division, 〈p〉≤p¯. Consequently, noise slows the rate of in vivo Michaelis-Menten reactions. These predictions are validated by extensive stochastic simulations using Gillespie's exact stochastic simulation algorithm. I specify the conditions under which these effects occur and when they vanish, therefore reconciling discrepancies among previous theoretical investigations of stochastic biochemical reactions. Stochastic slowdown of reaction flux caused by molecular noise in living cells may have functional consequences, which the present theory may be used to quantify. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Sensitivity of the photolysis rate to the uncertainties in spectral solar irradiance variability

    NASA Astrophysics Data System (ADS)

    Sukhodolov, Timofei; Rozanov, Eugene; Bais, Alkiviadis; Tourpali, Kleareti; Shapiro, Alexander; Telford, Paul; Peter, Thomas; Schmutz, Werner

    2014-05-01

    The state of the stratospheric ozone layer and temperature structure are mostly maintained by the photolytical processes. Therefore, the uncertainties in the magnitude and spectral composition of the spectral solar irradiance (SSI) evolution during the declining phase of 23rd solar cycle have substantial implications for the modeling of the middle atmosphere evolution, leading not only to a pronounced differences in the heating rates but also affecting photolysis rates. To estimate the role of SSI uncertainties we have compared the most important photolysis rates (O2, O3, and NO2) calculated with the reference radiation code libRadtran using SSI for June 2004 and February 2009 obtained from two models (NRL, COSI) and one observation data set based on SORCE observations. We found that below 40 km changes in the ozone and oxygen photolysis can reach several tenths of % caused by the changes of the SSI in the Harley and Huggins bands for ozone and several % for oxygen caused by the changes of the SSI in the Herzberg continuum and Schumann-Runge bands. For the SORCE data set these changes are 2-4 times higher. We have also evaluated the ability of the several photolysis rates calculation methods widely used in atmospheric models to reproduce the absolute values of the photolysis rates and their response to the implied SSI changes. With some remarks all schemes show good results in the middle stratosphere compare to libRadtran. However, in the troposphere and mesosphere there are more noticeable differences.

  6. Absolute rate constant for the reaction of Cl(/sup 2/P) with CINO

    SciTech Connect

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

    1987-09-24

    The room temperature rate constant for the reaction Cl + CINO yields Cl/sub 2/ + NO has been measured by the method of discharge flow mass spectrometry. The rate constant was determined from the decay of CINO in the presence of an excess of Cl atoms at a total pressure of 1 Torr. The rate constant obtained was (7.6 +/- 0.8) X 10/sup -11/ cm/sup 3/ s/sup -1/. This result is compared with previous determinations, the values of which ranged by more than an order of magnitude and all of which depended on knowledge of the absolute concentration of CINO. The authors suggest that the lack of agreement is attributable principally to uncertainties in (CINO) resulting from absorption of this reactive species on glass and metal surfaces. Our result does not depend directly on (CINO) and supports the highest values published for this rate constant.

  7. MERGERS IN {Lambda}CDM: UNCERTAINTIES IN THEORETICAL PREDICTIONS AND INTERPRETATIONS OF THE MERGER RATE

    SciTech Connect

    Hopkins, Philip F.; Bundy, Kevin; Wetzel, Andrew; Ma, Chung-Pei; Croton, Darren; Khochfar, Sadegh; Hernquist, Lars; Genel, Shy; Van den Bosch, Frank; Somerville, Rachel S.; Keres, Dusan; Stewart, Kyle; Younger, Joshua D.

    2010-12-01

    Different theoretical methodologies lead to order-of-magnitude variations in predicted galaxy-galaxy merger rates. We examine how this arises and quantify the dominant uncertainties. Modeling of dark matter and galaxy inspiral/merger times contribute factor of {approx}2 uncertainties. Different estimates of the halo-halo merger rate, the subhalo 'destruction' rate, and the halo merger rate with some dynamical friction time delay for galaxy-galaxy mergers, agree to within this factor of {approx}2, provided proper care is taken to define mergers consistently. There are some caveats: if halo/subhalo masses are not appropriately defined the major-merger rate can be dramatically suppressed, and in models with 'orphan' galaxies and under-resolved subhalos the merger timescale can be severely over-estimated. The dominant differences in galaxy-galaxy merger rates between models owe to the treatment of the baryonic physics. Cosmological hydrodynamic simulations without strong feedback and some older semi-analytic models (SAMs), with known discrepancies in mass functions, can be biased by large factors ({approx}5) in predicted merger rates. However, provided that models yield a reasonable match to the total galaxy mass function, the differences in properties of central galaxies are sufficiently small to alone contribute small (factor of {approx}1.5) additional systematics to merger rate predictions. But variations in the baryonic physics of satellite galaxies in models can also have a dramatic effect on merger rates. The well-known problem of satellite 'over-quenching' in most current SAMs-whereby SAM satellite populations are too efficiently stripped of their gas-could lead to order-of-magnitude under-estimates of merger rates for low-mass, gas-rich galaxies. Models in which the masses of satellites are fixed by observations (or SAMs adjusted to resolve this 'over-quenching') tend to predict higher merger rates, but with factor of {approx}2 uncertainties stemming from the

  8. Control of serpentinisation rate by reaction-induced cracking

    NASA Astrophysics Data System (ADS)

    Malvoisin, Benjamin; Brantut, Nicolas; Kaczmarek, Mary-Alix

    2017-10-01

    Serpentinisation of mantle rocks requires the generation and maintenance of transport pathways for water. The solid volume increase during serpentinisation can lead to stress build-up and trigger cracking, which ease fluid penetration into the rock. The quantitative effect of this reaction-induced cracking mechanism on reactive surface generation is poorly constrained, thus hampering our ability to predict serpentinisation rate in geological environments. Here we use a combined approach with numerical modelling and observations in natural samples to provide estimates of serpentinisation rate at mid-ocean ridges. We develop a micromechanical model to quantify the propagation of serpentinisation-induced cracks in olivine. The maximum crystallisation pressure deduced from thermodynamic calculations reaches several hundreds of megapascals but does not necessary lead to crack propagation if the olivine grain is subjected to high compressive stresses. The micromechanical model is then coupled to a simple geometrical model to predict reactive surface area formation during grain splitting, and thus bulk reaction rate. Our model reproduces quantitatively experimental kinetic data and the typical mesh texture formed during serpentinisation. We also compare the model results with olivine grain size distribution data obtained on natural serpentinised peridotites from the Marum ophiolite and the Papuan ultramafic belt (Papua New Guinea). The natural serpentinised peridotites show an increase of the number of olivine grains for a decrease of the mean grain size by one order of magnitude as reaction progresses from 5 to 40%. These results are in agreement with our model predictions, suggesting that reaction-induced cracking controls the serpentinisation rate. We use our model to estimate that, at mid-ocean ridges, serpentinisation occurs up to 12 km depth and reaction-induced cracking reduces the characteristic time of serpentinisation by one order of magnitude, down to values

  9. 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.

  10. Abundances in Astrophysical Environments: Reaction Network Simulations with Reaction Rates from Many-nucleon Modeling

    NASA Astrophysics Data System (ADS)

    Amason, Charlee; Dreyfuss, Alison; Launey, Kristina; Draayer, Jerry

    2017-01-01

    We use the ab initio (first-principle) symmetry-adapted no-core shell model (SA-NCSM) to calculate reaction rates of significance to type I X-ray burst nucleosynthesis. We consider the 18O(p,γ)19F reaction, which may influence the production of fluorine, as well as the 16O(α,γ)20Ne reaction, which is key to understanding the production of heavier elements in the universe. Results are compared to those obtained in the no-core sympletic shell model (NCSpM) with a schematic interaction. We discuss how these reaction rates affect the relevant elemental abundances. We thank the NSF for supporting this work through the REU Site in Physics & Astronomy (NSF grant #1560212) at Louisiana State University. This work was also supported by the U.S. NSF (OCI-0904874, ACI -1516338) and the U.S. DOE (DE-SC0005248).

  11. Quantification of rate constants for successive enzymatic reactions with DNP hyperpolarized MR.

    PubMed

    Allouche-Arnon, Hyla; Hovav, Yonatan; Friesen-Waldner, Lanette; Sosna, Jacob; Moshe Gomori, J; Vega, Shimon; Katz-Brull, Rachel

    2014-06-01

    A kinetic model is provided to obtain reaction rate constants in successive enzymatic reactions that are monitored using NMR spectroscopy and hyperpolarized substrates. The model was applied for simulation and analysis of the successive oxidation of choline to betaine aldehyde, and further to betaine, by the enzyme choline oxidase. This enzymatic reaction was investigated under two different sets of conditions: two different choline molecular probes were used, [1,1,2,2-D4 , 1-(13) C]choline chloride and [1,1,2,2-D4 , 2-(13) C]choline chloride, in different MR systems (clinical scanner and high-resolution spectrometer), as well as in different reactors and reaction volumes (4.8 and 0.7 mL). The kinetic analysis according to the model yielded similar results in both set-ups, supporting the robustness of the model. This was achieved despite the complex and negating influences of reaction kinetics and polarization decay, and in the presence of uncontrolled mixing characteristics, which may introduce uncertainties in both effective timing and effective pulses. The ability to quantify rate constants using hyperpolarized MR in the first seconds of consecutive enzyme activity is important for further development of the utilization of dynamic nuclear polarization-MR for biological determinations.

  12. Temperature Dependence of the Rate Constants of Charge Recombination Reactions in Bacterial Reaction Centers

    NASA Astrophysics Data System (ADS)

    Thuy, T. T.; Yen, V. T. H.; Thao, T. T.; Viet, Nguyen Ai

    The bacterial reaction center couples light-induced electron transfer via a tightly bound ubiquinone (QA) to a mobile ubiquinone (QB). Based on the electron transfer theory by Marcus, we have investigated the rate of charge recombination reactions from Rhodopseudomonas viridis and Rhodobacter sphaeroides, by mean of finding an approximation formula. The results obtained are verified for not only at high and low temperature as the previous works but also at the medium temperature range.

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

    SciTech Connect

    LESZCZYNSKI, FRANCISCO

    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.

  14. Reaction rate constant for radiative association of CF+

    NASA Astrophysics Data System (ADS)

    Ã-ström, Jonatan; Bezrukov, Dmitry S.; Nyman, Gunnar; Gustafsson, Magnus

    2016-01-01

    Reaction rate constants and cross sections are computed for the radiative association of carbon cations (C+) and fluorine atoms (F) in their ground states. We consider reactions through the electronic transition 11Π → X1Σ+ and rovibrational transitions on the X1Σ+ and a3Π potentials. Semiclassical and classical methods are used for the direct contribution and Breit-Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius-Kooij formula in five temperature intervals with a relative difference of <3%. The fit parameters will be added to the online database KIDA. For a temperature of 10-250 K, the rate constant is about 10-21 cm3 s-1, rising toward 10-16 cm3 s-1 for a temperature of 30 000 K.

  15. The temperature-dependence of elementary reaction rates: beyond Arrhenius.

    PubMed

    Smith, Ian W M

    2008-04-01

    The rates of chemical reactions and the dependence of their rate constants on temperature are of central importance in chemistry. Advances in the temperature-range and accuracy of kinetic measurements, principally inspired by the need to provide data for models of combustion, atmospheric, and astrophysical chemistry, show up the inadequacy of the venerable Arrhenius equation--at least, over wide ranges of temperature. This critical review will address the question of how to reach an understanding of the factors that control the rates of 'non-Arrhenius' reactions. It makes use of a number of recent kinetic measurements and shows how developments in advanced forms of transition state theory provide satisfactory explanations of complex kinetic behaviour (72 references).

  16. Nuclear fusion reaction rates for strongly coupled ionic mixtures

    SciTech Connect

    Chugunov, A. I.; DeWitt, H. E.

    2009-07-15

    We analyze the effect of plasma screening on nuclear reaction rates in dense matter composed of atomic nuclei of one or two types. We perform semiclassical calculations of the Coulomb barrier penetrability taking into account a radial mean-field potential of plasma ions. The mean-field potential is extracted from the results of extensive Monte Carlo calculations of radial pair distribution functions of ions in binary ionic mixtures. We calculate the reaction rates in a wide range of plasma parameters and approximate these rates by an analytical expression that is expected to be applicable to multicomponent ion mixtures. Also, we analyze Gamow-peak energies of reacting ions in various nuclear burning regimes. For illustration, we study nuclear burning in {sup 12}C-{sup 16}O mixtures.

  17. 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.

  18. 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.

  19. 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.

  20. Reevaluation of thermonuclear reaction rate of 50Fe(p, 𝜸)51Co

    NASA Astrophysics Data System (ADS)

    Zhang, Li-Ping; He, Jian-Jun; Chai, Wan-Dong; Hou, Su-Qing; Zhang, Li-Yong

    2016-11-01

    The thermonuclear rate of the 50Fe(p, 𝜸)51Co reaction in the Type I X-ray bursts (XRBs) temperature range has been reevaluated based on a recent precise mass measurement at CSRe Lanzhou, where the proton separation energy Sp = 142±77 keV has been determined firstly for the 51Co nucleus. Comparing to the previous theoretical predictions, the experimental Sp value has much smaller uncertainty. Based on the nuclear shell model and mirror nuclear structure information, we have calculated two sets of thermonuclear rates for the 50Fe(p, 𝜸)51Co reaction by utilizing the experimental Sp value. It shows that the statistical-model calculations are not ideally applicable for this reaction primarily because of the low density of low-lying excited states in 51Co. In this work, we recommend that a set of new reaction rates based on the mirror structure of 51Cr should be incorporated in future astrophysical network calculations. Supported by Natural Science Foundation of Inner Mongolia Autonomous Region of China (2013MS0916) and National Natural Science Foundation of China (11490562, 11405228)

  1. Comparison of DSMC reaction models with QCT reaction rates for nitrogen

    NASA Astrophysics Data System (ADS)

    Wysong, Ingrid J.; Gimelshein, Sergey F.

    2016-11-01

    Four empirical models of chemical reactions extensively used in the direct simulation Monte Carlo method in the past are analyzed via comparison of temperature and vibrational level dependent equilibrium and non-equilibrium reaction rates with available classical trajectory and direct molecular simulations for nitrogen dissociation. The considered models are total collision energy, quantum kinetic, vibration-dissociation favoring, and weak vibrational bias. The weak vibrational bias model was found to provide good agreement with benchmark vibrationally-specific dissociation rates, while significant differences were observed for the others.

  2. The role of rating curve uncertainty in real-time flood forecasting

    NASA Astrophysics Data System (ADS)

    Ocio, David; Le Vine, Nataliya; Westerberg, Ida; Pappenberger, Florian; Buytaert, Wouter

    2017-05-01

    Data assimilation has been widely tested for flood forecasting, although its use in operational systems is mainly limited to a simple statistical error correction. This can be due to the complexity involved in making more advanced formal assumptions about the nature of the model and measurement errors. Recent advances in the definition of rating curve uncertainty allow estimating a flow measurement error that includes both aleatory and epistemic uncertainties more explicitly and rigorously than in the current practice. The aim of this study is to understand the effect such a more rigorous definition of the flow measurement error has on real-time data assimilation and forecasting. This study, therefore, develops a comprehensive probabilistic framework that considers the uncertainty in model forcing data, model structure, and flow observations. Three common data assimilation techniques are evaluated: (1) Autoregressive error correction, (2) Ensemble Kalman Filter, and (3) Regularized Particle Filter, and applied to two locations in the flood-prone Oria catchment in the Basque Country, northern Spain. The results show that, although there is a better match between the uncertain forecasted and uncertain true flows, there is a low sensitivity for the threshold exceedances used to issue flood warnings. This suggests that a standard flow measurement error model, with a spread set to a fixed flow fraction, represents a reasonable trade-off between complexity and realism. Standard models are therefore recommended for operational flood forecasting for sites with well-defined stage-discharge curves that are based on a large range of flow observations.

  3. Rate of reaction of OH with CS/sub 2/

    SciTech Connect

    Wine, P.H.; Shah, R.C.; Ravishankara, A.R.

    1980-10-02

    The flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction OH + CS/sub 2/ ..-->.. products (k/sub 1/) over the temperature range 251-363 K. Complicating secondary reactions involving CS/sub 2/ photofragments were eliminated only when the photoflash was filtered by 10 torr cm of CS/sub 2/ and SF/sub 6/ was used as the buffer gas. The rate constant was found to be much slower than previous measurements indicated. Based on our experiments, upper limits for k/sub 1/ (in units of 10/sup -15/ cm/sup 3/ molecule/sup -1/s/sup -1/) are 9.9 at 251 K, 1.5 at 297 K, and 1.6 at 363 K. Our results suggest that the title reaction is unimportant as a source for COS in the atmosphere.

  4. Rate constants for reactions of perhaloalkylperoxyl radicals with alkenes

    SciTech Connect

    Alfassi, Z.B.; Huie, R.E.; Neta, P. )

    1993-07-01

    Trichloro- and tribromomethylperoxyl radicals were produced by radiolytic reduction of CCl[sub 4] and CBr[sub 4] in various aerated solvents. Rate constants for the reactions of these radicals with unsaturated organic compounds were determined in methanol solutions by competition kinetics, using mainly chloropromazine as a reference. The rate constants were in the range k = 10[sup 4]-10[sup 7] L mol[sup [minus]1] s[sup [minus]1], and a good correlation was obtained between log k and the Taft substituent constants [sigma]*. Steric effects were also noticeable in some cases. The reactivities of the radicals were in the order CBr[sub 3]O[sub 2][center dot] < CCl[sub 3]O[sub 2][center dot] < C[sub 4]F[sub 9]O[sub 2][center dot], which is in contrast with the order observed in electron-transfer reactions. The rate constants for reaction of CCl[sub 3]O[sub 2][center dot] with 2,3-dimethyl-2-butene (DMB) and cyclohexene (CH) were studied in 12 solvents. In all cases DMB is considerably more reactive than CH, indicating that at least in the case of DMB the reaction is predominantly via addition. The rate constant for addition of CCl[sub 3]O[sub 2][center dot] to DMB varies by a factor of 7 in the different solvents. No correlation was found between these rate constants and thermodynamic or polarity parameters of the solvents, although viscosity appears to have an effect. 19 refs., 2 figs., 2 tabs.

  5. Reaction rates from pressure-gauge measurements in reacting explosives

    SciTech Connect

    Ginsberg, M.J.; Anderson, A.B.; Wackerle, J.

    1981-01-01

    The proper hydrodynamic data and an equation of state are sufficient to describe quantitatively the reaction rates of explosives during the shock-to-detonation transition. Manganin pressure gauges embedded in the reacting explosive have provided these data for the explosives PETN, PBX 9404, TATB, and TNT. Once a pressure-field history has been assembled from individual pressure histories at different depths in the explosive, the conservation equations can be applied in a Lagrangian analysis of the data. The combination of a reactant-product equation of state with this analysis then allows the calculation of the extent of reaction and reaction rate. Successful correlation of the calculated reaction rate values with other thermodynamic variables, such as pressure or temperature, allows formulation of a rate law and the prediction of initiation behavior under circumstances quite different from the experiments that led to the rate law. The best dynamic piezoresistive pressure gauge for most applications would have a substantial output voltage and present negligible disturbance to the flow. In explosives, however, requirements for survival in the extreme temperature and pressure environment encountered by the gauge dictate compromise. Low electrical resistance (approx. 20 m..cap omega..) helps to minimize shunt conductivity failures, but this drastically reduces output and demands that much attention be given to reducingnoise. Although relatively thick insulation perturbs the flow to some extent, survivability requirements dictate its use. Pressure measurements in reactive flow can now be made routinely with gauges that successfully produce data leading to a description of the flow and a powerful predictive capability.

  6. Differences in rating curve and hydrograph uncertainty due to streamflow dynamics and number of discharge measurements

    NASA Astrophysics Data System (ADS)

    Rosenstand Poulsen, Jane; Bering Ovesen, Niels; Larsen, Søren Erik; Tornbjerg, Henrik

    2015-04-01

    The uncertainty related to the use of rating curves for hydrograph estimation is strongly affected if changes in cross-sectional geometry or friction properties occur, especially if the changes are abrupt. In lowland moderately sized streams in temperate regions, such flow changes are often associated with seasonal weed growth. The gradual increase in channel bed roughness caused by weed growth is commonly accounted for by a likewise gradual shift of the rating curve according to monthly discharge measurements. However, this measurement approach is sensitive to abrupt changes in flow, which occur for instance in dynamic streams exhibiting a large difference between maximum and minimum flow or during high summer flows or winter flooding. Hence, the purpose of this study is to investigate the role that dynamic versus stable streams play in terms of uncertainty of establishing rating curves and calculating hydrographs with the traditional stage-discharge approach. Such an analysis is highly valuable in terms of addressing the possibility of adapting hydrograph estimation procedures to the specific streamflow dynamics, thereby quantifying and potentially lowering the uncertainty of hydrograph estimates. Based on results from the Danish national rainfall-runoff model, ratios between yearly median maximum and median minimum stream discharge were calculated for 15 km2 sub-catchments for the entire country. Based on these values, ten gauging stations were selected, located to cover the range of flow regimes represented by the calculated max/min discharge ratios. The selected gauging stations were all stations that had at least three consecutive years with historical data series where direct stream discharge had been measured twenty or more times each year. Based on these data series, new sub-series were created by continuously thinning out the number of discharge measurements. Then, for each of these constructed data series a rating curve and a hydrograph were established

  7. Enhancement of thermonuclear reaction rates in extremely dense stellar plasmas

    NASA Astrophysics Data System (ADS)

    Itoh, Naoki; Kuwashima, Fumiyoshi; Munakata, Hiroharu

    1990-10-01

    The enhancement factor of the thermonuclear reaction rates is calculated for the extremely dense stellar plasmas in the liquid phase where the condition 3Gamma/tau less than or equal to 1.6 is not necessarily imposed. Here the parameter 3Gamma/tau corresponds to the ratio of the classical turning point radius at the Gamow peak and the mean interionic distance in the case of the pure Coulomb potential. Direct double integration is carried out to obtain the thermonuclear reaction rates. The result is presented in the form of an analytic fitting formula to facilitate applications. The present fitting formula is valid for 3Gamma/tau = 0-5.4. The present calculation is intended to serve as the best available one for the case that ions are in the semiquantum regime.

  8. 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.

  9. Rate constant and reaction channels for the reaction of atomic nitrogen with the ethyl radical

    SciTech Connect

    Stief, L.J.; Nesbitt, F.L.; Payne, W.A. ); Kuo, S.C.; Tao, W.; Klemm, R.B. )

    1995-04-01

    The absolute rate constant and primary reaction products have been determined at [ital T]=298 K for the atom--radical reaction N([sup 4][ital S])+C[sub 2]H[sub 5] in a discharge flow system with collision-free sampling to a mass spectrometer. The rate constant measurements employed low energy electron impact ionization while the product study used dispersed synchrotron radiation as the photoionization source. The rate constant was determined under pseudo-first-order conditions by monitoring the decay of C[sub 2]H[sub 5] or C[sub 2]D[sub 5] as a function of time in the presence of excess N atoms. The result is [ital k]=(1.1[plus minus]0.3)[times]10[sup [minus]10] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1]. For the reaction product experiments using photoionization mass spectrometry, products observed at 114 nm (10.9 eV) were CD[sub 3], D[sub 2]CN and C[sub 2]D[sub 4] for the N+C[sub 2]D[sub 5] reaction. The product identification is based on the unambiguous combination of product [ital m]/[ital z] values, the shift of the [ital m]/[ital z] peaks observed for the N+C[sub 2]D[sub 5] reaction products with respect to the N+C[sub 2]H[sub 5] reaction products and the photoionization threshold measured for the major products. The observed products are consistent with the occurrence of the reaction channels D[sub 2]CN+CD[sub 3](2a) and C[sub 2]D[sub 4]+ND(2c). Formation of C[sub 2]D[sub 4] product via channel (2c) accounts for approximately 65% of the C[sub 2]D[sub 5] reacted. Most, if not all, of the remaining 35% is probably accounted for by channel (2a). These rate constant and product results are compared with those for the N+CH[sub 3] reaction as well as other atom+C[sub 2]H[sub 5] reactions. The role of the N+C[sub 2]H[sub 5] reaction in the formation of HCN in the atmospheres of Titan and Neptune is briefly considered. (Abstract Truncated)

  10. Reaction Rate Measurements at the National Criticality Experiments Research Center

    NASA Astrophysics Data System (ADS)

    Bredeweg, T. A.; Bounds, J. A.; Brooks, G. H., Jr.; Favorite, J. A.; Goda, J. M.; Hayes, D. K.; Jackman, K. R.; Little, R. C.; Macinnes, M. R.; Myers, W. L.; Oldham, W. J.; Rundberg, R. S.; Sanchez, R. G.; Schake, A. R.; White, M. C.; Wilkerson, C. W., Jr.

    2014-09-01

    With the resumption of regular operations of the Los Alamos Critical Assemblies at the National Criticality Experiments Research Center (NCERC), located at the Nevada National Security Site, we have embarked upon a series of campaigns to restore the capability to perform integral reaction rate and fission product yield measurements using historical radiochemical methods. This talk will present an overview of the current and future experimental plans, including results from our experimental campaigns on the Comet/Zeus and Flattop assemblies.

  11. 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.

  12. 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.

  13. Application of semiclassical methods to reaction rate theory

    SciTech Connect

    Hernandez, Rigoberto

    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.

  14. Reaction rate calibration techniques at ZPPR for /sup 239/Pu fission, /sup 235/U fission, /sup 238/U fission, and /sup 238/U capture

    SciTech Connect

    Brumbach, S.B.; Maddison, D.W.

    1982-06-10

    Reaction-rate calibration techniques used at ZPPR are described for /sup 239/Pu fission, /sup 235/U fission, /sup 238/U fission and /sup 238/U capture. In addition to these absolute reaction rates, calibration techniques are described for fission-rate ratios and the ratio of /sup 238/U capture to /sup 239/U capture to /sup 239/Pu fission. Uncertainty estimates are presented for all calibrations. Intercomparison measurements are reported which support the validity of the calibration techniques and their estimated uncertainties.

  15. Absolute determination of the Na22(p,γ)Mg23 reaction rate in novae

    NASA Astrophysics Data System (ADS)

    Sallaska, A. L.; Wrede, C.; García, A.; Storm, D. W.; Brown, T. A. D.; Ruiz, C.; Snover, K. A.; Ottewell, D. F.; Buchmann, L.; Vockenhuber, C.; Hutcheon, D. A.; Caggiano, J. A.; José, J.

    2011-03-01

    Gamma-ray telescopes in orbit around the earth are searching for evidence of the elusive radionuclide Na22 produced in novae. Previously published uncertainties in the dominant destructive reaction, Na22(p,γ)Mg23, indicated new measurements in the proton energy range of 150 to 300 keV were needed to constrain predictions. We have measured the resonance strengths, energies, and branches directly and absolutely by using protons from the University of Washington accelerator with a specially designed beam line, which included beam rastering and cold vacuum protection of the Na22 implanted targets. The targets, fabricated at TRIUMF-ISAC, displayed minimal degradation over a ~20 C bombardment as a result of protective layers. We avoided the need to know the absolute stopping power, and hence the target composition, by extracting resonance strengths from excitation functions integrated over proton energy. Our measurements revealed that resonance strengths for Ep=213, 288, 454, and 610 keV are stronger by factors of 2.4-3.2 than previously reported. Upper limits have been placed on proposed resonances at 198, 209, and 232 keV. These substantially reduce the uncertainty in the reaction rate. We have re-evaluated the Na22(p,γ) reaction rate, and our measurements indicate the resonance at 213 keV makes the most significant contribution to Na22 destruction in novae. Hydrodynamic simulations including our rate indicate that the expected abundance of Na22 ejecta from a classical nova is reduced by factors between 1.5 and 2, depending on the mass of the white-dwarf star hosting the nova explosion.

  16. Network estimation of noise in GPS data with implications for uncertainty in intraplate strain-rate

    NASA Astrophysics Data System (ADS)

    Dmitrieva, K.; Segall, P.

    2012-12-01

    Geological evidence suggests that large earthquakes strike the New Madrid Seismic Zone (NMSZ) on average every 500 years. However, continuous GPS observations spanning over a decade show little or possibly no strain rate in this region. The uncertainty in geodetically derived strain-rates is dominated by time-dependent noise in GPS time series - typically modeled as power-law noise, including random walk and flicker noise. Hence a good understanding of GPS noise is essential for quantifying strain rates and their uncertainties in continental interiors. We develop a network noise estimator that is able to determine the time-dependent noise properties of GPS time series in regions of low deformation rates. Specifically, we investigate spatial correlations of different components of the data. In our filtering approach we decompose the signal within a stable plate interior into a spatially coherent plate rotation (possibly plus post-glacial rebound) and noise. Currently the noise is a sum of flicker, random walk, and white noise. Assuming that there are no other signals in stable parts of the plate, we process all stations simultaneously use a Kalman filter to estimate the different components of the data. We use maximum likelihood estimation (MLE) to solve for the best fitting variance parameters in the noise model. Preliminary work using synthetic data shows that our method can recover even low levels of time-dependent noises in the data. We compare our network method with commonly used "baseline fit" MLE techniques by running both methods on sets of synthetic data with constant white and flicker noise, but varying random walk variance. Each method can determine flicker noise and white noise values well; however, the baseline fit fails to detect random walk if its magnitude is significantly lower than flicker noise. For example, for flicker noise of 2 mm/yr^0.25 and random walk of 0.38 mm/yr^0.5, the baseline fit finds no random walk, and yet our network approach

  17. Temperature Dependent Rate Coefficients for the OH + Pinonaldehyde Reaction

    NASA Astrophysics Data System (ADS)

    Davis, M. E.; Talukdar, R.; Notte, G.; Ellison, G. B.; Ravishankara, A. R.; Burkholder, J. B.

    2005-12-01

    The biogenic emission of monoterpenes is an important source of volatile organic compounds (VOCs) to the atmosphere, approximately 10% of the biogenic hydrocarbons emitted yearly. The oxidation of alpha-pinene, the most abundant monoterpene in the atmosphere, by OH leads to the formation of pinonaldehyde (3-acetyl-2,2-dimethyl-cyclobutyl-ethanal) as a major oxidation product formed in yields > 50%. The atmospheric oxidation of pinonaldehyde will impact radical cycling, ozone formation and air quality on a regional scale. Previous laboratory studies of the OH + pinonaldehyde rate coefficient have used relative rate methods and were limited to room temperature. The reported rate coefficients are in poor agreement with values ranging from 4.0 to 9.1 × 10-11 cm#3 molecule-1 s-1. In this study we have measured absolute rate coefficients to resolve these discrepancies and have extended the measurements to include the temperature dependence. The rate coefficient for the gas phase reaction of OH with pinonaldehyde was measured over the temperature range 297 to 374 K and between 55 and 96 Torr under pseudo first order conditions in OH. Laser-induced fluorescence (LIF) was used to monitor the OH radical which was produced by pulsed laser photolysis. The pinonaldehyde concentration was determined in situ using Fourier transform infrared (FTIR) and UV (185 nm) absorption spectroscopy. The rate coefficient for the OH + pinonaldehyde reaction will be presented. Our results will be compared with previous rate coefficient measurements and the discrepancies and the atmospheric implications of these measurements will be discussed.

  18. Determination of the (24)Mg(p,gamma)(25)Al reaction rate at low stellar temperatures

    NASA Astrophysics Data System (ADS)

    Powell, Denise Catherine

    Recent observations of isotopic abundances in the atmospheres of M13 red giant branch stars show an anticorrelation between Al and 24Mg abundances. These correlations are thought to be the result of deep mixing of material from the surface of the star into regions where the temperature is high enough to allow proton captures to take place. Production of Al and destruction of 24Mg depend on the 24Mg( p, γ)25Al reaction rate at stellar temperatures T9 ~ 0.04 (where T9 denotes temperature in units of 109 K). However, the commonly used rate is too low to account for the observations within the present mixing models. There exists an uncertainty in the total width Γ of the ER = 223-keV (Ex = 2485 keV) resonance in the 24Mg(p,γ)25Al reaction which could lead to enhancements in the reaction rate up to a factor of 32 at T9 = 0.04. The main goal of this thesis is to accurately determine the properties of the ER = 223-keV resonance in order to improve the reaction rate estimate for 24Mg(p, γ) 25Al. Resonance strength ωγ-, γ-ray branching ratios Γ γ/Γ, and mean lifetimes τ were determined for the E R = 223- and 419-keV resonances in 24Mg(p, γ) 25Al. These parameters allow for the determination of proton partial widths Γp, γ-ray partial widths Γ γ, and total widths Γ necessary for the calculation of the resonant cross section at Ep < 500 keV. The rate for the 24Mg(p, γ)25Al reaction for temperatures of T9 = 0.02 - 2 was calculated. The reaction rate deviates from the previous estimates by 18% to 45%, and therefore, the total width of the ER = 223-keV resonance does not have a significant influence on the reaction rate. In addition, branching ratios were determined for the 223-, 419-, 1616-, and 1654-keV resonances in 24Mg(p, γ) 25Al, and for the 406-keV resonance in 27Al( p, γ)28Si. Spectroscopic factors were determined from the proton partial widths for the states corresponding to the E R = 223- and 419-keV resonances. Resonance strength values were also

  19. Gas-phase reaction of ( E)-β-farnesene with ozone: Rate coefficient and carbonyl products

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Bejan, Iustinian; Sodeau, John R.; Wenger, John C.

    The gas-phase ozonolysis of ( E)-β-farnesene was investigated in a 3.91 m 3 atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10 -16 cm 3 molecule -1 s -1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and ( E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of ( E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of ( E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.

  20. Neutron detectors for fusion reaction-rate measurements

    SciTech Connect

    Lerche, R.A.; Phillion, D.W.; Landen, O.L.; Murphy, T.J.; Jaanimagi, P.A.

    1994-02-10

    Fusion reactions in an inertial-confinement fusion (ICF) target filled with deuterium or a deuterium/tritium fuel release nearly monoenergetic neutrons. Because most the neutrons leave the compressed target without collision, they preserve reaction-rate information as they travel radially outward from their point of origin. Three fast, neutron detector techniques, each capable of measuring the fusion reaction-rate of ICF targets, have been demonstrated. The most advanced detector is based on the fast rise-time of a commercial plastic scintillator material (BC-422) which acts as a neutron-to-light converter. Signals, which are recorded with a fast optical streak camera, have a resolution of 25 ps. Good signals can be recorded for targets producing only 5 x 10{sup 7} DT neutrons. Two other detectors use knock-on collisions between neutrons and protons in a thin polyethylene (CH{sub 2}) converter. In one, the converter is placed in front of the photocathode of an x-ray streak camera. Recoil protons pass through the photocathode and knock out electrons which are accelerated and deflected to produce a signal. Resolutions < 25 ps are possible. In the other, the converter is placed in front of a microchannel plate (MCP) with a gated microstrip. Recoil protons eject electrons from the gold layer forming the microstrip. If a gate pulse is present, the signal is amplified. Present gate times are about 80 ps.

  1. 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.

  2. Reaction rate constant for radiative association of CF{sup +}

    SciTech Connect

    Öström, Jonatan Gustafsson, Magnus; Bezrukov, Dmitry S.; Nyman, Gunnar

    2016-01-28

    Reaction rate constants and cross sections are computed for the radiative association of carbon cations (C{sup +}) and fluorine atoms (F) in their ground states. We consider reactions through the electronic transition 1{sup 1}Π → X{sup 1}Σ{sup +} and rovibrational transitions on the X{sup 1}Σ{sup +} and a{sup 3}Π potentials. Semiclassical and classical methods are used for the direct contribution and Breit–Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius–Kooij formula in five temperature intervals with a relative difference of <3%. The fit parameters will be added to the online database KIDA. For a temperature of 10–250 K, the rate constant is about 10{sup −21} cm{sup 3} s{sup −1}, rising toward 10{sup −16} cm{sup 3} s{sup −1} for a temperature of 30 000 K.

  3. Thermal energy reaction rates of titanium monomer cation

    SciTech Connect

    MacTaylor, R.S.; Vann, W.D.; Castleman, A.W. Jr.

    1996-03-28

    New determinations of quantitative forward rate constants for reactions of titanium monomer cation with C{sub 2}H{sub 6}, C{sub 3}H{sub 8}, H{sub 2}O, NH{sub 3}, and O{sub 2} are accomplished using a high-pressure (multicollision) flow tube reactor. These experiments were prompted by our observation of conflicting reports in the literature. The reaction rates we consider have been determined previously by both single-collision and multicollision methods, with some systems having generated notably contrasting results. An effort is made to reconcile the difference in values by explicitly addressing possible potential sources of error which have been suggested in earlier publications as the most likely reasons for the discrepancies. A `titration` technique is employed which allows controlled collisional quenching of excited state titanium cations with nitrogen gas such that excited state ion effects can be selectively observed and subsequently eliminated. No evidence is found to cast doubt upon the validity of multicollision methods for the determination of thermal energy rate constants. 20 refs., 4 figs., 1 tab.

  4. Reaction rate constant for radiative association of CF(.).

    PubMed

    Öström, Jonatan; Bezrukov, Dmitry S; Nyman, Gunnar; Gustafsson, Magnus

    2016-01-28

    Reaction rate constants and cross sections are computed for the radiative association of carbon cations (C(+)) and fluorine atoms (F) in their ground states. We consider reactions through the electronic transition 1(1)Π → X(1)Σ(+) and rovibrational transitions on the X(1)Σ(+) and a(3)Π potentials. Semiclassical and classical methods are used for the direct contribution and Breit-Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius-Kooij formula in five temperature intervals with a relative difference of <3%. The fit parameters will be added to the online database KIDA. For a temperature of 10-250 K, the rate constant is about 10(-21) cm(3) s(-1), rising toward 10(-16) cm(3) s(-1) for a temperature of 30,000 K.

  5. 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.

  6. ZGB surface reaction model with high diffusion rates

    NASA Astrophysics Data System (ADS)

    Evans, J. W.

    1993-02-01

    The diffusionless ZGB (monomer-dimer) surface reaction model exhibits a discontinuous transition to a monomer-poisoned state when the fraction of monomer adsorption attempts exceeds 0.525. It has been claimed that this transition shifts to 2/3 with introduction of rapid diffusion of the monomer species, or of both species. We show this is not the case, 2/3 representing the spinodal rather than the transition point. For equal diffusion rates of both species, we find that the transition only shifts to 0.5951±0.0002.

  7. ZGB surface reaction model with high diffusion rates

    SciTech Connect

    Evans, J.W. )

    1993-02-01

    The diffusionless ZGB (monomer--dimer) surface reaction model exhibits a discontinuous transition to a monomer-poisoned state when the fraction of monomer adsorption attempts exceeds 0.525. It has been claimed that this transition shifts to 2/3 with introduction of rapid diffusion of the monomer species, or of both species. We show this is not the case, 2/3 representing the spinodal rather than the transition point. For equal diffusion rates of both species, we find that the transition only shifts to 0.5951[plus minus]0.0002.

  8. Novel technique for Constraining r -Process (n , γ ) Reaction Rates

    NASA Astrophysics Data System (ADS)

    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 76Ga 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 75Ge (n ,γ )76Ge cross section and reaction rate.

  9. Metal-silicon reaction rates - The effects of capping

    NASA Technical Reports Server (NTRS)

    Weizer, Victor G.; Fatemi, Navid S.

    1989-01-01

    Evidence is presented showing that the presence of the commonly used anti-reflection coating material Ta2O5 on the free surface of contact metallization can either suppress or enhance, depending on the system, the interaction that takes place at elevated temperatures between the metallization and the underlying Si. The cap layer is shown to suppress both the generation and annihilation of vacancies at the free surface of the metal which are necessary to support metal-Si interactons. Evidence is also presented indicating that the mechanical condition of the free metal surface has a significant effect on the metal-silicon reaction rate.

  10. Effect of gas flow rate on titanium sponge reaction

    NASA Astrophysics Data System (ADS)

    Wang, Zhiliang; Feng, Gaoping; Wang, Mingdong; Hong, Yanji

    2017-08-01

    This paper expounds the important application of titanium sponge adsorption in inert gas purification, the reaction mechanism of titanium with nitrogen and oxygen was introduced. Explored the relationship between the absorption capacity of sponge titanium on the active gas in air samples and the gas flow rate. The model of sponge titanium for flowing air absorption was established by data analysis. The designed experiment verified the relationship between the titanium processing capacity and the gas collecting device. Finally, the influence of the mass of the sponge titanium on the degassing capacity was studied through experiments.

  11. Uncertainty evaluation of nuclear reaction model parameters using integral and microscopic measurements. Covariances evaluation with CONRAD code

    NASA Astrophysics Data System (ADS)

    de Saint Jean, C.; Habert, B.; Archier, P.; Noguere, G.; Bernard, D.; Tommasi, J.; Blaise, P.

    2010-10-01

    In the [eV;MeV] energy range, modelling of the neutron induced reactions are based on nuclear reaction models having parameters. Estimation of co-variances on cross sections or on nuclear reaction model parameters is a recurrent puzzle in nuclear data evaluation. Major breakthroughs were asked by nuclear reactor physicists to assess proper uncertainties to be used in applications. In this paper, mathematical methods developped in the CONRAD code[2] will be presented to explain the treatment of all type of uncertainties, including experimental ones (statistical and systematic) and propagate them to nuclear reaction model parameters or cross sections. Marginalization procedure will thus be exposed using analytical or Monte-Carlo solutions. Furthermore, one major drawback found by reactor physicist is the fact that integral or analytical experiments (reactor mock-up or simple integral experiment, e.g. ICSBEP, …) were not taken into account sufficiently soon in the evaluation process to remove discrepancies. In this paper, we will describe a mathematical framework to take into account properly this kind of information.

  12. Uncertainty estimation of spectral matching ratio based power rating of CPV modules

    NASA Astrophysics Data System (ADS)

    Steiner, Marc; Siefer, Gerald; Bett, Andreas W.

    2017-09-01

    The concentrator standard conditions are defined in the standard IEC 62670-1. Those conditions demand for spectral conditions equivalent to AM1.5d as described in IEC 60904-3. The power output of CPV modules has to be rated at the concentrator standard conditions and thus at AM1.5d spectral irradiance. According to IEC standard 62670-3 the prevailing spectral conditions have to be characterized using spectral matching ratios (SMR). The SMR values have to be within three percent of unity to allow for standardized power ratings. The SMR values are calculated from component cell sensor readings. The most commonly used component cells are based on lattice-matched triple-junction cell structures with bandgaps of 1.9, 1.4 and 0.7 eV. In this work, the usage of these component cells for power ratings on CPV modules equipped with other types of multi-junction cells is investigated. This investigation is based on representative power outputs of CPV modules. These power outputs were calculated using i) the spectral irradiance modeling software SMARTS2, ii) measured external quantum efficiencies and iii) the two-diode model. The outcome of this investigation is an estimation for the measurement uncertainty of rated CPV module power output when using the SMR filtering approach recommended in IEC 62670-3.

  13. Comparison of DSMC Reaction Models with QCT Reaction Rates for Nitrogen

    DTIC Science & Technology

    2016-07-17

    Distribution A: Approved for Public Release, Distribution Unlimited PA #16299 Non-Equilibrium Reaction Rates N2-N2, Tv≠ Tt =Tr • TCE, QK, and VFD are over an...Release, Distribution Unlimited PA #16299 Non-Equilibrium Rates for Bias Model N2-N2, Tv≠ Tt =Tr • Bias model provides much better fit than Park 2-T model...Higher vibrational favoring for lower Tt : λ>2 works better than λ=4 for Tt >20,000 K Distribution A: Approved for Public Release, Distribution

  14. 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.

  15. Investigation of the reaction rates between uranium and liquid aluminum

    SciTech Connect

    Strum, M.J.; Sedillo, E.; Smugeresky, J.

    1995-05-05

    A limited study consisting of scoping experiments was carried out to determine if a uranium-niobium alloy was weakly or strongly resistant to penetration by liquid aluminum alloy 6061. Our investigation was limited to temperatures between 700{degrees}and 900{degrees}C and carried out using small cylindrical coupons of U-6wt.%Nb and unalloyed U in unsaturated molten aluminum and aluminum alloy 6061 baths. The results indicate that indeed, significant dissolution of uranium into molten aluminum occurs and in relatively short times. The diameters of U-6wt.%Nb test cylinders immersed in unsaturated Al-6061 decreased linearly with time at 700{degrees}C, 800{degrees}C, and 900{degrees}C at rates of 1.14 mm/h, 3.0 mm/h, and 3.5 mm/h, respectively. However, we have found that the reaction rates were significantly reduced by the alloying elements niobium and magnesium. These results suggest that a more detailed investigation could lead to a predictive capability for control of these reaction rates. In unalloyed U, the rate of U dissolution increased by up to a factor of ten relative to that in U- 6wt.%Nb. In both materials, the dissolution of the U core was found to occur by advance of a continuous intermetallic layer, which redissolves into the unsaturated liquid Al bath. The Nb additions resulted in the formation of a thick transition layer composed of intermetallic and U-saturated liquid. In unalloyed U, however, the transition layer was largely reduced in thickness, allowing unsaturated liquid adjacent to the continuous intermetallic layer. Another important variable identified was the influence of surface condition on interface reactivity. At 900{degrees}C, liquid attack was completely absent over large regions of U-6wt.% Nb samples immersed in Al-6061. Surface analysis by EDX identified the presence of up to 24 at.% Mg in unattacked areas.

  16. 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)

  17. 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)

  18. Intolerance of uncertainty and startle potentiation in relation to different threat reinforcement rates.

    PubMed

    Chin, Brian; Nelson, Brady D; Jackson, Felicia; Hajcak, Greg

    2016-01-01

    Fear conditioning research on threat predictability has primarily examined the impact of temporal (i.e., timing) predictability on the startle reflex. However, there are other key features of threat that can vary in predictability. For example, the reinforcement rate (i.e., frequency) of threat is a crucial factor underlying fear learning. The present study examined the impact of threat reinforcement rate on the startle reflex and self-reported anxiety during a fear conditioning paradigm. Forty-five participants completed a fear learning task in which the conditioned stimulus was reinforced with an electric shock to the forearm on 50% of trials in one block and 75% of trials in a second block, in counter-balanced order. The present study also examined whether intolerance of uncertainty (IU), the tendency to perceive or experience uncertainty as stressful or unpleasant, was associated with the startle reflex during conditions of low (50%) vs. high (75%) reinforcement. Results indicated that, across all participants, startle was greater during the 75% relative to the 50% reinforcement condition. IU was positively correlated with startle potentiation (i.e., increased startle response to the CS+ relative to the CS-) during the 50%, but not the 75%, reinforcement condition. Thus, despite receiving fewer electric shocks during the 50% reinforcement condition, individuals with high IU uniquely demonstrated greater defense system activation when impending threat was more uncertain. The association between IU and startle was independent of state anxiety. The present study adds to a growing literature on threat predictability and aversive responding, and suggests IU is associated with abnormal responding in the context of uncertain threat.

  19. Reader Reaction On the generalized Kruskal-Wallis test for genetic association studies incorporating group uncertainty

    PubMed Central

    Wu, Baolin; Guan, Weihua

    2015-01-01

    Summary Acar and Sun (2013, Biometrics, 69, 427-435) presented a generalized Kruskal-Wallis (GKW) test for genetic association studies that incorporated the genotype uncertainty and showed its robust and competitive performance compared to existing methods. We present another interesting way to derive the GKW test via a rank linear model. PMID:25351417

  20. Bayesian analysis of stage-fall-discharge rating curves and their uncertainties

    NASA Astrophysics Data System (ADS)

    Mansanarez, V.; Le Coz, J.; Renard, B.; Lang, M.; Pierrefeu, G.; Vauchel, P.

    2016-09-01

    Stage-fall-discharge (SFD) rating curves are traditionally used to compute streamflow records at sites where the energy slope of the flow is variable due to variable backwater effects. We introduce a model with hydraulically interpretable parameters for estimating SFD rating curves and their uncertainties. Conventional power functions for channel and section controls are used. The transition to a backwater-affected channel control is computed based on a continuity condition, solved either analytically or numerically. The practical use of the method is demonstrated with two real twin-gauge stations, the Rhône River at Valence, France, and the Guthusbekken stream at station 0003ṡ0033, Norway. Those stations are typical of a channel control and a section control, respectively, when backwater-unaffected conditions apply. The performance of the method is investigated through sensitivity analysis to prior information on controls and to observations (i.e., available gaugings) for the station of Valence. These analyses suggest that precisely identifying SFD rating curves requires adapted gauging strategy and/or informative priors. The Madeira River, one of the largest tributaries of the Amazon, provides a challenging case typical of large, flat, tropical river networks where bed roughness can also be variable in addition to slope. In this case, the difference in staff gauge reference levels must be estimated as another uncertain parameter of the SFD model. The proposed Bayesian method is a valuable alternative solution to the graphical and empirical techniques still proposed in hydrometry guidance and standards.

  1. Uncertainties of stormwater characteristics and removal rates of stormwater treatment facilities: implications for stormwater handling.

    PubMed

    Langeveld, J G; Liefting, H J; Boogaard, F C

    2012-12-15

    Stormwater runoff is a major contributor to the pollution of receiving waters. This study focuses at characterising stormwater in order to be able to determine the impact of stormwater on receiving waters and to be able to select the most appropriate stormwater handling strategy. The stormwater characterisation is based on determining site mean concentrations (SMCs) and their uncertainties as well as the treatability of stormwater by monitoring specific pollutants concentration levels (TSS, COD, BOD, TKN, TP, Pb, Cu, Zn, E.coli) at three full scale stormwater treatment facilities in Arnhem, the Netherlands. This has resulted in 106 storm events being monitored at the lamella settler, 59 at the high rate sand filter and 132 at the soil filter during the 2 year monitoring period. The stormwater characteristics in Arnhem in terms of SMCs for main pollutants TSS and COD and settling velocities differ from international data. This implies that decisions for stormwater handling made on international literature data will very likely be wrong due to assuming too high concentrations of pollutants and misjudgement of the treatability of stormwater. The removal rates monitored at the full scale treatment facilities are within the expected range, with the soil filter and the sand filter having higher removal rates than the lamella settler. The full scale pilots revealed the importance of incorporating gross solids removal in the design of stormwater treatment facilities, as the gross solids determine operation and maintenance requirements.

  2. Rate constant measurements for the overall reaction of OH + 1-butanol → products from 900 to 1200 K.

    PubMed

    Pang, Genny A; Hanson, Ronald K; Golden, David M; Bowman, Craig T

    2012-03-15

    The rate constant for the overall reaction OH + 1-butanol → products was determined in the temperature range 900 to 1200 K from measurements of OH concentration time histories in reflected shock wave experiments of tert-butyl hydroperoxide (TBHP) as a fast source of OH radicals with 1-butanol in excess. Narrow-linewidth laser absorption was employed for the quantitative OH concentration measurement. A detailed kinetic mechanism was constructed that includes updated rate constants for 1-butanol and TBHP kinetics that influence the near-first-order OH concentration decay under the present experimental conditions, and this mechanism was used to facilitate the rate constant determination. The current work improves upon previous experimental studies of the title rate constant by utilizing a rigorously generated kinetic model to describe secondary reactions. Additionally, the current work extends the temperature range of experimental data in the literature for the title reaction under combustion-relevant conditions, presenting the first measurements from 900 to 1000 K. Over the entire temperature range studied, the overall rate constant can be expressed in Arrhenius form as 3.24 × 10(-10) exp(-2505/T [K]) cm(3) molecule(-1) s(-1). The influence of secondary reactions on the overall OH decay rate is discussed, and a detailed uncertainty analysis is performed yielding an overall uncertainty in the measured rate constant of ±20% at 1197 K and ±23% at 925 K. The results are compared with previous experimental and theoretical studies on the rate constant for the title reaction and reasonable agreement is found when the earlier experimental data were reinterpreted.

  3. 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.

  4. 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.

  5. Application of Semiclassical Methods to Reaction Rate Theory

    NASA Astrophysics Data System (ADS)

    Hernandez, Rigoberto

    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. ^dagger. 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. ^ddagger 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 "pre-reactive" partition function depending on the action of the reactive mode), and the ability to go beyond the perturbative approximation. ^S. In addition, the distribution of unimolecular decay rates at threshold energies to dissociation has been modeled by describing the quasi-bound states as strongly -mixed. The possible existence of globally conserved symmetries --which would break this ansatz--is included by treating each symmetry block of the Hamiltonian separably and assuming the ansatz for each symmetry manifold. Use of SCTST to

  6. Manual choice reaction times in the rate-domain.

    PubMed

    Harris, Christopher M; Waddington, Jonathan; Biscione, Valerio; Manzi, Sean

    2014-01-01

    Over the last 150 years, human manual reaction times (RTs) have been recorded countless times. Yet, our understanding of them remains remarkably poor. RTs are highly variable with positively skewed frequency distributions, often modeled as an inverse Gaussian distribution reflecting a stochastic rise to threshold (diffusion process). However, latency distributions of saccades are very close to the reciprocal Normal, suggesting that "rate" (reciprocal RT) may be the more fundamental variable. We explored whether this phenomenon extends to choice manual RTs. We recorded two-alternative choice RTs from 24 subjects, each with 4 blocks of 200 trials with two task difficulties (easy vs. difficult discrimination) and two instruction sets (urgent vs. accurate). We found that rate distributions were, indeed, very close to Normal, shifting to lower rates with increasing difficulty and accuracy, and for some blocks they appeared to become left-truncated, but still close to Normal. Using autoregressive techniques, we found temporal sequential dependencies for lags of at least 3. We identified a transient and steady-state component in each block. Because rates were Normal, we were able to estimate autoregressive weights using the Box-Jenkins technique, and convert to a moving average model using z-transforms to show explicit dependence on stimulus input. We also found a spatial sequential dependence for the previous 3 lags depending on whether the laterality of previous trials was repeated or alternated. This was partially dissociated from temporal dependency as it only occurred in the easy tasks. We conclude that 2-alternative choice manual RT distributions are close to reciprocal Normal and not the inverse Gaussian. This is not consistent with stochastic rise to threshold models, and we propose a simple optimality model in which reward is maximized to yield to an optimal rate, and hence an optimal time to respond. We discuss how it might be implemented.

  7. Application of Monte Carlo Methods to Perform Uncertainty and Sensitivity Analysis on Inverse Water-Rock Reactions with NETPATH

    SciTech Connect

    McGraw, David; Hershey, Ronald L.

    2016-06-01

    Methods were developed to quantify uncertainty and sensitivity for NETPATH inverse water-rock reaction models and to calculate dissolved inorganic carbon, carbon-14 groundwater travel times. The NETPATH models calculate upgradient groundwater mixing fractions that produce the downgradient target water chemistry along with amounts of mineral phases that are either precipitated or dissolved. Carbon-14 groundwater travel times are calculated based on the upgradient source-water fractions, carbonate mineral phase changes, and isotopic fractionation. Custom scripts and statistical code were developed for this study to facilitate modifying input parameters, running the NETPATH simulations, extracting relevant output, postprocessing the results, and producing graphs and summaries. The scripts read userspecified values for each constituent’s coefficient of variation, distribution, sensitivity parameter, maximum dissolution or precipitation amounts, and number of Monte Carlo simulations. Monte Carlo methods for analysis of parametric uncertainty assign a distribution to each uncertain variable, sample from those distributions, and evaluate the ensemble output. The uncertainty in input affected the variability of outputs, namely source-water mixing, phase dissolution and precipitation amounts, and carbon-14 travel time. Although NETPATH may provide models that satisfy the constraints, it is up to the geochemist to determine whether the results are geochemically reasonable. Two example water-rock reaction models from previous geochemical reports were considered in this study. Sensitivity analysis was also conducted to evaluate the change in output caused by a small change in input, one constituent at a time. Results were standardized to allow for sensitivity comparisons across all inputs, which results in a representative value for each scenario. The approach yielded insight into the uncertainty in water-rock reactions and travel times. For example, there was little

  8. Transcriptional dynamics with time-dependent reaction rates

    NASA Astrophysics Data System (ADS)

    Nandi, Shubhendu; Ghosh, Anandamohan

    2015-02-01

    Transcription is the first step in the process of gene regulation that controls cell response to varying environmental conditions. Transcription is a stochastic process, involving synthesis and degradation of mRNAs, that can be modeled as a birth-death process. We consider a generic stochastic model, where the fluctuating environment is encoded in the time-dependent reaction rates. We obtain an exact analytical expression for the mRNA probability distribution and are able to analyze the response for arbitrary time-dependent protocols. Our analytical results and stochastic simulations confirm that the transcriptional machinery primarily act as a low-pass filter. We also show that depending on the system parameters, the mRNA levels in a cell population can show synchronous/asynchronous fluctuations and can deviate from Poisson statistics.

  9. 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.

  10. Analysis of reaction rates of single molecules on metal surfaces

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    2017-10-01

    The experimental results of the action spectra i.e., reaction rate R(V) as a function of a bias voltage V are analyzed for rotation of a single CCH (D) molecule on a Cu (100) surface [5] and hopping of a single H(D)2O molecule on Pd(111) surface [6]. In the former system it is identified that rotation occurs if enough energy stored in the C-H (D) in-plane bending (IPB) mode excited by tunneling electron is transferred to the C-H (D) out of plane bending (OPB) mode (reaction coordinate mode) via the anharmonic mode coupling in a single electron process. The calculated R(V) shows an excellent agreement with the experimental results except at the low bias voltages below V ≃ 60 mV where no experimental data is available for the nonlinear current I dependence of R(I). A reproduction of the experimental R(V) at the higher voltage region allows us to determine the vibrational density of states of the C-H IPB mode and its coupling rate to the C-H (D) OPB mode as well as the inelastic tunneling current to excite IPB mode. A change of a conductance upon excitation of the C-H IPB mode enables us to evaluate the electron-vibration coupling strength inducing the rotation motion of CCH molecule. In the latter system investigated at a high temperature of about 40 K, the constant R(V) due to thermal hopping followed by the rapid increase is satisfactory explained by anharmonic inter-mode coupling between the scissor mode excited by tunneling electrons and the frustrated translation mode for H(D)2O molecule on Pd(111).

  11. Effects of triple-α and 12C(α, γ)16O reaction rates on the supernova nucleosynthesis in a massive star of 25 Mʘ

    NASA Astrophysics Data System (ADS)

    Kikuchi, Yukihiro; Hashimoto, Masa-aki; Ono, Masaomi; Fukuda, Ryohei

    2015-06-01

    We investigate the effects of triple-α and ^{12}{C}(α ,γ )^{16}O reaction rates on the production of supernova yields for a massive star of 25 M_{⊙}. We combine the reaction rates to examine the rate dependence, where the rates are considered to cover the possible variation of the rates based on experiments on the earth and on theory. We adopt four combinations of the reaction rates from two triple-α reaction rates and two ^{12}C(α ,γ )^{16}O ones. First, we examine the evolution of massive stars of 20 M_{⊙} and 25 M_{⊙} whose helium cores correspond to helium stars of 6 M_{⊙} and 8 M_{⊙}, respectively. While the 25 M_{⊙} stars evolve to the presupernova stages for all combinations of the reaction rates, the evolutionary paths of the 20 M_{⊙} stars proceed significantly differently for some combinations, which are unacceptable for progenitors of supernovae. Second, we perform calculations of supernova explosions within the limitation of spherical symmetry and compare the calculated abundance ratios with solar system abundances. We can deduce some constraints to the reaction rates. The results show that a conventional rate is adequate for a triple-α reaction rate and a rather higher value of the reaction rate within the upper limit for the experimental uncertainties is favorable for a ^{12}{C}(α ,γ )^{16}O rate.

  12. Manual choice reaction times in the rate-domain

    PubMed Central

    Harris, Christopher M.; Waddington, Jonathan; Biscione, Valerio; Manzi, Sean

    2014-01-01

    Over the last 150 years, human manual reaction times (RTs) have been recorded countless times. Yet, our understanding of them remains remarkably poor. RTs are highly variable with positively skewed frequency distributions, often modeled as an inverse Gaussian distribution reflecting a stochastic rise to threshold (diffusion process). However, latency distributions of saccades are very close to the reciprocal Normal, suggesting that “rate” (reciprocal RT) may be the more fundamental variable. We explored whether this phenomenon extends to choice manual RTs. We recorded two-alternative choice RTs from 24 subjects, each with 4 blocks of 200 trials with two task difficulties (easy vs. difficult discrimination) and two instruction sets (urgent vs. accurate). We found that rate distributions were, indeed, very close to Normal, shifting to lower rates with increasing difficulty and accuracy, and for some blocks they appeared to become left-truncated, but still close to Normal. Using autoregressive techniques, we found temporal sequential dependencies for lags of at least 3. We identified a transient and steady-state component in each block. Because rates were Normal, we were able to estimate autoregressive weights using the Box-Jenkins technique, and convert to a moving average model using z-transforms to show explicit dependence on stimulus input. We also found a spatial sequential dependence for the previous 3 lags depending on whether the laterality of previous trials was repeated or alternated. This was partially dissociated from temporal dependency as it only occurred in the easy tasks. We conclude that 2-alternative choice manual RT distributions are close to reciprocal Normal and not the inverse Gaussian. This is not consistent with stochastic rise to threshold models, and we propose a simple optimality model in which reward is maximized to yield to an optimal rate, and hence an optimal time to respond. We discuss how it might be implemented. PMID:24959134

  13. Rate coefficients for the reaction of formaldehyde with HO2 radicals from fluorescence spectroscopy of HOCH2OO radicals

    NASA Astrophysics Data System (ADS)

    Bunkan, Arne; Amédro, Damien; Crowley, John

    2017-04-01

    The reaction of formaldehyde with HO2 radicals constitutes a minor, but significant sink of formaldehyde in the troposphere as well as a possible interference in other formaldehyde photooxidation experiments. HCHO + HO2 ⇌ HOCH2OO (1) Due to the difficulty of simultaneously monitoring the reactant and product concentrations while preventing interfering secondary chemistry, there is a considerable uncertainty in the literature values for the reaction rate coefficients. We have used two photon, excited fragment spectroscopy (TPEFS), originally developed for monitoring HNO3 formation in kinetic experiments, to monitor the formation of the HOCH2OO radical. Dispersed and single wavelength fluorescence emission following the 193 nm photolysis of HOCH2OO have been recorded and analysed. Characterisation of the method is presented along with rate coefficients for the reaction of HCHO with HO2 radicals at tropospheric temperatures.

  14. Faster rates with less catalyst in template-directed reactions

    NASA Technical Reports Server (NTRS)

    Kanavarioti, A.; Baird, E. E.

    1995-01-01

    We have recently shown that the polycytidylic acid-directed polymerization of guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) is amenable to kinetic study and that rate determinations as a function of 2-MeImpG concentration can reveal much mechanistic detail (Kanavarioti et al. 1993). Here we report kinetic data which show that, once the reaction has been initiated by the formation of dimers, the elongation of dimers to form longer oligomers is accelerated by decreasing polycytidylate (poly(C)) concentration from 0.05 to 0.002 M. This result is consistent with the previously proposed mechanism. The increase in the observed pseudo-first order rate constant for formation of the trimer, k3', and the corresponding constant for formation of oligomers longer than the trimer, ki' (ki' is independent of oligomer length for i > or = 4), with decreasing template concentration for a given monomer concentration is attributed to an increase in template occupancy as template concentration is reduced.

  15. Estimating radar reflectivity - snowfall rate relationships and their uncertainties over Antarctica by combining disdrometer and radar observations

    NASA Astrophysics Data System (ADS)

    Souverijns, Niels; Gossart, Alexandra; Lhermitte, Stef; Gorodetskaya, Irina; Kneifel, Stefan; Maahn, Maximilian; Bliven, Francis; van Lipzig, Nicole

    2017-04-01

    The Antarctic Ice Sheet (AIS) is the largest ice body on earth, having a volume equivalent to 58.3 m global mean sea level rise. Precipitation is the dominant source term in the surface mass balance of the AIS. However, this quantity is not well constrained in both models and observations. Direct observations over the AIS are also not coherent, as they are sparse in space and time and acquisition techniques differ. As a result, precipitation observations stay mostly limited to continent-wide averages based on satellite radar observations. Snowfall rate (SR) at high temporal resolution can be derived from the ground-based radar effective reflectivity factor (Z) using information about snow particle size and shape. Here we present reflectivity snowfall rate relations (Z = aSRb) for the East Antarctic escarpment region using the measurements at the Princess Elisabeth (PE) station and an overview of their uncertainties. A novel technique is developed by combining an optical disdrometer (NASA's Precipitation Imaging Package; PIP) and a vertically pointing 24 GHz FMCW micro rain radar (Metek's MRR) in order to reduce the uncertainty in SR estimates. PIP is used to obtain information about snow particle characteristics and to get an estimate of Z, SR and the Z-SR relation. For PE, located 173 km inland, the relation equals Z = 18SR1.1. The prefactor (a) of the relation is sensitive to the median diameter of the particles. Larger particles, found closer to the coast, lead to an increase of the value of the prefactor. More inland locations, where smaller snow particles are found, obtain lower values for the prefactor. The exponent of the Z-SR relation (b) is insensitive to the median diameter of the snow particles. This dependence of the prefactor of the Z-SR relation to the particle size needs to be taken into account when converting radar reflectivities to snowfall rates over Antarctica. The uncertainty on the Z-SR relations is quantified using a bootstrapping approach

  16. Flow Rates Measurement and Uncertainty Analysis in Multiple-Zone Water-Injection Wells from Fluid Temperature Profiles.

    PubMed

    Reges, José E O; Salazar, A O; Maitelli, Carla W S P; Carvalho, Lucas G; Britto, Ursula J B

    2016-07-13

    This work is a contribution to the development of flow sensors in the oil and gas industry. It presents a methodology to measure the flow rates into multiple-zone water-injection wells from fluid temperature profiles and estimate the measurement uncertainty. First, a method to iteratively calculate the zonal flow rates using the Ramey (exponential) model was described. Next, this model was linearized to perform an uncertainty analysis. Then, a computer program to calculate the injected flow rates from experimental temperature profiles was developed. In the experimental part, a fluid temperature profile from a dual-zone water-injection well located in the Northeast Brazilian region was collected. Thus, calculated and measured flow rates were compared. The results proved that linearization error is negligible for practical purposes and the relative uncertainty increases as the flow rate decreases. The calculated values from both the Ramey and linear models were very close to the measured flow rates, presenting a difference of only 4.58 m³/d and 2.38 m³/d, respectively. Finally, the measurement uncertainties from the Ramey and linear models were equal to 1.22% and 1.40% (for injection zone 1); 10.47% and 9.88% (for injection zone 2). Therefore, the methodology was successfully validated and all objectives of this work were achieved.

  17. Flow Rates Measurement and Uncertainty Analysis in Multiple-Zone Water-Injection Wells from Fluid Temperature Profiles

    PubMed Central

    Reges, José E. O.; Salazar, A. O.; Maitelli, Carla W. S. P.; Carvalho, Lucas G.; Britto, Ursula J. B.

    2016-01-01

    This work is a contribution to the development of flow sensors in the oil and gas industry. It presents a methodology to measure the flow rates into multiple-zone water-injection wells from fluid temperature profiles and estimate the measurement uncertainty. First, a method to iteratively calculate the zonal flow rates using the Ramey (exponential) model was described. Next, this model was linearized to perform an uncertainty analysis. Then, a computer program to calculate the injected flow rates from experimental temperature profiles was developed. In the experimental part, a fluid temperature profile from a dual-zone water-injection well located in the Northeast Brazilian region was collected. Thus, calculated and measured flow rates were compared. The results proved that linearization error is negligible for practical purposes and the relative uncertainty increases as the flow rate decreases. The calculated values from both the Ramey and linear models were very close to the measured flow rates, presenting a difference of only 4.58 m³/d and 2.38 m³/d, respectively. Finally, the measurement uncertainties from the Ramey and linear models were equal to 1.22% and 1.40% (for injection zone 1); 10.47% and 9.88% (for injection zone 2). Therefore, the methodology was successfully validated and all objectives of this work were achieved. PMID:27420068

  18. Rate coefficients for the OH + CFH2CH2OH reaction between 238 and 355 K.

    PubMed

    Rajakumar, B; Burkholder, James B; Portmann, R W; Ravishankara, A R

    2005-06-21

    The rate coefficient for the reaction OH + CFH2CH2OH --> products (k1) between 238 and 355 K was measured using the pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique to be (5.15 +/- 0.88)x 10(-12) exp[-(330 +/- 45)/T] cm3 molecule(-1) s(-1); k1(298 K)= 1.70 x 10(-12) cm3 molecule(-1) s(-1). The quoted uncertainties are 2sigma(95% confidence level) and include estimated systematic errors. The present results are discussed in relation to the measured rate coefficients for the reaction of OH with other fluorinated alcohols and those calculated using recently reported structure additivity relationships for fluorinated compounds (K. Tokuhashi, H. Nagai, A. Takahashi, M. Kaise, S. Kondo, A. Sekiya, M. Takahashi, Y. Gotoh and A. Suga, J. Phys. Chem. A, 1999, 103, 2664-2672, ). Infrared absorption cross sections for CFH2CH2OH are reported and they are used to calculate the global warming potentials (GWP) for CFH2CH2OH of approximately 8, approximately 2, and approximately 1, respectively, for the 20, 100 and 500 year horizons. A brief discussion of the atmospheric degradation of CFH2CH2OH is provided. It is concluded that CFH2CH2OH is an acceptable substitute for CFCs in terms of its impact on Earth's climate and the composition of the atmosphere. The room temperature rate coefficient for the reaction OH + CFH2CH2OH --> products (k10) was measured to be 3.26 x 10(-12) cm3 molecule(-1) s(-1), in good agreement with recent measurements from this laboratory.

  19. 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)

  20. 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)

  1. 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.

  2. 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.

  3. 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

  4. Reaction rate theory of radiation exposure:Effects of dose rate on mutation frequency

    NASA Astrophysics Data System (ADS)

    Bando, Masako; Nakamura, Issei; Manabe, Yuichiro

    2014-03-01

    We revisit the linear no threshold (LNT) hypothesis deduced from the prominent works done by H. J. Muller for the DNA mutation induced by the artificial radiation and by W. L. Russell and E. M. Kelly for that of mega-mouse experiments, developing a new kinetic reaction theory. While the existing theoretical models primarily rely on the dependence of the total dose D on the mutation frequency, the key ingredient in our theory is the dose rate d(t) that accounts for decrease in the mutation rate during the time course of the cellular reactions. The general form for the mutation frequency with the constant dose rate d is simply expressed as, dFm(t)/dt = A - BFm(t) , with A =a0 +a1(d +deff) and B =b0 +b1(d +deff) . We discuss the solution for a most likely case with B > 0 ; Fm(t) = [A/B -Fm(0) ] (1 -e-Bt) +Fm(0) with the control value Fm(0) . We show that all the data of mega-mouse experiments by Russel with different dose rates fall on the universal scaling function Φ(τ) ≡ [Fm(τ) -Fm(0) ]/[ A / B -Fm(0) ] = 1 - exp(- τ) with scaled time τ = Bt . The concept of such a scaling rule provides us with a strong tool to study different species in a unified manner.

  5. γ spectroscopy of states in 32Cl relevant for the 31S(p ,γ )32Cl reaction rate

    NASA Astrophysics Data System (ADS)

    Afanasieva, L.; Blackmon, J. C.; Deibel, C. M.; Lai, J.; Linhardt, L. E.; Rasco, B. C.; Seweryniak, D.; Alcorta, M.; Carpenter, M. P.; Clark, J. A.; Hoffman, C. R.; Janssens, R. V. F.; Zhu, S.

    2017-09-01

    Background: The 31S(p ,γ )32Cl reaction becomes important for sulfur production in novae if the 31P(p ,α )28Si reaction rate is somewhat greater than currently accepted. The rate of the 31S(p ,γ )32Cl reaction is uncertain, primarily due to the properties of resonances at Ec .m .=156 and 549 keV. Purpose: We precisely determined the excitation energies of states in 32Cl through high-resolution γ spectroscopy including the two states most important for the 31S(p ,γ )32Cl reaction at nova temperatures. Method: Excited states in 32Cl were populated using the 10B(24Mg,2 n )32Cl reaction with a 24Mg beam from the ATLAS facility at Argonne National Laboratory. The reaction channel of interest was selected using recoils in the Fragment Mass Analyzer, and precise level energies were determined by detecting γ rays with Gammasphere. Results: We observed γ rays from the decay of six excited states in 32Cl. The excitation energies for two unbound levels at Ex=1738.1 (6) keV and 2130.5 (10) keV were determined and found to be in agreement with a previous high-precision measurement of the 32S(3He,t )32Cl reaction [1]. Conclusions: An updated 31S(p ,γ )32Cl reaction rate is presented. With the excitation energies of important levels firmly established, the dominant uncertainty in the reaction rate at nova temperatures is due to the strength of the resonance corresponding to the 2131-keV state in 32Cl.

  6. γ spectroscopy of states in Cl32 relevant for the S31(p,γ)Cl32 reaction rate

    DOE PAGES

    Afanasieva, L.; Blackmon, J. C.; Deibel, C. M.; ...

    2017-09-01

    Background: The 31S(p,gamma) 32Cl reaction becomes important for sulfur production in novae if the P-31(p, alpha)Si-28 reaction rate is somewhat greater than currently accepted. The rate of the S-31(p,gamma) Cl-32 reaction is uncertain, primarily due to the properties of resonances at E-c.m. = 156 and 549 keV. Purpose: We precisely determined the excitation energies of states in Cl-32 through high-resolution. spectroscopy including the two states most important for the S-31(p,gamma) Cl-32 reaction at nova temperatures. Method: Excited states in Cl-32 were populated using the B-10(Mg-24, 2n) Cl-32 reaction with a Mg-24 beam from the ATLAS facility at Argonne National Laboratory.more » The reaction channel of interest was selected using recoils in the Fragment Mass Analyzer, and we determined precise level energies by detecting. rays with Gammasphere. Results: We also observed. rays from the decay of six excited states in Cl-32. The excitation energies for two unbound levels at E-x = 1738.1 (6) keV and 2130.5 (10) keV were determined and found to be in agreement with a previous high-precision measurement of the S-32(He-3, t) Cl-32 reaction [1]. Conclusions: An updated 31S(p,gamma) Cl-32 reaction rate is presented. With the excitation energies of important levels firmly established, the dominant uncertainty in the reaction rate at nova temperatures is due to the strength of the resonance corresponding to the 2131-keV state in Cl-32.« less

  7. Effects of occurrence and time uncertainties on reaction and movement times of children.

    PubMed

    Ozmun, J C; Surburg, P R; Cleland, F E

    1989-06-01

    This study investigated the influence of catch trial (CT) occurrence and foreperiod variation on reaction time and movement time of children of different ages. 48 children were randomly assigned to a CT group or a no-CT group. All received randomly ordered foreperiods. The presence of CTs and varying foreperiods played an inhibitory role in the motor performance of children.

  8. Sum over Histories Representation for Kinetic Sensitivity Analysis: How Chemical Pathways Change When Reaction Rate Coefficients Are Varied.

    PubMed

    Bai, Shirong; Davis, Michael J; Skodje, Rex T

    2015-11-12

    The sensitivity of kinetic observables is analyzed using a newly developed sum over histories representation of chemical kinetics. In the sum over histories representation, the concentrations of the chemical species are decomposed into the sum of probabilities for chemical pathways that follow molecules from reactants to products or intermediates. Unlike static flux methods for reaction path analysis, the sum over histories approach includes the explicit time dependence of the pathway probabilities. Using the sum over histories representation, the sensitivity of an observable with respect to a kinetic parameter such as a rate coefficient is then analyzed in terms of how that parameter affects the chemical pathway probabilities. The method is illustrated for species concentration target functions in H2 combustion where the rate coefficients are allowed to vary over their associated uncertainty ranges. It is found that large sensitivities are often associated with rate limiting steps along important chemical pathways or by reactions that control the branching of reactive flux.

  9. The Sum over Histories Representation for Kinetic Sensitivity Analysis: How Chemical Pathways Change when Reaction Rate Coefficients are Varied

    SciTech Connect

    Bai, Shirong; Davis, Michael J.; Skodje, Rex T.

    2015-11-12

    The sensitivity of kinetic observables is analyzed using a newly developed sum over histories representation of chemical kinetics. In the sum over histories representation, the concentrations of the chemical species are decomposed into the sum of probabilities for chemical pathways that follow molecules from reactants to products or intermediates. Unlike static flux methods for reaction path analysis, the sum over histories approach includes the explicit time dependence of the pathway probabilities. Using the sum over histories representation, the sensitivity of an observable with respect to a kinetic parameter such as a rate coefficient is then analyzed in terms of how that parameter affects the chemical pathway probabilities. The method is illustrated for species concentration target functions in H-2 combustion where the rate coefficients are allowed to vary over their associated uncertainty ranges. It is found that large sensitivities are often associated with rate limiting steps along important chemical pathways or by reactions that control the branching of reactive flux

  10. Estimation of the nitrogen ionization reaction rate using electric arc shock tube data and Bayesian model analysis

    NASA Astrophysics Data System (ADS)

    Miki, K.; Panesi, M.; Prudencio, E. E.; Prudhomme, S.

    2012-02-01

    In this paper, we apply a Bayesian analysis to calibrate the parameters of a model for atomic nitrogen ionization using experimental data from the electric arc shock tube (EAST) wind-tunnel at NASA. We use a one-dimensional plasma flow solver coupled with a radiation solver for the simulation of the radiative signature emitted in the shock-heated air plasma as well as a Park's two-temperature model for the thermal and chemical non-equilibrium effects. We simultaneously quantify model parameter uncertainties and physical model inadequacies when solving the statistical inverse problem. Prior to the solution of such a problem, we perform a sensitivity analysis of the radiative heat flux in order to identify important sources of uncertainty. This analysis clearly shows the importance of the direct ionization of atomic nitrogen as it mostly influences the radiative heating. We then solve the statistical inverse problem and compare the calibrated reaction rates against values available in the literature. Our calculations estimate the reaction rate of the atomic nitrogen ionization to be (3.7 ± 1.5) × 1011 cm3 mol-1 s-1 at 10 000 K, a range consistent with Park's estimation. Finally, in order to assess the validity of the estimated parameters, we propagate their uncertainties through a statistical forward problem defined on a prediction scenario different from the calibration scenarios and compare the model predictions against other experimental data.

  11. 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.

  12. Enhanced reaction rates in NDP analysis with neutron scattering

    NASA Astrophysics Data System (ADS)

    Downing, R. Gregory

    2014-04-01

    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.

  13. Enhanced reaction rates in NDP analysis with neutron scattering.

    PubMed

    Downing, R Gregory

    2014-04-01

    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.

  14. Neutron detector for fusion reaction-rate measurements

    SciTech Connect

    Lerche, R.A.; Phillion, D.W.; Tietbohl, G.L.

    1993-09-03

    We have developed a fast, sensitive neutron detector for recording the fusion reaction-rate history of inertial-confinement fusion (ICF) experiments. The detector is based on the fast rise-time of a commercial plastic scintillator (BC-422) and has a response < 25-ps FWHM. A thin piece of scintillator material acts as a neutron-to- light converter. A zoom lens images light from the scintillator surface to a high-speed (15 ps) optical streak camera for recording. The zoom lens allows the scintillator to be positioned between 1 and 50 cm from a target. The camera simulaneously records an optical fiducial pulse which allows the camera time base to be calibrated relative to the incident laser power. Bursts of x rays formed by focusing 20-ps, 2.5-TW laser pulses onto gold disk targets demonstrate the detector resolution to be < 25 ps. We have recorded burn histories for deuterium/tritium-filled targets producing as few as 3 {times} 10{sup 7} neutrons.

  15. 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.

  16. On the mechanism of effective chemical reactions with turbulent mixing of reactants and finite rate of molecular reactions

    NASA Astrophysics Data System (ADS)

    Vorotilin, V. P.

    2017-01-01

    A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into "active" and "passive" classes; the reactants of the first class are not mixed and react by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.

  17. The Science-Policy Link: Stakeholder Reactions to the Uncertainties of Future Sea Level Rise

    NASA Astrophysics Data System (ADS)

    Plag, H.; Bye, B.

    2011-12-01

    Policy makers and stakeholders in the coastal zone are equally challenged by the risk of an anticipated rise of coastal Local Sea Level (LSL) as a consequence of future global warming. Many low-lying and often densely populated coastal areas are under risk of increased inundation. More than 40% of the global population is living in or near the coastal zone and this fraction is steadily increasing. A rise in LSL will increase the vulnerability of coastal infrastructure and population dramatically, with potentially devastating consequences for the global economy, society, and environment. Policy makers are faced with a trade-off between imposing today the often very high costs of coastal protection and adaptation upon national economies and leaving the costs of potential major disasters to future generations. They are in need of actionable information that provides guidance for the development of coastal zones resilient to future sea level changes. Part of this actionable information comes from risk and vulnerability assessments, which require information on future LSL changes as input. In most cases, a deterministic approach has been applied based on predictions of the plausible range of future LSL trajectories as input. However, there is little consensus in the scientific community on how these trajectories should be determined, and what the boundaries of the plausible range are. Over the last few years, many publications in Science, Nature and other peer-reviewed scientific journals have revealed a broad range of possible futures and significant epistemic uncertainties and gaps concerning LSL changes. Based on the somewhat diffuse science input, policy and decision makers have made rather different choices for mitigation and adaptation in cases such as Venice, The Netherlands, New York City, and the San Francisco Bay area. Replacing the deterministic, prediction-based approach with a statistical one that fully accounts for the uncertainties and epistemic gaps

  18. Uncertainty in action-value estimation affects both action choice and learning rate of the choice behaviors of rats.

    PubMed

    Funamizu, Akihiro; Ito, Makoto; Doya, Kenji; Kanzaki, Ryohei; Takahashi, Hirokazu

    2012-04-01

    The estimation of reward outcomes for action candidates is essential for decision making. In this study, we examined whether and how the uncertainty in reward outcome estimation affects the action choice and learning rate. We designed a choice task in which rats selected either the left-poking or right-poking hole and received a reward of a food pellet stochastically. The reward probabilities of the left and right holes were chosen from six settings (high, 100% vs. 66%; mid, 66% vs. 33%; low, 33% vs. 0% for the left vs. right holes, and the opposites) in every 20-549 trials. We used Bayesian Q-learning models to estimate the time course of the probability distribution of action values and tested if they better explain the behaviors of rats than standard Q-learning models that estimate only the mean of action values. Model comparison by cross-validation revealed that a Bayesian Q-learning model with an asymmetric update for reward and non-reward outcomes fit the choice time course of the rats best. In the action-choice equation of the Bayesian Q-learning model, the estimated coefficient for the variance of action value was positive, meaning that rats were uncertainty seeking. Further analysis of the Bayesian Q-learning model suggested that the uncertainty facilitated the effective learning rate. These results suggest that the rats consider uncertainty in action-value estimation and that they have an uncertainty-seeking action policy and uncertainty-dependent modulation of the effective learning rate. © 2012 The Authors. European Journal of Neuroscience © 2012 Federation of European Neuroscience Societies and Blackwell Publishing Ltd.

  19. Uncertainty in action-value estimation affects both action choice and learning rate of the choice behaviors of rats

    PubMed Central

    Funamizu, Akihiro; Ito, Makoto; Doya, Kenji; Kanzaki, Ryohei; Takahashi, Hirokazu

    2012-01-01

    The estimation of reward outcomes for action candidates is essential for decision making. In this study, we examined whether and how the uncertainty in reward outcome estimation affects the action choice and learning rate. We designed a choice task in which rats selected either the left-poking or right-poking hole and received a reward of a food pellet stochastically. The reward probabilities of the left and right holes were chosen from six settings (high, 100% vs. 66%; mid, 66% vs. 33%; low, 33% vs. 0% for the left vs. right holes, and the opposites) in every 20–549 trials. We used Bayesian Q-learning models to estimate the time course of the probability distribution of action values and tested if they better explain the behaviors of rats than standard Q-learning models that estimate only the mean of action values. Model comparison by cross-validation revealed that a Bayesian Q-learning model with an asymmetric update for reward and non-reward outcomes fit the choice time course of the rats best. In the action-choice equation of the Bayesian Q-learning model, the estimated coefficient for the variance of action value was positive, meaning that rats were uncertainty seeking. Further analysis of the Bayesian Q-learning model suggested that the uncertainty facilitated the effective learning rate. These results suggest that the rats consider uncertainty in action-value estimation and that they have an uncertainty-seeking action policy and uncertainty-dependent modulation of the effective learning rate. PMID:22487046

  20. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. 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.

  2. Volcanic Event Recurrence Rate Model (VERRM): Incorporating Radiometric Ages, Volcanic Stratigraphy and Paleomagnetic Data into a Monte Carlo Simulation to Estimate Uncertainty in Recurrence Rate through Time

    NASA Astrophysics Data System (ADS)

    Wilson, J. A.; Richardson, J. A.

    2015-12-01

    Traditional methods used to calculate recurrence rate of volcanism, such as linear regression, maximum likelihood and Weibull-Poisson distributions, are effective at estimating recurrence rate and confidence level, but these methods are unable to estimate uncertainty in recurrence rate through time. We propose a new model for estimating recurrence rate and uncertainty, Volcanic Event Recurrence Rate Model. VERRM is an algorithm that incorporates radiometric ages, volcanic stratigraphy and paleomagnetic data into a Monte Carlo simulation, generating acceptable ages for each event. Each model run is used to calculate recurrence rate using a moving average window. These rates are binned into discrete time intervals and plotted using the 5th, 50th and 95th percentiles. We present recurrence rates from Cima Volcanic Field (CA), Yucca Mountain (NV) and Arsia Mons (Mars). Results from Cima Volcanic Field illustrate how several K-Ar ages with large uncertainties obscure three well documented volcanic episodes. Yucca Mountain results are similar to published rates and illustrate the use of using the same radiometric age for multiple events in a spatially defined cluster. Arsia Mons results show a clear waxing/waning of volcanism through time. VERRM output may be used for a spatio-temporal model or to plot uncertainty in quantifiable parameters such as eruption volume or geochemistry. Alternatively, the algorithm may be reworked to constrain geomagnetic chrons. VERRM is implemented in Python 2.7 and takes advantage of NumPy, SciPy and matplotlib libraries for optimization and quality plotting presentation. A typical Monte Carlo simulation of 40 volcanic events takes a few minutes to couple hours to complete, depending on the bin size used to assign ages.

  3. 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.

  4. Study of Uncertainties of Predicting Space Shuttle Thermal Environment. [impact of heating rate prediction errors on weight of thermal protection system

    NASA Technical Reports Server (NTRS)

    Fehrman, A. L.; Masek, R. V.

    1972-01-01

    Quantitative estimates of the uncertainty in predicting aerodynamic heating rates for a fully reusable space shuttle system are developed and the impact of these uncertainties on Thermal Protection System (TPS) weight are discussed. The study approach consisted of statistical evaluations of the scatter of heating data on shuttle configurations about state-of-the-art heating prediction methods to define the uncertainty in these heating predictions. The uncertainties were then applied as heating rate increments to the nominal predicted heating rate to define the uncertainty in TPS weight. Separate evaluations were made for the booster and orbiter, for trajectories which included boost through reentry and touchdown. For purposes of analysis, the vehicle configuration is divided into areas in which a given prediction method is expected to apply, and separate uncertainty factors and corresponding uncertainty in TPS weight derived for each area.

  5. First measurement of the 34S(p ,γ )35Cl reaction rate through indirect methods for presolar nova grains

    NASA Astrophysics Data System (ADS)

    Gillespie, S. A.; Parikh, A.; Barton, C. J.; Faestermann, T.; José, J.; Hertenberger, R.; Wirth, H.-F.; de Séréville, N.; Riley, J. E.; Williams, M.

    2017-08-01

    Sulphur isotopic ratio measurements may help to establish the astrophysical sites in which certain presolar grains were formed. Nova model predictions of the 34S/32S ratio are, however, unreliable due to the lack of an experimental 34S(p ,γ )35Cl reaction rate. To this end, we have measured the 34S(3He,d )35Cl reaction at 20 MeV using a high resolution quadrupole-dipole-dipole-dipole magnetic spectrograph. Twenty-two levels over 6.2 MeV reaction rate has been determined using a Monte Carlo method. Hydrodynamic nova model calculations have been performed using this new reaction rate. These models show that remaining uncertainties in the 34S(p ,γ ) rate affect nucleosynthesis predictions by less than a factor of 1.4, and predict a 34S/32S isotopic ratio of 0.014-0.017. Since recent type II supernova models predict 34S/32S=0.026 -0.053 , the 34S/32S isotopic ratio may be used, in conjunction with other isotopic signatures, to distinguish presolar grains from oxygen-neon nova and type II supernova origin. Our results address a key nuclear physics uncertainty on which recent considerations discounting the nova origin of several grains depend.

  6. Pop-It Beads to Introduce Catalysis of Reaction Rate and Substrate Depletion Effects

    ERIC Educational Resources Information Center

    Gehret, Austin U.

    2017-01-01

    A kinesthetic classroom activity was designed to help students understand enzyme activity and catalysis of reaction rate. Students served the role of enzymes by manipulating Pop-It Beads as the catalytic event. This activity illuminates the relationship between reaction rate and reaction progress by allowing students to experience first-hand the…

  7. A Priori Estimation of Rate Constants for Unimolecular Decomposition Reactions

    DTIC Science & Technology

    1979-02-01

    priori theoretical predictions for the decomposition rate of the formyl and the methoxy radicals have been made by application of the Rice-Ramsperger...Kassel-Marcus Theory. An ArrheniLus rate coefficient expression is derived for the formyl radical decomposition, and a modified Arrhenius type rate...9 IV. A PREDICTED RATE CONSTANT FOR FORMYL RADICAL DECOMPOSITION. .. .... .................... ........19 V. SUMMtARY

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    1987-04-01

    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.

  10. 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.

  11. 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)

  12. Direct and Indirect Determinations of Elementary Rate Constants H + O2: Chain Branching; the Dehydration of tertiary-Butanol; the Retro Diels-Alder Reaction of Cyclohexene; the Dehydration of Isopropanol

    NASA Astrophysics Data System (ADS)

    Heyne, Joshua S.

    Due to growing environmental concern over the continued use of fossil fuels, methods to limit emissions and partially replace fossil fuel use with renewable biofuels are of considerable interest. Developing chemical kinetic models for the chemistry that affects combustion properties is important to understanding how new fuels affect combustion energy conversion processes in transportation devices. This thesis reports the experimental study of several important reactions (the H + O2 branching reaction, the key decomposition reactions of tertiary-butanol, the dehydration reaction of isopropanol, and the retro Diels-Alder reaction of cyclohexene) and develops robust analysis methods to estimate the absolute uncertainties of specific elementary rate constants derived from the experimental data. In the study of the above reactions, both a direct and indirect rate constant determination technique with associated uncertainty estimation methodologies are developed. In the study of the decomposition reactions, a direct determination technique is applied to experimental data gathered in preparation of this thesis. In the case of the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, both of which are used as internal standards for relative rate studies (Herzler et al. 1997) and chemical thermometry (Rosado-Reyes et al. 2013) , analysis showed an ˜20 K difference in the reaction rate between the reported results and the previous recommendations. In light of these discrepancies, an uncertainty estimation of previous recommendations illuminated an uncertainty of at least 20 K for the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, thus resolving the discrepancies. The determination of the H + O2 branching reaction and decomposition reactions of isopropanol used an indirect determination technique. The uncertainty of the H + O2 branching reaction rate is shown to be underestimated by previous

  13. 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…

  14. 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…

  15. Experimental measurements of the 15O(alpha,gamma)19Ne reaction rate and the stability of thermonuclear burning on accreting neutron stars

    SciTech Connect

    Fisker, J; Tan, W; Goerres, J; Wiescher, M; Cooper, R

    2007-05-08

    Neutron stars in close binary star systems often accrete matter from their companion stars. Thermonuclear ignition of the accreted material in the atmosphere of the neutron star leads to a thermonuclear explosion which is observed as an X-ray burst occurring periodically between hours and days depending on the accretion rate. The ignition conditions are characterized by a sensitive interplay between the accretion rate of the fuel supply and its depletion rate by nuclear burning in the hot CNO cycle and the rp-process. For accretion rates close to stable burning the burst ignition therefore depends critically on the hot CNO breakout reaction {sup 15}O({alpha}, {gamma}){sup 19}Ne that regulates the flow between the hot CNO cycle and the rapid proton capture process. Until recently, the {sup 15}O({alpha}, {gamma}){sup 19}Ne reaction rate was not known experimentally and the theoretical estimates carried significant uncertainties. In this paper we perform a parameter study of the uncertainty of this reaction rate and determine the astrophysical consequences of the first measurement of this reaction rate. Our results corroborate earlier predictions and show that theoretically burning remains unstable up to accretion rates near the Eddington limit, in contrast to astronomical observations.

  16. 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.

  17. What is the Rate-Limiting Step of a Multistep Reaction?

    ERIC Educational Resources Information Center

    Murdoch, Joseph R.

    1981-01-01

    Presents information concerning a fundamental concept for understanding reaction rate, the idea of a rate-limiting step for a chemical reaction. Discusses problems in using flow analogies and introduces an alternative approach to finding the rate-limiting step based on locating the transition state of highest energy. (CS)

  18. Uncertainty Evaluation of the New Setup for Measurement of Water-Vapor Permeation Rate by a Dew-Point Sensor

    NASA Astrophysics Data System (ADS)

    Hudoklin, D.; Šetina, J.; Drnovšek, J.

    2012-09-01

    The measurement of the water-vapor permeation rate (WVPR) through materials is very important in many industrial applications such as the development of new fabrics and construction materials, in the semiconductor industry, packaging, vacuum techniques, etc. The demand for this kind of measurement grows considerably and thus many different methods for measuring the WVPR are developed and standardized within numerous national and international standards. However, comparison of existing methods shows a low level of mutual agreement. The objective of this paper is to demonstrate the necessary uncertainty evaluation for WVPR measurements, so as to provide a basis for development of a corresponding reference measurement standard. This paper presents a specially developed measurement setup, which employs a precision dew-point sensor for WVPR measurements on specimens of different shapes. The paper also presents a physical model, which tries to account for both dynamic and quasi-static methods, the common types of WVPR measurements referred to in standards and scientific publications. An uncertainty evaluation carried out according to the ISO/IEC guide to the expression of uncertainty in measurement (GUM) shows the relative expanded ( k = 2) uncertainty to be 3.0 % for WVPR of 6.71 mg . h-1 (corresponding to permeance of 30.4 mg . m-2. day-1 . hPa-1).

  19. The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

    NASA Technical Reports Server (NTRS)

    Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

    1982-01-01

    The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

  20. The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

    NASA Technical Reports Server (NTRS)

    Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

    1982-01-01

    The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

  1. Diffusion-controlled reaction rate to an active site

    NASA Astrophysics Data System (ADS)

    Traytak, S. D.

    1995-02-01

    The diffusion-controlled reactions of chemically anisotropic reactants are treated for the simplest model of Solc and Stockmayer (Intern. J. Chem. Kinet. 5 (1973) 733) in the absence of rotational diffusion. Using the dual series relations approach we can find the effective steric factor with any necessary accuracy. A few simple analytical approximations for the effective steric factor are proposed. The derived results we compare with the relevant analytical approximations and numerical calculations available in the literature.

  2. Fluctuation enhanced electrochemical reaction rates at the nanoscale

    PubMed Central

    García-Morales, Vladimir; Krischer, Katharina

    2010-01-01

    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

  3. The sensitivity of oxidant formation rates to uncertainties in temperature, water vapor, and cloud cover

    SciTech Connect

    Walcek, C.J.; Yuan, H.H.

    1994-12-31

    Photochemical reaction mechanisms have been used for several decades to understand the formation of acids, oxidants, and other pollutants in the atmosphere. With complex chemical reaction mechanisms, it is useful to perform sensitivity studies to identify the most important or uncertain components within the system of reactions. In this study, we quantify the sensitivity of a chemical reaction mechanism to changes in three meteorological factors: temperature, relative humidity, and sunlight intensity. We perform these sensitivity studies over a wide range of nitrogen oxides (NO{sub x} = NO + NO{sub 2}) and nonmethane hydrocarbon (NMHC) concentrations, since these two chemicals are the dominant controllable pollutants that influence the chemical reactivity of the atmosphere.

  4. Rate of adverse reactions to more than 1 series of viscosupplementation.

    PubMed

    Webber, Tracy A; Webber, Anthony E; Matzkin, Elizabeth

    2012-04-01

    Viscosupplementation, hyaluronic acid treatment, is an ancillary method for treating patients with symptomatic stage I or II osteoarthritis. Previous studies reported that local reactions occurred more frequently in patients receiving >1 course of treatment compared with patients receiving their first course of treatment. One (2%) of 42 first series patients and 4 (21%) of 19 of repeated series patients had adverse reactions severe enough to seek unscheduled care.This study was performed to determine whether patients receiving >1 series of viscosupplementation had an increased adverse reaction rate. A retrospective chart review was performed on all patients who received >1 series of viscosupplementation during the study. A local adverse reaction was defined as acute swelling and pain in the knee, with no injury or trauma within 72 hours after hyaluronic acid injection.Twenty-eight knees received >1 series of viscosupplementation. The adverse reaction rate to second series injections was 1.28% (3.57% of knees). The adverse reaction rate to ≥3 series was 0.9% (6.67% of knees). This adverse reaction rate was significantly less than the 21% reported in previous studies for multiple series injections (z=-1.90; P<.05) and is not significantly different than the 2% rate of adverse reactions reported for first series injections. No significant difference existed in the adverse reaction rates between 2 series and ≥3 series of viscosupplementation.The current study suggests that the rate of adverse reaction was low at 1.28% of second series viscosupplementation.

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

    DOE PAGES

    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

  6. Determination of astrophysical thermonuclear rates with a bubble chamber: The {sup 12}C(αγ){sup 16}O reaction case

    SciTech Connect

    DiGiovine, B.; Henderson, D.; Holt, R. J.; Rehm, K. E.; Grames, J.; Meekins, D.; Poelker, M.; Suleiman, R.; Robinson, A.; Ugalde, C.; Sonnenschein, A.

    2013-11-07

    The {sup 12}C(αγ){sup 16}O reaction rate is considered one of the most important unknown parameters in the physics of structure and evolution of massive stars. While extensive experimental campaigns have been performed trying to improve the quality of the measurements, the rate still holds very large uncertainties. Here we discuss a new experimantal scheme to measure the cross section of this reaction with a bubble chamber and a bremsstrahlung beam. The main advantage of the technique is a gain in the luminosity of several orders of magnitude when compared to other ongoing experiments.

  7. 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.

  8. Mentally Retarded and Normal Children's Performance on Gross Motor Reaction- and Movement-Time Tasks with Varying Degrees of Uncertainty of Movement.

    ERIC Educational Resources Information Center

    Distefano, Emily A.; Brunt, Denis

    1982-01-01

    The effect of uncertainty of movement increased reaction time and movement time significantly in a simple task of running for mildly retarded eight- and ten-year old children. No change in performance was noted for normal children. (Author/PN)

  9. High-precision (p,t) reaction measurement to determine Ne18(α,p)Na21 reaction rates

    NASA Astrophysics Data System (ADS)

    Matic, A.; van den Berg, A. M.; Harakeh, M. N.; Wörtche, H. J.; Berg, G. P. A.; Couder, M.; Fisker, J. L.; Görres, 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.; Fujita, H.; Wakasa, T.; Hess, P. O.; Brown, B. A.; Schatz, H.

    2009-11-01

    x-ray bursts are identified as thermonuclear explosions in the outer atmosphere of accreting neutron stars. The thermonuclear runaway is fueled by the αp process that describes a sequence of (α,p) reactions triggered by the Ne18(α,p)Na21 breakout reaction from the hot CNO cycles. We studied the level structure of the compound nucleus Mg22 by measuring the Mg24(p,t)Mg22 reaction at the Grand Raiden spectrometer at Research Center for Nuclear Physics, Osaka. A large number of α-unbound states was identified and precise excitation energies were determined. Based on shell model and α-cluster model calculations we predict the level parameters for determining the stellar reaction rate of Ne18(α,p)Na21 for a wide temperature range. x-ray burst simulations have been performed to study the impact of the reaction on the x-ray burst luminosity.

  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. 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.

  12. 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.

  13. 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.

  14. Determination of photochemical reaction rates using thermal lens spectrometry

    NASA Astrophysics Data System (ADS)

    Astrath, N. G. C.; Astrath, F. B. G.; Shen, J.; Zhou, J.; Michaelian, K. H.; Fairbridge, C.; Malacarne, L. C.; Pedreira, P. R. B.; Baesso, M. L.

    2010-03-01

    Considering the time dependence of the absorption coefficient due to the photo-induced chemical reaction (PCR) and species diffusion, we calculate the temperature rise in the thermal lens (TL) effect and the TL signal at the detector plane. This theoretical approach removes the restriction that the PCR time constant is much greater than the characteristic TL time constant, which was assumed in a previously published model. Aqueous Cr(VI)-diphenylcarbazide solution is investigated, and quantitative experimental results for the thermal, optical and PCR properties of the sample are obtained. The relative difference between the parameters extracted from the same experimental data of the Cr(VI) solution using the previous and present models is found to be less than 5%, showing the present model can be used to study the PCR. Moreover the present model is more general than the previous one.

  15. Communication: rate coefficients from quasiclassical trajectory calculations from the reverse reaction: The Mu + H2 reaction re-visited.

    PubMed

    Homayoon, Zahra; Jambrina, Pablo G; Aoiz, F Javier; Bowman, Joel M

    2012-07-14

    In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011)] various calculations of the rate coefficient for the Mu + H(2) → MuH + H reaction were presented and compared to experiment. The widely used standard quasiclassical trajectory (QCT) method was shown to overestimate the rate coefficients by several orders of magnitude over the temperature range 200-1000 K. This was attributed to a major failure of that method to describe the correct threshold for the reaction owing to the large difference in zero-point energies (ZPE) of the reactant H(2) and product MuH (∼0.32 eV). In this Communication we show that by performing standard QCT calculations for the reverse reaction and then applying detailed balance, the resulting rate coefficient is in very good agreement with the other computational results that respect the ZPE, (as well as with the experiment) but which are more demanding computationally.

  16. REACTION RATES OF {sup 64}Ge(p,γ){sup 65}As AND {sup 65}As(p,γ){sup 66}Se AND THE EXTENT OF NUCLEOSYNTHESIS IN TYPE I X-RAY BURSTS

    SciTech Connect

    Lam, Y. H.; He, J. J.; Wang, M.; Zhang, Y. H.; Zhou, X. H.; Xu, H. S.; Parikh, A.; Schatz, H.; Brown, B. A.; Guo, B. E-mail: anuj.r.parikh@upc.edu

    2016-02-10

    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 {sup 64}Ge waiting point. Using the well known mass of {sup 64}Ge, the recently measured {sup 65}As mass, and large-scale shell model calculations, we have determined new thermonuclear rates of the {sup 64}Ge(p,γ){sup 65}As and {sup 65}As(p,γ){sup 66}Se 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 {sup 64}Ge 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 {sup 64}Ge rp-process waiting point cannot be ruled out. The nuclear physics uncertainties strongly affect XRB model predictions of the synthesis of {sup 64}Zn, 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 {sup 64}Ge waiting point in XRBs. These include the remaining uncertainty in the {sup 65}As mass, the uncertainty of the {sup 66}Se mass, and the remaining uncertainty in the {sup 65}As(p,γ){sup 66}Se reaction rate, which mainly originates from uncertain resonance energies.

  17. Critical evaluation and rate constants of chemoselective ligation reactions for stoichiometric conjugations in water.

    PubMed

    Saito, Fumito; Noda, Hidetoshi; Bode, Jeffrey W

    2015-04-17

    Chemoselective ligation reactions have contributed immensely to the development of organic synthesis and chemical biology. However, the ligation of stoichiometric amounts of large molecules for applications such as protein-protein conjugates is still challenging. Conjugation reactions need to be fast enough to proceed under dilute conditions and chemoselective in the presence of unprotected functional groups; the starting materials and products must be stable under the reaction conditions. To compare known ligation reactions for their suitability under these conditions, we determined the second-order rate constants of ligation reactions using peptide substrates with unprotected functional groups. The reaction conditions, the chemoselectivity of the reactions, and the stability of the starting materials and products were carefully evaluated. In some cases, the stability could be improved by modifying the substrate structure. These data obtained under the ligation conditions provide a useful guide to choose an appropriate ligation reaction for synthesis of large molecules by covalent ligation reactions of unprotected substrates in water.

  18. Reaction rates between water and some modified rapidly-reacting Karl Fischer reagents.

    PubMed

    Cedergren, A

    1978-04-01

    Rate constants were determined for the reaction between water and various modified Karl Fischer reagents containing formamide, dimethylformamide or N-methylformamide. It was shown that the reaction rate can be increased by a factor of 100 by using a reagent containing 40% v/v formamide in pyridine compared to that obtained by use of the conventional methanolic reagent.

  19. Putting Reaction Rates and Collision Theory in the Hands of Your Students.

    ERIC Educational Resources Information Center

    Evenson, Andy

    2002-01-01

    Describes a simulation that can be used to give concrete analogies of collision theory and the factors that affect reaction rates including temperature, concentration, catalyst, and molecular orientation. The simulation works best if done as an introduction to the concepts to help prevent misconceptions about reaction rates and collision theory.…

  20. Absolute rate parameters for the reaction of ground state atomic oxygen with carbonyl sulfide

    NASA Technical Reports Server (NTRS)

    Klemm, R. B.; Stief, L. J.

    1974-01-01

    The rate parameters for the reaction of O(3P) with carbonyl sulfide, O(3P) + OCS yields CO + SO, have been determined directly by monitoring O(3P) using the flash photolysis-resonance fluorescence technique. The value for reaction rate was measured over a temperature range of 263-502 K and the data were fitted to an Arrhenius expression with good linearity. A comparison of the present results with those from previous studies of this reaction is also presented.

  1. 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.

  2. Reducing uncertainties in nucleation rates: A comparison of measurements and simulations

    SciTech Connect

    Nadykto, A. B.; Nazarenko, K. M.; Markov, P. N.; Yu, F.

    2016-06-08

    Recently, large uncertainties in amine nucleation thermodynamics associated with the description of interactions of H{sub 2}SO{sub 4}, the key atmospheric nucleation precursor, with pre-nucleation clusters have been revealed. Here we investigate the formation of (H{sub 2}SO{sub 4}){sub 2}(H{sub 2}O){sub n} (n=0-5) clusters via H{sub 2}O–induced dimerization using conventional RI-MP2 and PW91PW91 methods and recently developed multistep BRIMP2 and B3RICC2 methods widely used in nucleation studies and compare the obtained results with measurements for equilibrium constants of H{sub 2}O–induced dimerization. Variations in K{sub p} and Gibbs free energies predicted by different methods were found to be unexpectedly large, several times of those in hydration free energies commonly used to benchmark computational quantum methods. This means that the common hydration benchmarks are not fully representative of nucleation and that the validation of quantum methods to be recommended for use in nucleation studies is impossible without a thorough assessment of H{sub 2}SO{sub 4}-H{sub 2}SO{sub 4} interactions. We show clearly that only conventional RI-MP2 and PW91PW91 methods are consistent with experiments and that a thorough validation of theoretical predictions against experimental data on H{sub 2}SO{sub 4} clustering is needed prior to recommending a quantum–chemical method for use in nucleation research. We also shows that conclusions about the role of Amine-Enhanced Ternary Homogeneous Nucleation (ATHN) in atmospheric nucleation may be affected by the large uncertainties in nucleation thermodynamics associated with the application of B3RICC2 and BRIMP2 methods and may need a thorough revision.

  3. Reducing uncertainties in nucleation rates: A comparison of measurements and simulations

    NASA Astrophysics Data System (ADS)

    Nadykto, A. B.; Nazarenko, K. M.; Markov, P. N.; Yu, F.

    2016-06-01

    Recently, large uncertainties in amine nucleation thermodynamics associated with the description of interactions of H2SO4, the key atmospheric nucleation precursor, with pre-nucleation clusters have been revealed. Here we investigate the formation of (H2SO4)2(H2O)n (n=0-5) clusters via H2O-induced dimerization using conventional RI-MP2 and PW91PW91 methods and recently developed multistep BRIMP2 and B3RICC2 methods widely used in nucleation studies and compare the obtained results with measurements for equilibrium constants of H2O-induced dimerization. Variations in Kp and Gibbs free energies predicted by different methods were found to be unexpectedly large, several times of those in hydration free energies commonly used to benchmark computational quantum methods. This means that the common hydration benchmarks are not fully representative of nucleation and that the validation of quantum methods to be recommended for use in nucleation studies is impossible without a thorough assessment of H2SO4-H2SO4 interactions. We show clearly that only conventional RI-MP2 and PW91PW91 methods are consistent with experiments and that a thorough validation of theoretical predictions against experimental data on H2SO4 clustering is needed prior to recommending a quantum-chemical method for use in nucleation research. We also shows that conclusions about the role of Amine-Enhanced Ternary Homogeneous Nucleation (ATHN) in atmospheric nucleation may be affected by the large uncertainties in nucleation thermodynamics associated with the application of B3RICC2 and BRIMP2 methods and may need a thorough revision.

  4. Evaluating release alternatives for a long-lived bird species under uncertainty about long-term demographic rates

    USGS Publications Warehouse

    Moore, Clinton T.; Converse, Sarah J.; Folk, Martin J.; Runge, Michael C.; Nesbitt, Stephen A.

    2012-01-01

    The release of animals to reestablish an extirpated population is a decision problem that is often attended by considerable uncertainty about the probability of success. Annual releases of captive-reared juvenile Whooping Cranes (Grus americana) were begun in 1993 in central Florida, USA, to establish a breeding, non-migratory population. Over a 12-year period, 286 birds were released, but by 2004, the introduced flock had produced only four wild-fledged birds. Consequently, releases were halted over managers' concerns about the performance of the released flock and uncertainty about the efficacy of further releases. We used data on marked, released birds to develop predictive models for addressing whether releases should be resumed, and if so, under what schedule. To examine the outcome of different release scenarios, we simulated the survival and productivity of individual female birds under a baseline model that recognized age and breeding-class structure and which incorporated empirically estimated stochastic elements. As data on wild-fledged birds from captive-reared parents were sparse, a key uncertainty that confronts release decision-making is whether captive-reared birds and their offspring share the same vital rates. Therefore, we used data on the only population of wild Whooping Cranes in existence to construct two alternatives to the baseline model. The probability of population persistence was highly sensitive to the choice of these three models. Under the baseline model, extirpation of the population was nearly certain under any scenario of resumed releases. In contrast, the model based on estimates from wild birds projected a high probability of persistence under any release scenario, including cessation of releases. Therefore, belief in either of these models suggests that further releases are an ineffective use of resources. In the third model, which simulated a population Allee effect, population persistence was sensitive to the release decision

  5. 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.

  6. Pop-it beads to introduce catalysis of reaction rate and substrate depletion effects.

    PubMed

    Gehret, Austin U

    2017-03-04

    A kinesthetic classroom activity was designed to help students understand enzyme activity and catalysis of reaction rate. Students served the role of enzymes by manipulating Pop-It Beads as the catalytic event. This activity illuminates the relationship between reaction rate and reaction progress by allowing students to experience first-hand the effect of substrate depletion on catalyzed reaction rate. Preliminary findings based on survey results and exam performance suggest the activity could prove beneficial to students in the targeted learning outcomes. Unique to previous kinesthetic approaches that model Michaelis-Menten kinetics, this activity models the effects of substrate depletion on catalyzed reaction rate. Therefore, it could prove beneficial for conveying the reasoning behind the initial rate simplification used in Michaelis-Menten kinetics. © 2016 by The International Union of Biochemistry and Molecular Biology, 45(2):179-183, 2017. © 2016 The International Union of Biochemistry and Molecular Biology.

  7. Reaction Rates in Deformation and Hydrostatic Experiments in the Anhydrous System Anorthite - Forsterite

    NASA Astrophysics Data System (ADS)

    Stunitz, H.; de Ronde, A.; Tullis, J.

    2004-12-01

    The reaction anorthite + forsterite --> cpx + opx + spinel ± gnt proceeds at high temperatures and elevated pressures in the lower crust and upper mantle. This solid-solid reaction was studied experimentally at 900° C in the pressure range of 1000 to 1600 MPa in both shearing deformation and hydrostatic experiments. Powder mixtures (1:1 by vol) of anorthite (An92) and forsterite (Fo93) are hot pressed at 970° C, 750 MPa for 48 hrs in a Griggs apparatus and deformed (˙ γ = 5 × 105 sec-1) after adjustment of P and T to run conditions. H2O content of the samples has been measured by FTIR and is < 30 ppm. At small pressure overstepping (ca. 200 to 300 MPa) undeformed samples show only 10 % reaction progress after 168 hrs, whereas reaction progress in deformed samples after 72 hrs is 60 %. At greater pressure overstepping (700 to 800 MPa) the difference between deformed and undeformed samples is less pronounced (95 % after 60 hrs deformed, 75 % after 168 hrs undeformed) but still present. At greater pressure overstepping, undeformed samples show an exponential reaction rate, whereas that of deformed samples is always linear. Samples initially deformed and then kept hydrostatically show a fast initial reaction rate (85 % of total reaction progress after 0.25 of total run time), followed by a slower reaction progress (15 % reaction after 0.75 of total time) under hydrostatic conditions. The difference in reaction progress is mainly attributed to different nucleation rates. In all experiments, enstatite rims form around olivine grains separating those from other reaction products. Such coronas are indicative of diffusion-controlled reactions. Plots of rim thickness vs time indicate a relative increase of the bulk diffusion coefficient by a factor 5 in the deformed samples compared to undeformed. However, as the grain size of reaction products of deformed samples is 10 times smaller than in undeformed ones, the nucleation rate in deformed samples is ˜ 5000 times

  8. An Experiment to Demonstrate How a Catalyst Affects the Rate of a Reaction

    NASA Astrophysics Data System (ADS)

    Copper, Christine L.; Koubek, Edward

    1999-12-01

    By performing this experiment, students in general and introductory physical chemistry can learn more about the effect of a catalyst on a chemical reaction. This experiment, which is a modified version of the traditional iodine clock reaction, allows students to calculate rates of reaction, orders of reactants, and activation energies. It also lets students discover that to increase a reaction's rate, a catalyst need only provide any additional pathway for the reaction, not necessarily a pathway having a lower activation energy. This experiment is designed so that students will notice that the amount of catalyst used is important. Furthermore, the slight amount (~10-5 M MoO42-) of catalyst needed to increase the overall reaction rate and the abrupt color change that occurs seem to pique the interest of our students.

  9. 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.

  10. Reaction of singlet oxygen with tryptophan in proteins: a pronounced effect of the local environment on the reaction rate.

    PubMed

    Jensen, Rasmus Lybech; Arnbjerg, Jacob; Ogilby, Peter R

    2012-06-13

    Singlet molecular oxygen, O(2)(a(1)Δ(g)), can influence many processes pertinent to the function of biological systems, including events that result in cell death. Many of these processes involve a reaction between singlet oxygen and a given amino acid in a protein. As a result, the behavior of that protein can change, either because of a structural alteration and/or a direct modification of an active site. Surprisingly, however, little is known about rate constants for reactions between singlet oxygen and amino acids when the latter are in a protein. In this report, we demonstrate using five separate proteins, each containing only a single tryptophan residue, that the rate constant for singlet oxygen reaction with tryptophan depends significantly on the position of this amino acid in the protein. Most importantly, the reaction rate constant depends not only on the accessibility of the tryptophan residue to oxygen, but also on factors that characterize the local molecular environment of the tryptophan in the protein. The fact that the local protein environment can either appreciably inhibit or accelerate the reaction of singlet oxygen with a given amino acid can have significant ramifications for singlet-oxygen-mediated events that perturb cell function.

  11. Renormalization-scale uncertainty in the decay rate of false vacuum

    NASA Astrophysics Data System (ADS)

    Endo, Motoi; Moroi, Takeo; Nojiri, Mihoko M.; Shoji, Yutaro

    2016-01-01

    We study radiative corrections to the decay rate of false vacua, paying particular attention to the renormalization-scale dependence of the decay rate. The decay rate exponentially depends on the bounce action. The bounce action itself is renormalization-scale dependent. To make the decay rate scale-independent, radiative corrections, which are due to the field fluctuations around the bounce, have to be included. We show quantitatively that the inclusion of the fluctuations suppresses the scale dependence, and hence is important for the precise calculation of the decay rate. We also apply our analysis to a supersymmetric model and show that the radiative corrections are important for the Higgs-stau system with charge breaking minima.

  12. 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

  13. 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

  14. An uncertainty framework to estimate dense water formation rates : case study in the Northwestern Mediterranean.

    NASA Astrophysics Data System (ADS)

    Waldman, Robin; Somot, Samuel; Herrmann, Marine; Sevault, Florence; Estournel, Claude; Testor, Pierre

    2015-04-01

    The Northwestern Mediterranean (NWMed) sea is a key region for the Mediterranean thermohaline circulation as it includes the main deep water formation sites of the Western Mediterranean. The Mediterranean Ocean Observing System for the Environment (MOOSE) has been implemented since 2007 over that region to characterize the space and time variability of the main water masses up to interannual (yearly summer cruises) scale. However, despite a large covering of the NWMed region, the limited number of conductivity, temperature and depth (CTD) casts leads to subsampling errors and advocates for an uncertainty assessment of large-scale hydrology estimates. This study aims at estimating the error related to subsampling in time and space. For that purpose, an Observing System Simulation Experiment (OSSE) is performed with an eddy-permitting Mediterranean sea model (NEMOMED12) and an eddy-resolving NWMed sea model (SYMPHONIE). A subsampling of the full model fields in time and space allows for an error estimate in terms of large-scale hydrology. The methodology is applied to dense water volume estimates for the period july 2012 - july 2013. Secondly, an optimization framework is proposed to evaluate and improve MOOSE network's performances under a series of scientific constraints. The results will be discussed for an application in MOOSE observing network, as well as the main assumptions, the stakes and limitations of this framework.

  15. 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.

  16. Reaction kinetics and critical phenomena: rates of some first order gas evolution reactions in binary solvents with a consolute point.

    PubMed

    Kim, Yeong Woo; Baird, James K

    2005-06-02

    We have measured the rate of carbon dioxide evolution in the aniline catalyzed decomposition of acetone dicarboxylic acid in a mixture of isobutyric acid + water near its consolute point. Within a temperature interval of 1 degrees C, which included the critical solution temperature, the first-order rate constant oscillated in magnitude by about 10% as it passed through three complete cycles of slowing down followed by speeding up. Whereas we can find no ready explanation for the speeding up, we suggest that, because the mixture contained no inert components, the slowing down should belong to the Griffiths-Wheeler class of strong critical effects [Phys. Rev. A 1970, 2, 1047]. As a check on this conclusion, we have measured the rate of the SN1 decomposition of benzene diazonium tetrafluoroborate in 2-butoxyethanol + water near the lower critical solution temperature and also the rate of the acid-catalyzed decomposition of ethyl diazoacetate in isobutyric acid + water near the upper critical solution temperature. Both of these reactions evolve nitrogen. In the first reaction, 2-butoxyethanol is inert, whereas in the second, isobutyric acid is inert. In both cases, because there was one inert component, we regarded the response of the rate constant to temperature in the critical region to be representative of the Griffiths-Wheeler class of weak critical effects. Within our accuracy of measurement of about 2% in the rate constant and about 1 mK in the temperature, we could detect no effect of the critical point on the rates of either of these reactions, suggesting that a weak effect may be too small to be seen with our experimental apparatus. The successful observation of a critical effect in the rate of decomposition of acetone dicarboxylic acid proves, however, that kinetic critical phenomena are observable in heterogeneous reactions.

  17. Chiral Polymerization in Open Systems From Chiral-Selective Reaction Rates

    NASA Astrophysics Data System (ADS)

    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.

  18. 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.

  19. 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.

  20. Rate variations of a hetero-Diels--Alder reaction in supercritical fluid CO{sub 2}

    SciTech Connect

    Thompson, R.L.; Glaeser, R.; Bush, D.; Liotta, C.L.; Eckert, C.A.

    1999-11-01

    The hetero-Diels-Alder reaction between anthracene and excess 4-phenyl-1,2,4-triazoline-3,5-dione has been investigated in supercritical CO{sub 2} at 40 C and pressures between 75 and 216 bar. Biomolecular reaction rate constants have been measured via fluorescence spectroscopy by following the decrease in anthracene concentration with reaction time. The reaction rate is elevated in the vicinity of the critical pressure. This difference is consistent with local composition enhancement and can be modeled with the Peng-Robinson equation of state.

  1. Mathematical model of reaction rate oscillations on a chain of nm-sized catalyst particles

    NASA Astrophysics Data System (ADS)

    Peskov, N. V.; Slinko, M. M.; Jaeger, N. I.

    2003-05-01

    The model of reaction rate oscillations over the surface of nanoparticles embedded into zeolite matrix is numerically investigated. The reaction rate oscillations on each particle are described by a lumped model. The reactions on separate particles interact via the gas diffusion through the pores, which is modeled in the frame of the Maxwell-Stefan approach. The reaction reveals a complex dynamical behavior if a nonhomogeneous distribution of reagent concentrations exists along the chain of particles with a sufficiently large gradient near the ends of the chain.

  2. Stochastic behavior and stirring rate effects in the chlorite-iodide reaction

    NASA Astrophysics Data System (ADS)

    Nagypál, István; Epstein, Irving R.

    1988-12-01

    The autocatalytic reaction between chlorite and iodide ions in a closed system is a clock reaction, showing a sudden appearance of brown I2 followed by a rapid disappearance of the color. Under certain conditions, the reaction time displays a striking irreproducibility. This stochastic behavior is studied potentiometrically and spectrophotometrically as a function of initial [I- ], stirring rate and solution volume. The results imply that the irreproducibility is an inherent feature of the reaction generated by fluctuations in the solution after it is ``well mixed.'' The key contributors to the stochasticity are local concentration inhomogeneities resulting from imperfect stirring and the ``supercatalytic'' reaction kinetics. A qualitative explanation is given that incorporates these aspects.

  3. 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

  4. 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

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

    PubMed

    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

    2014-07-01

    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. 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 1(st) January - 31(st) 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 reactions. 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. 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 are required in Namibia.

  6. Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

    PubMed

    Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

    2017-02-09

    The reaction of the simplest Criegee intermediate CH2OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10(-13) cm(3) s(-1). The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH2OO with H2S is 2-3 orders of magnitude faster than the reaction with H2O monomer. Though rates of CH2OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H2S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH2OO + H2S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

  7. 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

    2016-11-05

    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.

  8. Characterization of shock-dependent reaction rates in an aluminum/perfluoropolyether pyrolant

    NASA Astrophysics Data System (ADS)

    Wilson, Dennis; Granier, John; Johnson, Richard; Littrell, Donald

    2017-01-01

    Energetic formulations of perfluoropolyether (PFPE) and aluminum are highly non-ideal. They release energy via a fast self-oxidized combustion wave rather than a true self-sustaining detonation. Unlike high explosives, the reactions are shock dependent and can be overdriven to control energy release rate. Reaction rate experiments show that the velocity can vary from 1.25 to 3 km/s. This paper examines the effect of the initial shock conditions upon the reaction rate of the explosive. The following conditions were varied in a series of reaction rate experiments: the high explosive booster mass and geometry; shock attenuation; confinement; and rate stick diameter and length. Several experiments designed to isolate and quantify these dependencies are described and summarized.

  9. Atmospheric chemistry of toxic contaminants. 1. Reaction rates and atmospheric persistence

    SciTech Connect

    Grosjean, D. )

    1990-10-01

    Using structure-reactivity relationships between reaction rate constants and ionization potentials for structural homologues, estimates are presented for the rate constants of the reactions of ozone, the hydroxyl radical, and the nitrate radical with forty toxic air contaminants for which no or little data are available. These rate constants are in turn used to estimate the atmospheric persistence of saturated aliphatics, unsaturated aliphatics, and aromatic toxic organics. The corresponding atmospheric half-lives for removal by chemical reactions range from a few hours for the most reactive toxics (chloroprene, hexachlorocyclo-pentadiene, cresols, nitrosamines, maleic anhydride) to several months for the least reactive compounds (nitrobenzene, methyl bromide, phosgene).

  10. Rate constants of the reaction of C2-C4 peroxy radicals with OH radicals

    NASA Astrophysics Data System (ADS)

    Assaf, Emmanuel; Tanaka, Shisei; Kajii, Yoshizumi; Schoemaecker, Coralie; Fittschen, Christa

    2017-09-01

    The rate constants for the reaction of three peroxy radicals with OH have been measured using different precursors. Peroxy radicals have been prepared by either the reaction of Cl-atoms with C2H6, C3H8 and n-C4H10 or through photolysis of the corresponding alkyliodide. Using Cl-atoms, the following rate constants have been measured: Experiments using 248 nm photolysis of the corresponding alkyliodides as precursor enhances the rate constants by a factor of two, bringing up the suspicion of a fast reaction between I-atoms and OH radicals.

  11. A mixed-phase relative rates technique for measuring aerosol reaction kinetics

    NASA Astrophysics Data System (ADS)

    Hearn, John D.; Smith, Geoffrey D.

    2006-09-01

    A mixed-phase relative rates approach for measuring rates of reaction in aerosols is presented. Using this method the rate of reaction of methyl oleate (MO) particles, normalized to the gas-particle collision rate, was measured to be γMO = 1.12 (+/-0.36) × 10-3 with 2-methyl-2-butene as the gas-phase reference. This value compares favorably with our previously published value of 1.23 × 10-3 measured using an absolute technique. Reaction of bis(2-ethylhexyl) sebacate (BES) particles with Cl and OH radicals was also studied using acetone and hexanal, respectively, as the gas-phase references. The rates of reaction of BES, normalized to the gas-particle collision rate, were measured to be γBES = 1.8 (-0.3+0.8) and γBES = 2.0 (-0.1+0.6) with Cl and OH, respectively. These fast rates of reaction (γBES > 1) imply that secondary reactions, perhaps involving radical chain mechanisms, could impact the rate at which organic particles are oxidized in the atmosphere.

  12. Imaginary time approach for reaction rate of triple-alpha process

    NASA Astrophysics Data System (ADS)

    Yabana, Kazuhiro; Akahori, Takahiko; Funaki, Yasuro

    2014-09-01

    We propose a new theoretical approach for the radiative capture reaction rate, which we call the imaginary-time theory. In the theory, inverse temperature is identified with the temperature. Since reaction rates can be calculated without solving any scattering problem in the theory, it is ideally suited for the triple-alpha process in which scattering problem of three charged particles has caused difficulties. Using the imaginary-time theory, we obtain the triple-alpha reaction rate in the quantum three-body model treating alpha particles as structureless point particles. The calculated rate is almost identical to the standard NACRE rate. We have also found that the reaction mechanism of the triple-alpha process changes at exactly the same temperatures as those in empirical theories. We may show that it is possible to derive an analytical formula close to that of the NACRE rate, if we introduce some assumptions in the three-body model. We demonstrate that, if we introduce a coupled-channel expansion with a truncation, reaction rate is substantially overestimated. This finding may help to explain the very different reaction rates obtained so far using different theoretical approaches.

  13. Comparing transfusion reaction rates for various plasma types: a systematic review and meta-analysis/regression.

    PubMed

    Saadah, Nicholas H; van Hout, Fabienne M A; Schipperus, Martin R; le Cessie, Saskia; Middelburg, Rutger A; Wiersum-Osselton, Johanna C; van der Bom, Johanna G

    2017-09-01

    We estimated rates for common plasma-associated transfusion reactions and compared reported rates for various plasma types. We performed a systematic review and meta-analysis of peer-reviewed articles that reported plasma transfusion reaction rates. Random-effects pooled rates were calculated and compared between plasma types. Meta-regression was used to compare various plasma types with regard to their reported plasma transfusion reaction rates. Forty-eight studies reported transfusion reaction rates for fresh-frozen plasma (FFP; mixed-sex and male-only), amotosalen INTERCEPT FFP, methylene blue-treated FFP, and solvent/detergent-treated pooled plasma. Random-effects pooled average rates for FFP were: allergic reactions, 92/10(5) units transfused (95% confidence interval [CI], 46-184/10(5) units transfused); febrile nonhemolytic transfusion reactions (FNHTRs), 12/10(5) units transfused (95% CI, 7-22/10(5) units transfused); transfusion-associated circulatory overload (TACO), 6/10(5) units transfused (95% CI, 1-30/10(5) units transfused); transfusion-related acute lung injury (TRALI), 1.8/10(5) units transfused (95% CI, 1.2-2.7/10(5) units transfused); and anaphylactic reactions, 0.8/10(5) units transfused (95% CI, 0-45.7/10(5) units transfused). Risk differences between plasma types were not significant for allergic reactions, TACO, or anaphylactic reactions. Methylene blue-treated FFP led to fewer FNHTRs than FFP (risk difference = -15.3 FNHTRs/10(5) units transfused; 95% CI, -24.7 to -7.1 reactions/10(5) units transfused); and male-only FFP led to fewer cases of TRALI than mixed-sex FFP (risk difference = -0.74 TRALI/10(5) units transfused; 95% CI, -2.42 to -0.42 injuries/10(5) units transfused). Meta-regression demonstrates that the rate of FNHTRs is lower for methylene blue-treated compared with FFP, and the rate of TRALI is lower for male-only than for mixed-sex FFP; whereas no significant differences are observed between plasma types for allergic

  14. New reaction rate for {sup 16}O(p,{gamma}){sup 17}F and its influence on the oxygen isotopic ratios in massive AGB stars

    SciTech Connect

    Iliadis, C.; Angulo, C.; Descouvemont, P.; Lugaro, M.; Mohr, P.

    2008-04-15

    The {sup 16}O(p,{gamma}){sup 17}F reaction rate is revisited with special emphasis on the stellar temperature range of T=60-100 MK, important for hot bottom burning in asymptotic giant branch (AGB) stars. We evaluate existing cross-section data that were obtained since 1958 and, if appropriate, correct published data for systematic errors that were not noticed previously, including the effects of coincidence summing and updated effective stopping powers. The data are interpreted by using two different models of nuclear reactions, that is, a potential model and R-matrix theory. A new astrophysical S factor and recommended thermonuclear reaction rates are presented. As a result of our work, the {sup 16}O(p,{gamma}){sup 17}F reaction has now the most precisely known rate involving any target nucleus in the mass A{>=}12 range, with reaction rate errors of about 7% over the entire temperature region of astrophysical interest (T=0.01-2.5 GK). The impact of the present improved reaction rate with its significantly reduced uncertainties on the hot bottom burning in AGB stars is discussed. In contrast to earlier results we find now that there is not clear evidence to date for any stellar grain origin from massive AGB stars.

  15. A methodology to reduce uncertainties in the high-flow portion of a rating curve

    USDA-ARS?s Scientific Manuscript database

    Flow monitoring at watershed scale relies on the establishment of a rating curve that describes the relationship between stage and flow and is developed from actual flow measurements at various stages. Measurement errors increase with out-of-bank flow conditions because of safety concerns and diffic...

  16. Supernova Relic Neutrinos and the Supernova Rate Problem: Analysis of Uncertainties and Detectability of ONeMg and Failed Supernovae

    NASA Astrophysics Data System (ADS)

    Mathews, Grant J.; Hidaka, Jun; Kajino, Toshitaka; Suzuki, Jyutaro

    2014-08-01

    Direct measurements of the core collapse supernova rate (R SN) in the redshift range 0 <= z <= 1 appear to be about a factor of two smaller than the rate inferred from the measured cosmic massive star formation rate (SFR). This discrepancy would imply that about one-half of the massive stars that have been born in the local observed comoving volume did not explode as luminous supernovae. In this work, we explore the possibility that one could clarify the source of this "supernova rate problem" by detecting the energy spectrum of supernova relic neutrinos with a next generation 106 ton water Čerenkov detector like Hyper-Kamiokande. First, we re-examine the supernova rate problem. We make a conservative alternative compilation of the measured SFR data over the redshift range 0 <=z <= 7. We show that by only including published SFR data for which the dust obscuration has been directly determined, the ratio of the observed massive SFR to the observed supernova rate R SN has large uncertainties {\\sim }1.8^{+1.6}_{-0.6} and is statistically consistent with no supernova rate problem. If we further consider that a significant fraction of massive stars will end their lives as faint ONeMg SNe or as failed SNe leading to a black hole remnant, then the ratio reduces to {\\sim }1.1^{+1.0}_{-0.4} and the rate problem is essentially solved. We next examine the prospects for detecting this solution to the supernova rate problem. We first study the sources of uncertainty involved in the theoretical estimates of the neutrino detection rate and analyze whether the spectrum of relic neutrinos can be used to independently identify the existence of a supernova rate problem and its source. We consider an ensemble of published and unpublished core collapse supernova simulation models to estimate the uncertainties in the anticipated neutrino luminosities and temperatures. We illustrate how the spectrum of detector events might be used to establish the average neutrino temperature and

  17. Supernova relic neutrinos and the supernova rate problem: Analysis of uncertainties and detectability of ONeMg and failed supernovae

    SciTech Connect

    Mathews, Grant J.; Hidaka, Jun; Kajino, Toshitaka; Suzuki, Jyutaro

    2014-08-01

    Direct measurements of the core collapse supernova rate (R{sub SN}) in the redshift range 0 ≤ z ≤ 1 appear to be about a factor of two smaller than the rate inferred from the measured cosmic massive star formation rate (SFR). This discrepancy would imply that about one-half of the massive stars that have been born in the local observed comoving volume did not explode as luminous supernovae. In this work, we explore the possibility that one could clarify the source of this 'supernova rate problem' by detecting the energy spectrum of supernova relic neutrinos with a next generation 10{sup 6} ton water Čerenkov detector like Hyper-Kamiokande. First, we re-examine the supernova rate problem. We make a conservative alternative compilation of the measured SFR data over the redshift range 0 ≤z ≤ 7. We show that by only including published SFR data for which the dust obscuration has been directly determined, the ratio of the observed massive SFR to the observed supernova rate R{sub SN} has large uncertainties ∼1.8{sub −0.6}{sup +1.6} and is statistically consistent with no supernova rate problem. If we further consider that a significant fraction of massive stars will end their lives as faint ONeMg SNe or as failed SNe leading to a black hole remnant, then the ratio reduces to ∼1.1{sub −0.4}{sup +1.0} and the rate problem is essentially solved. We next examine the prospects for detecting this solution to the supernova rate problem. We first study the sources of uncertainty involved in the theoretical estimates of the neutrino detection rate and analyze whether the spectrum of relic neutrinos can be used to independently identify the existence of a supernova rate problem and its source. We consider an ensemble of published and unpublished core collapse supernova simulation models to estimate the uncertainties in the anticipated neutrino luminosities and temperatures. We illustrate how the spectrum of detector events might be used to establish the average

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

    NASA Astrophysics Data System (ADS)

    Skakun, Ye.; Rauscher, T.

    2010-08-01

    Astrophysical S-factors of (p, n) reactions on 99Ru, 100Ru, 101Ru, and 102Ru 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.

  19. 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.

  20. 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.

  1. Reducing Uncertainties in the Production of the Gamma-emitting Nuclei 26Al, 44Ti, and 60Fe in Core-collapse Supernovae by Using Effective Helium Burning Rates

    NASA Astrophysics Data System (ADS)

    Austin, Sam M.; West, Christopher; Heger, Alexander

    2017-04-01

    We have used effective reaction rates (ERRs) for the helium burning reactions to predict the yield of the gamma-emitting nuclei 26Al, 44Ti, and 60Fe in core-collapse supernovae (SNe). The variations in the predicted yields for values of the reaction rates allowed by the ERR are much smaller than obtained previously, and smaller than other uncertainties. A “filter” for SN nucleosynthesis yields based on pre-SN structure was used to estimate the effect of failed SNe on the initial mass function averaged yields; this substantially reduced the yields of all these isotopes, but the predicted yield ratio 60Fe/26Al was little affected. The robustness of this ratio is promising for comparison with data, but it is larger than observed in nature; possible causes for this discrepancy are discussed.

  2. Recommended Thermal Rate Coefficients for the C + H3 + Reaction and Some Astrochemical Implications

    NASA Astrophysics Data System (ADS)

    Vissapragada, S.; Buzard, C. F.; Miller, K. A.; O'Connor, A. P.; de Ruette, N.; Urbain, X.; Savin, D. W.

    2016-11-01

    We incorporate our experimentally derived thermal rate coefficients for C + {{{H}}}3+ forming CH+ and CH2 + into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and instead we use a more versatile fitting formula. At a temperature of 10 K and a density of 104 cm-3, we find no significant differences in the predicted chemical abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. In addition, we find that the relatively small error on our thermal rate coefficients, ˜15%, significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.

  3. Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

    NASA Technical Reports Server (NTRS)

    Hsu, K.-J.; DeMore, W. B.

    1995-01-01

    Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

  4. Development of Theoretical Methods for Predicting Solvent Effects on Reaction Rates in Supercritical Water Oxidation Processes

    DTIC Science & Technology

    2007-11-02

    Tucker, manuscript in preparation. “Examination of Nonequilibrium Solvent Effects on an SN2 Reaction in Supercritical Water,” R. Behera, B...DATES COVERED Final: 7/1/99 - 12/31/02 4. TITLE AND SUBTITLE Development of theoretical methods for predicting solvent effects on reactions ...computational methods for predicting how reaction rate constants will vary with thermodynamic condition in supercritical water (SCW). Towards this

  5. 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.

  6. 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.

  7. Quantitative rate determination by dynamic nuclear polarization enhanced NMR of a Diels-Alder reaction.

    PubMed

    Zeng, Haifeng; Lee, Youngbok; Hilty, Christian

    2010-11-01

    Emerging techniques for hyperpolarization of nuclear spins, foremost dynamic nuclear polarization (DNP), lend unprecedented sensitivity to nuclear magnetic resonance spectroscopy. Sufficient signal can be obtained from a single scan, and reactions even far from equilibrium can be studied in real-time. When following the progress of a reaction by nuclear magnetic resonance, however, spin relaxation occurs concomitantly with the reaction to alter resonance line intensities. Here, we present a model for accounting for spin-relaxation in such reactions studied by hyperpolarized NMR. The model takes into account auto- and cross-relaxation in dipole-dipole coupled spin systems and is therefore applicable to NMR of hyperpolarized protons, the most abundant NMR-active nuclei. Applied to the Diels-Alder reaction of 1,4-dipheneylbutadiene (DPBD) with 4-phenyl-1,2,4-triazole-3,5-dione (PTD), reaction rates could be obtained accurately and reproducibly. Additional parameters available from the same experiment include relaxation rates of the reaction product, which may yield further information about the molecular properties of the product. The method presented is also compatible with an experiment where a single spin in the reactant is labeled in its spin-state by a selective radio frequency pulse for subsequent tracking through the reaction, allowing the unambiguous identification of its position in the product molecule. In this case, the chemical shift specificity of high-resolution NMR can allow for the simultaneous determination of reaction rates and mechanistic information in one experiment.

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

    NASA Astrophysics Data System (ADS)

    Newton, J. R.; Longland, R.; Iliadis, C.

    2008-08-01

    We address the problem of extrapolating experimental thermonuclear reaction rates toward high stellar temperatures (T>1 GK) by using statistical model (Hauser-Feshbach) results. Reliable reaction rates at such temperatures are required for studies of advanced stellar burning stages, supernovae, and x-ray bursts. Generally accepted methods are based on the concept of a Gamow peak. We follow recent ideas that emphasized the fundamental shortcomings of the Gamow peak concept for narrow resonances at high stellar temperatures. Our new method defines the effective thermonuclear energy range (ETER) by using the 8th, 50th, and 92nd percentiles of the cumulative distribution of fractional resonant reaction rate contributions. This definition is unambiguous and has a straightforward probability interpretation. The ETER is used to define a temperature at which Hauser-Feshbach rates can be matched to experimental rates. This matching temperature is usually much higher compared to previous estimates that employed the Gamow peak concept. We suggest that an increased matching temperature provides more reliable extrapolated reaction rates since Hauser-Feshbach results are more trustwhorthy the higher the temperature. Our ideas are applied to 21 (p,γ), (p,α), and (α,γ) reactions on A=20-40 target nuclei. For many of the cases studied here, our extrapolated reaction rates at high temperatures differ significantly from those obtained using the Gamow peak concept.

  9. Oxidation of CO by N/sub 2/O between 1076 and 1228 K: determination of the rate constant of the exchange reaction

    SciTech Connect

    Loirat, H.; Caralp, F.; Destriau, M.; Lesclaux, R.

    1987-12-17

    New measurements of the rate constant of the direct reaction of CO with N/sub 2/O are reported with the principal purpose of removing some of the remaining discrepancies on its value. Experiments were performed at lower temperatures (1076-1228 K) and lower pressure (approx. 15 Torr) than those prevailing in most of previous works, by using a static reactor. It is shown that, under these experimental conditions, the reaction proceeds essentially according to the direct reaction CO + N/sub 2/O ..-->.. CO/sub 2/ + N/sub 2/ (1). The previously proposed wet mechanism is not significant under our experimental conditions. It has to be taken into account, however, to describe the observed production and consumption of molecular oxygen. The Arrhenius expression derived from these experiments is k/sub 1/ = 10/sup 14.4 +/- 0.3 exp(-(46 +- 2) kcal mol/sup -1/RT) cm/sup 3/ mol/sup -1/ s/sup -1/. A detailed analysis of the results shows that the uncertainties in side reactions do not greatly influence the value of k/sub 1/. A critical discussion of the data reported in the literature is presented. In spite of remaining uncertainties in the reaction mechanism, the present results, obtained in a low-temperature range, show that the low activation energy values of reaction 1, reported in several works performed at higher temperatures, are highly unlikely

  10. The homogeneous ice nucleation rate of water droplets produced in a microfluidic device and the role of temperature uncertainty.

    PubMed

    Riechers, Birte; Wittbracht, Frank; Hütten, Andreas; Koop, Thomas

    2013-04-28

    Ice nucleation was investigated experimentally in water droplets with diameters between 53 and 96 micrometres. The droplets were produced in a microfluidic device in which a flow of methyl-cyclohexane and water was combined at the T-junction of micro-channels yielding inverse (water-in-oil) emulsions consisting of water droplets with small standard deviations. In cryo-microscopic experiments we confirmed that upon cooling of such emulsion samples ice nucleation in individual droplets occurred independently of each other as required for the investigation of a stochastic process. The emulsion samples were then subjected to cooling at 1 Kelvin per minute in a differential scanning calorimeter with high temperature accuracy. From the latent heat released by freezing water droplets we inferred the volume-dependent homogeneous ice nucleation rate coefficient of water at temperatures between 236.5 and 237.9 Kelvin. A comparison of our newly derived values to existing rate coefficients from other studies suggests that the volume-dependent ice nucleation rate in supercooled water is slightly lower than previously thought. Moreover, a comprehensive error analysis suggests that absolute temperature accuracy is the single most important experimental parameter determining the uncertainty of the derived ice nucleation rates in our experiments, and presumably also in many previous experiments. Our analysis, thus, also provides a route for improving the accuracy of future ice nucleation rate measurements.

  11. 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.

  12. 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.

  13. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Coloring Rate of Phenolphthalein by Reaction with Alkaline Solution Observed by Liquid-Droplet Collision.

    PubMed

    Takano, Yuuka; Kikkawa, Shigenori; Suzuki, Tomoko; Kohno, Jun-ya

    2015-06-11

    Many important chemical reactions are induced by mixing two solutions. This paper presents a new way to measure rates of rapid chemical reactions induced by mixing two reactant solutions using a liquid-droplet collision. The coloring reaction of phenolphthalein (H2PP) by a reaction with NaOH is investigated kinetically. Liquid droplets of H2PP/ethanol and NaOH/H2O solutions are made to collide, which induces a reaction that transforms H2PP into a deprotonated form (PP(2-)). The concentration of PP(2-) is evaluated from the RGB values of pixels in the colored droplet images, and is measured as a function of the elapsed time from the collision. The obtained rate constant is (2.2 ± 0.7) × 10(3) M(-1) s(-1), which is the rate constant for the rate-determining step of the coloring reaction of H2PP. This method was shown to be applicable to determine rate constants of rapid chemical reactions between two solutions.

  15. OPPORTUNITIES TO CONSTRAIN ASTROPHYSICAL REACTION RATES FOR THE s-PROCESS VIA DETERMINATION OF THE GROUND-STATE CROSS-SECTIONS

    SciTech Connect

    Rauscher, T.; Mohr, P.; Dillmann, I.; Plag, R.

    2011-09-10

    Modern models of s-process nucleosynthesis in stars require stellar reaction rates of high precision. Most neutron-capture cross-sections in the s-process have been measured, and for an increasing number of reactions the required precision is achieved. This does not necessarily mean, however, that the stellar rates are constrained equally well, because only the capture of the ground state of a target is measured in the laboratory. Captures of excited states can contribute considerably to stellar rates that are already at typical s-process temperatures. We show that the ground-state contribution X to a stellar rate is the relevant measure to identify reactions that are or could be well constrained by experiments and apply it to (n,{gamma}) reactions in the s-process. We further show that the maximum possible reduction in uncertainty of a rate via determination of the ground-state cross-section is given directly by X. An error analysis of X is presented, and it is found that X is a robust measure with mostly small uncertainties. Several specific examples (neutron capture of {sup 79}Se, {sup 95}Zr, {sup 121}Sn, {sup 187}Os, and {sup 193}Pt) are discussed in detail. The ground-state contributions for a set of 412 neutron-capture reactions around the s-process path are presented in a table. This allows identification of reactions that may be better constrained by experiments and that cannot be constrained solely by measuring ground-state cross-sections (and thus require supplementary studies). General trends and implications are discussed.

  16. GPS and Geologic Deformation Rates Agree to Within Uncertainties in the Arabia-Africa- Eurasia Zone of Plate Interaction

    NASA Astrophysics Data System (ADS)

    Reilinger, R. E.; McClusky, S.

    2008-12-01

    Geodetically-derived motions for Arabia and Nubia relative to Eurasia agree within 1 standard deviation with plate rates estimated from geologic observations (McQuarrie et al., GRL, 2003) for the past 11 Myr for Nubia and greater than 25 Myr for Arabia. Furthermore, fault slip rates derived from an elastic block model constrained by GPS agree within uncertainties (about +/- 15 percent) with geologically determined, long-term slip rates in this complex area of plate interaction. Detailed geomorphological studies of the central North Anatolian fault (NAF) constrained by quantitative dating (Kozaci et a al., Geology, 2007) indicate slip rates that agree within uncertainties, but appear to be systematically lower than geodetic rates. While real rate changes of a few mm/yr cannot be ruled out at present, we note that geodetic inversions for coseismic fault slip on the NAF, and most other faults well constrained by geodetic observations, indicate larger slip at depth than at the surface. If this difference persists throughout the earthquake deformation cycle, it would account for the small difference in geodetic and geologic rates. Extrapolating present-day geodetic motions for Arabia relative to Nubia and Somalia to the time of initiation of Red Sea and Gulf of Aden extension indicates that Arabia separated from Nubia and Somalia simultaneously along the full extent of both rifts at about 25 Myr BP, consistent with independent geologic estimates for the style, and age of initiation of Red Sea extension (Omar and Steckler, 1995, Science). In addition, structural offsets across the Gulf of Suez (GoS) and Gulf of Aqaba (GoA) are consistent with a transfer of strain form the GoS to the GoA at around 12 Ma BP, roughly consistent with the age on initiation of the Dead Sea fault system. We further show that the apparent discrepancy between geodetic deformation of the Aegean (plate-like motion with low internal deformation), and geologic deformation (extensive crustal thinning

  17. 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.

  18. The Hydroxyl Radical Reaction Rate Constant and Products of Dimethyl Succinate

    DTIC Science & Technology

    2008-03-01

    AFRL-RX-TY-TR-2008-4522 THE HYDROXYL RADICAL REACTION RATE CONSTANT AND PRODUCTS OF DIMETHYL SUCCINATE Sheryl E. Calidonna and...the gas-phase hydroxyl radical reaction with dimethyl succinate. Additional reports and publications resulting from this work unit are not described...herein but are listed below for reference. Baxley, J.Steven and J.R. Wells, “The Hydroxyl Radical Rate Constant and Atmospheric Transforamtion

  19. The Effect of the Triple-α Reaction Rate on Stellar Evolution at Low-Metallicity

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

    We investigate the effect of the triple-α reaction rates on the evolution of low-mass stars and massive stars. The former is compared with the observations of metal-poor stars known to date. For the latter, we discuss the impact of recent calculation of triple-α reaction rate by Ogata et al. (2009, PTP, 122, 1055) on the evolution until carbon burning.

  20. Uncertainties in Instantaneous Rainfall Rate Estimates: Satellite vs. Ground-Based Observations

    NASA Astrophysics Data System (ADS)

    Amitai, E.; Huffman, G. J.; Goodrich, D. C.

    2012-12-01

    High-resolution precipitation intensities are significant in many fields. For example, hydrological applications such as flood forecasting, runoff accommodation, erosion prediction, and urban hydrological studies depend on an accurate representation of the rainfall that does not infiltrate the soil, which is controlled by the rain intensities. Changes in the rain rate pdf over long periods are important for climate studies. Are our estimates accurate enough to detect such changes? While most evaluation studies are focusing on the accuracy of rainfall accumulation estimates, evaluation of instantaneous rainfall intensity estimates is relatively rare. Can a speceborne radar help in assessing ground-based radar estimates of precipitation intensities or is it the other way around? In this presentation we will provide some insight on the relative accuracy of instantaneous precipitation intensity fields from satellite and ground-based observations. We will examine satellite products such as those from the TRMM Precipitation Radar and those from several passive microwave imagers and sounders by comparing them with advanced high-resolution ground-based products taken at overpass time (snapshot comparisons). The ground based instantaneous rain rate fields are based on in situ measurements (i.e., the USDA/ARS Walnut Gulch dense rain gauge network), remote sensing observations (i.e., the NOAA/NSSL NMQ/Q2 radar-only national mosaic), and multi-sensor products (i.e., high-resolution gauge adjusted radar national mosaics, which we have developed by applying a gauge correction on the Q2 products).

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

    PubMed

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

    2012-10-28

    Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S((1)D) + H(2) → 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)] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009)]. 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((1)D).

  2. Effect of vibrational excitation of the reagents on the rates of chemical reactions. The reaction Li + H/sub 2/

    SciTech Connect

    Grigor'eva, T.M.; Levitskii, A.A.; Polak, L.S.

    1986-09-01

    The classical trajectories method was used to calculate the smoothed cross sections and rate constants for the exchange reaction Li(/sub 2/S) + H/sup 2/ (X/sup 2/..sigma../sub g/ /sup +/, v) ..-->.. LiH (X/sup 1/..sigma../sup +/) + H(/sup 2/S) and dissociation reaction Li (/sup 2/S) + H/sub 2/ (X/sup 1/..sigma../sub g/ /sup +/, v) ..-->.. Li(/sup 2/S) + H(/sup 2/S) + H(/sup 2/S) for different vibrational levels v of the hydrogen molecule. The smoothed cross sections were approximated by the expression epsilon about theta(..beta..E/sub +/ + ..gamma..E/sub v/ -epsilon epsilon), where epsilon is the reaction threshold, theta (x) a Heaviside function, and ..beta.. and ..gamma.. represent the degrees of participation of translational (E/sub t/ ) and vibrational (E/sub v/ ) energy in the reaction. For the exchange reaction the values ..beta.. = 0.3, ..gamma.. = 1.0 were obtained; consequently in this case vibrational energy is more efficient than translational energy in overcoming the activation barrier.

  3. NACRE II: an update of the NACRE compilation of charged-particle-induced thermonuclear reaction rates for nuclei with mass number A<16

    NASA Astrophysics Data System (ADS)

    Xu, Y.; Takahashi, K.; Goriely, S.; Arnould, M.; Ohta, M.; Utsunomiya, H.

    2013-11-01

    An update of the NACRE compilation [3] is presented. This new compilation, referred to as NACRE II, reports thermonuclear reaction rates for 34 charged-particle induced, two-body exoergic reactions on nuclides with mass number A<16, of which fifteen are particle-transfer reactions and the rest radiative capture reactions. When compared with NACRE, NACRE II features in particular (1) the addition to the experimental data collected in NACRE of those reported later, preferentially in the major journals of the field by early 2013, and (2) the adoption of potential models as the primary tool for extrapolation to very low energies of astrophysical S-factors, with a systematic evaluation of uncertainties.

  4. 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.

  5. Proton-capture Nucleosynthesis In Low Mass Stars: Effects of New Reaction Rates

    SciTech Connect

    Palmerini, S.; Busso, M.; La Cognata, M.; Cristallo, S.

    2011-10-28

    We present computations of nucleosynthesis in low-mass asymptotic-giant-branch stars of solar metallicity experiencing deep mixing. In this framework, we discuss the effects of recent improvements in relevant reaction rates for proton captures on intermediate-mass nuclei. The calculations are then performed on the basis of a parameterized circulation, where the effects of the new nuclear inputs are best compared to previous works. We find that especially the new reaction rate for the {sup 14}N(p,{gamma}){sup 15}O reaction implies considerable modifications in the composition of low mass red giant stars.

  6. Measurement of Fluorine Atom Concentrations and Reaction Rates in Chemical Laser Systems.

    DTIC Science & Technology

    1981-09-01

    AD-A1RA 070 AERODYNEERESEARCHUINC BEDFORDM MA F/6_20/5 MEASURE MENT OF FLUORINE ATOM CONCENTRATIONS AND REACTION RATFS -ETC(U) SEP_ A A C STANT ON...0772 LEVELIg 00 ~ARI-RR-272 cO0 MEASUREMENT OF FLUORINE ATOM CONCENTRATIONS AND REACTION RATES IN CHEMICAL LASER SYSTEMS ANNUAL TECHNICAL REPORT by...MEASUREMENT OF FLUORINE ATOM CONCENTRATIONS AND Annual Report REACTION RATES IN CHEMICAL LASER SYSTEMS 23 July 1980 - 23 July 1981 S. PERFORMING ORG. REPORT

  7. 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.

  8. Atmospheric chemistry of (Z)-CF3CH═CHCF3: OH radical reaction rate coefficient and global warming potential.

    PubMed

    Baasandorj, Munkhbayar; Ravishankara, A R; Burkholder, James B

    2011-09-29

    Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-CF(3)CH═CHCF(3) (cis-1,1,1,4,4,4-hexafluoro-2-butene) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis (PLP) to produce OH and laser-induced fluorescence (LIF) to detect it. Rate coefficients were measured over a range of temperatures (212-374 K) and bath gas pressures (20-200 Torr; He, N(2)) and found to be independent of pressure over this range of conditions. The rate coefficient has a non-Arrhenius behavior that is well-described by the expression k(1)(T) = (5.73 ± 0.60) × 10(-19) × T(2) × exp[(678 ± 10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (4.91 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1) and the uncertainties are at the 2σ level and include estimated systematic errors. Rate coefficients for the analogous OD radical reaction were determined over a range of temperatures (262-374 K) at 100 Torr (He) to be k(2)(T) = (4.81 ± 0.20) × 10(-19) × T(2) × exp[(776 ± 15)/T], with k(2)(296 K) = (5.73 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1). OH radical rate coefficients were also measured at 296, 345, and 375 K using a relative rate technique and found to be in good agreement with the PLP-LIF results. A room-temperature rate coefficient for the O(3) + (Z)-CF(3)CH═CHCF(3) reaction was measured using an absolute method with O(3) in excess to be <6 × 10(-21) cm(3) molecule(-1) s(-1). The atmospheric lifetime of (Z)-CF(3)CH═CHCF(3) due to loss by OH reaction was estimated to be ~20 days. Infrared absorption spectra of (Z)-CF(3)CH═CHCF(3) measured in this work were used to determine a (Z)-CF(3)CH═CHCF(3) global warming potential (GWP) of ~9 for the 100 year time horizon. A comparison of the OH reactivity of (Z)-CF(3)CH═CHCF(3) with other unsaturated fluorinated compounds is presented.

  9. New determination of 12C(α,γ)16O reaction rate

    NASA Astrophysics Data System (ADS)

    Oulebsir, N.

    2015-12-01

    The reaction 12C(α,γ)16O was investigated through the direct α-transfer reaction (7Li,t) at 28 and 34 MeV incident energies. We determined the reduced α-widths of the sub-threshold 2+ and 1- states of 16O from the DWBA analysis of the transfer reaction 12C(7Li,t)16O performed at two incident energies. The obtained result for the 2+ and 1- sub-threshold resonances as introduced in the R-matrix fitting of radiative capture and elastic-scattering data to determine the E2 and E1 S-factor from 0.01MeV to 4.2MeV in the center-of-mass energy. After determining the astrophysic factor of 12C(α,γ)16O S(E) with Pierre Descouvement code, I determined numerically the new reaction rate of this reaction at a different stellar temperature (0.06 Gk-2 GK). The 12C(α,γ)16O reaction rate at T9 = 0.2 is [7.21-2.25+2.15] × 10-15 cm3 s-1 mol-1. Some comparisons and discussions about our new 12C(α,γ)16O reaction rate are presented. The agreements of the reaction rate below T9 = 2 between our results and with those proposed by NACRE indicate that our results are reliable, and they could be included in the astrophysical reaction rate network.

  10. Experimental determination of the {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates

    SciTech Connect

    Chafa, A.; Ouichaoui, S.; Tatischeff, V.; Coc, A.; Garrido, F.; Kiener, J.; Lefebvre-Schuhl, A.; Thibaud, J.-P.; Aguer, P.; Barhoumi, S.; Hernanz, M.; Jose, J.; Sereville, N. de

    2007-03-15

    The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reactions are of major importance to hydrogen-burning nucleosynthesis in a number of different stellar sites. In particular, {sup 17}O and {sup 18}F nucleosynthesis in classical novae is strongly dependent on the thermonuclear rates of these two reactions. The previously estimated rate for {sup 17}O(p,{alpha}){sup 14}N carries very large uncertainties in the temperature range of classical novae (T=0.01-0.4 GK), whereas a recent measurement has reduced the uncertainty of the {sup 17}O(p,{gamma}){sup 18}F rate. We report on the observation of a previously undiscovered resonance at E{sub c.m.}=183.3 keV in the {sup 17}O(p,{alpha}){sup 14}N reaction, with a measured resonance strength {omega}{gamma}{sub p{alpha}}=(1.6{+-}0.2)x10{sup -3} eV. We studied in the same experiment the {sup 17}O(p,{gamma}){sup 18}F reaction by an activation method, and the resonance strength was found to amount to {omega}{gamma}{sub p{gamma}}=(2.2{+-}0.4)x10{sup -6} eV. The excitation energy of the corresponding level in {sup 18}F was determined to be 5789.8{+-}0.3 keV in a Doppler shift attenuation method measurement, which yielded a value of {tau}<2.6 fs for the level lifetime. The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates were calculated using the measured resonance properties and reconsidering some previous analyses of the contributions of other levels or processes. The {sup 17}O(p,{alpha}){sup 14}N rate is now well established below T=1.5 GK, with uncertainties reduced by orders of magnitude in the temperature range T=0.1-0.4 GK. The uncertainty in the {sup 17}O(p,{gamma}){sup 18}F rate is somewhat larger because of remaining obscurities in the knowledge of the direct capture process. These new resonance properties have important consequences for {sup 17}O nucleosynthesis and {gamma}-ray emission of classical novae.

  11. Calorimetric determination of rate constants and enthalpy changes for zero-order reactions.

    PubMed

    Almeida e Sousa, Luis; Beezer, Anthony E; Hansen, Lee D; Clapham, David; Connor, Joseph A; Gaisford, Simon

    2012-06-07

    Calorimetry is a general method for determination of the rates of zero-order processes, but analysis of the data for the rate constant and reaction enthalpy is difficult because these occur as a product in the rate equation so evaluation of one requires knowledge of the other. Three methods for evaluation of both parameters, without prior knowledge, are illustrated with examples and compared with literature data. Method 1 requires the reaction to be studied in two buffers with different enthalpies of ionization. Method 2 is based on calculation of reaction enthalpy from group additivity functions. Method 3 applies when reaction progresses to completion. The methods are applied to the enzymatic hydrolysis of urea, the hydrolysis of acetylsalicylic acid, and the photodegradation of nifedipine, respectively.

  12. 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.

  13. Material interactions with the Low Earth Orbital (LEO) environment: Accurate reaction rate measurements

    NASA Technical Reports Server (NTRS)

    Visentine, James T.; Leger, Lubert J.

    1987-01-01

    To resolve uncertainties in estimated LEO atomic oxygen fluence and provide reaction product composition data for comparison to data obtained in ground-based simulation laboratories, a flight experiment has been proposed for the space shuttle which utilizes an ion-neutral mass spectrometer to obtain in-situ ambient density measurements and identify reaction products from modeled polymers exposed to the atomic oxygen environment. An overview of this experiment is presented and the methodology of calibrating the flight mass spectrometer in a neutral beam facility prior to its use on the space shuttle is established. The experiment, designated EOIM-3 (Evaluation of Oxygen Interactions with Materials, third series), will provide a reliable materials interaction data base for future spacecraft design and will furnish insight into the basic chemical mechanisms leading to atomic oxygen interactions with surfaces.

  14. Reaction rates of ozone and terpenes adsorbed to model indoor surfaces.

    PubMed

    Springs, M; Wells, J R; Morrison, G C

    2011-08-01

    Reaction rates and reaction probabilities have been quantified on model indoor surfaces for the reaction of ozone with two monoterpenes (Δ(3) -carene and d-limonene). Molar surface loadings were obtained by performing breakthrough experiments in a plug-flow reactor (PFR) packed with beads of glass, polyvinylchloride or zirconium silicate. Reaction rates and probabilities were determined by equilibrating the PFR with both the terpene and the ozone and measuring the ozone consumption rate. To mimic typical indoor conditions, temperatures of 20, 25, and 30°C were used in both types of experiments along with a relative humidity ranging from 10% to 80%. The molar surface loading decreased with increased relative humidity, especially on glass, suggesting that water competed with the terpenes for adsorption sites. The ozone reactivity experiments indicate that higher surface loadings correspond with higher ozone uptake. The reaction probability for Δ(3) -carene with ozone ranged from 2.9 × 10(-6) to 3.0 × 10(-5) while reaction probabilities for d-limonene ranged from 2.8 × 10(-5) to 3.0 × 10(-4) . These surface reaction probabilities are roughly 10-100 times greater than the corresponding gas-phase values. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially for lower volatility terpenoids. At present, it is unclear how important heterogeneous reactions will be in influencing indoor concentrations of terpenes, ozone and their reaction products. We observe that surface reaction probabilities were 10 to 100 times greater than their corresponding gas-phase values. Thus indoor surfaces do enhance effective reaction rates and adsorption of terpenes will increase ozone flux to otherwise low-reactivity surfaces. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially

  15. 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.

  16. Improving the 33S(p,γ)34Cl Reaction Rate for Models of Classical Nova Explosions

    NASA Astrophysics Data System (ADS)

    Parikh, A.; Faestermann, Th.; Krücken, R.; Bildstein, V.; Bishop, S.; Eppinger, K.; Herlitzius, C.; Lepyoshkina, O.; Maierbeck, P.; Seiler, D.; Wimmer, K.; Hertenberger, R.; Wirth, H.-F.; Fallis, J.; Hager, U.; Hutcheon, D.; Ruiz, Ch.; Buchmann, L.; Ottewell, D.; Freeman, B.; Wrede, Ch.; García, A.; Delbridge, B.; Knecht, A.; Sallaska, A.; Chen, A. A.; Clark, J. A.; Deibel, C. M.; Fulton, B.; Laird, A.; Greife, U.; Guo, B.; Li, E.; Li, Z.; Lian, G.; Wang, Y.; Liu, W.; Parker, P. D.; Setoodehnia, K.

    2011-10-01

    Reduced uncertainty in the thermonuclear rate of the 33S(p,γ)34Cl reaction would help to improve our understanding of nucleosynthesis in classical nova explosions. At present, models are generally in concordance with observations that nuclei up to roughly the calcium region may be produced in these explosive phenomena; better knowledge of this rate would help with the quantitative interpretation of nova observations over the S-Ca mass region, and contribute towards the firm establishment of a nucleosynthetic endpoint. As well, models find that the ejecta of nova explosions on massive oxygen-neon white dwarfs may contain as much as 150 times the solar abundance of 33S. This characteristic isotopic signature of a nova explosion could possibly be observed through the analysis of microscopic grains formed in the environment surrounding a nova and later embedded within primitive meteorites. An improved 33S(p,γ)34Cl rate (the principal destruction mechanism for 33S in novae) would help to ensure a robust model prediction for the amount of 33S that may be produced. Finally, constraining this rate could confirm or rule out the decay of an isomeric state of 34Cl (Ex = 146 keV, t1/2 = 32 m) as a source for observable gamma-rays from novae. We have performed several complementary experiments dedicated to improving our knowledge of the 33S(p,γ)34Cl rate, using both indirect methods (measurement of the 34S(3He,t)34Cl and 33S(3He,d)34Cl reactions with the Munich Q3D spectrograph) and direct methods (in normal kinematics at CENPA, University of Washington, and in inverse kinematics with the DRAGON recoil mass separator at TRIUMF). Our results will be used with nova models to facilitate comparisons of model predictions with present and future nova observables.

  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. Simulation of chemical reaction via particle tracking: Diffusion-limited versus thermodynamic rate-limited regimes

    NASA Astrophysics Data System (ADS)

    Benson, David A.; Meerschaert, Mark M.

    2008-12-01

    Chemical reactions may be simulated without regard to local concentrations by applying simple probabilistic rules of particle interaction and combination. The forward reaction A + B→ C is coded by calculating the probability that any A and B particles will occupy the same volume over some time interval. This becomes a convolution of the location densities of the two particles. The backward reaction is a simple exponential decay of C particles into A and B particles. When the mixing of reactants is not a limiting process, the classical thermodynamic reaction rates are reproduced. When low mixing (as by diffusion) limits the reaction probabilities, the reaction rates drop significantly, including the rate of approach to global equilibrium. At long enough times, the law of mass action is reproduced exactly in the mean, with some irreducible deviation in the local equilibrium saturations (the equilibrium constant divided by the mass action expression) away from unity. The saturation variability is not sensitive to numerical parameters but depends strongly on how far from equilibrium the system is initiated. This is simply due to a relative paucity of particles of some species as the reaction moves far to one side or the other.

  19. Low rate of cetuximab hypersensitivity reactions in Northeast Tennessee: An Appalachian effect?

    PubMed

    Adams, C Brooke; Street, D Sierra; Crass, Melanie; Bossaer, John B

    2016-12-01

    Cetuximab is a monoclonal antibody with a known risk of hypersensitivity reactions. Early studies showed hypersensitivity reaction rates of 3%, but there appears to be a higher incidence in the southeastern United States. To confirm the findings from nearby institutions that cetuximab-associated hypersensitivity reactions occur in approximately 20% of patients in the southeastern United States. A retrospective chart review was conducted at Johnson City Medical Center in Johnson City, Tennessee. Each patient's first infusion was analyzed for hypersensitivity reaction, as well as for demographic information such as allergy and smoking history, pre-medications, and malignancy type. Data from the first infusion of cetuximab were collected for a total of 71 patients with various malignancies. The overall rate of grade 3 or higher hypersensitivity reaction was 1.4%, and total rate of hypersensitivity reaction was 8.5%. These findings more closely correlate to the early clinical trials and package insert. Both severe (p = 0.001) and any-grade (p = 0.002) hypersensitivity reaction occurred less frequently in one Southeastern Appalachian medical center compared to academic medical centers directly to the east and west. Patients in southern Appalachia may be less likely to develop cetuximab hypersensitivity reactions compared to surrounding areas in the Southeastern U.S. These results lend support to the theory that exposure to lonestar ticks (Amblyomma americanum) may be responsible for the development of IgE antibodies to cetuximab that cause hypersensitivity reactions. The development of quick and reliable bedside predictors of cetuximab hypersensitivity reactions may aid clinicians considering the use of cetuximab. © The Author(s) 2015.

  20. 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.

  1. 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.

  2. Evolutionary implications of the new triple-α nuclear reaction rate for low mass stars

    NASA Astrophysics Data System (ADS)

    Dotter, A.; Paxton, B.

    2009-12-01

    Context: Ogata et al. (2009, Progr. Theor. Phys., 122, 1055) presented a theoretical determination of the ^4He(αα,γ)12C, or triple-α, nuclear reaction rate. Their rate differs from the NACRE rate by many orders of magnitude at temperatures relevant for low mass stars. Aims: We explore the evolutionary implications of adopting the OKK triple-α reaction rate in low mass stars and compare the results with those obtained using the NACRE rate. Methods: The triple-α reaction rates are compared by following the evolution of stellar models at 1 and 1.5 M⊙ with Z = 0.0002 and Z = 0.02. Results: Results show that the OKK rate has severe consequences for the late stages of stellar evolution in low mass stars. Most notable is the shortening-or disappearance-of the red giant phase. Conclusions: The OKK triple-α reaction rate is incompatible with observations of extended red giant branches and He burning stars in old stellar systems.

  3. 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.

  4. Gamma Spectroscopy of States in {sup 32}Cl Relevant for the {sup 31}S({ital p},{gamma}){sup 32}Cl Reaction Rate

    DOE PAGES

    Afanasieva, L.; Blackmon, J. C.; Deibel, C. M.; ...

    2017-09-01

    Background: The 31S(p,gamma) 32Cl reaction becomes important for sulfur production in novae if the P-31(p, alpha)Si-28 reaction rate is somewhat greater than currently accepted. The rate of the S-31(p,gamma) Cl-32 reaction is uncertain, primarily due to the properties of resonances at E-c.m. = 156 and 549 keV. Purpose: We precisely determined the excitation energies of states in Cl-32 through high-resolution. spectroscopy including the two states most important for the S-31(p,gamma) Cl-32 reaction at nova temperatures. Method: Excited states in Cl-32 were populated using the B-10(Mg-24, 2n) Cl-32 reaction with a Mg-24 beam from the ATLAS facility at Argonne National Laboratory.more » The reaction channel of interest was selected using recoils in the Fragment Mass Analyzer, and precise level energies were determined by detecting. rays with Gammasphere. Results: We observed. rays from the decay of six excited states in Cl-32. The excitation energies for two unbound levels at E-x = 1738.1 (6) keV and 2130.5 (10) keV were determined and found to be in agreement with a previous high-precision measurement of the S-32(He-3, t) Cl-32 reaction [1]. Conclusions: An updated 31S(p,gamma) Cl-32 reaction rate is presented. With the excitation energies of important levels firmly established, the dominant uncertainty in the reaction rate at nova temperatures is due to the strength of the resonance corresponding to the 2131-keV state in Cl-32.« less

  5. 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.

  6. 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.

  7. 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.

  8. Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications

    DOE PAGES

    Suleimanov, Yury V.; Aoiz, F. Javier; Guo, Hua

    2016-09-14

    This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques formore » calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.« less

  9. Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications.

    PubMed

    Suleimanov, Yury V; Aoiz, F Javier; Guo, Hua

    2016-11-03

    This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.

  10. Reaction rates of Criegee intermediates with water vapor and hydrogen sulfide

    NASA Astrophysics Data System (ADS)

    Smith, M. C.; Boering, K. A.

    2016-12-01

    Criegee intermediates are byproducts of the reaction of alkenes with ozone. Bimolecular reactions of Criegee intermediates can lead to the production of low-volatility organic compounds and acids in the atmosphere, which in turn play a role in determining the concentration, size, and optical properties of aerosols. Recently, a novel method for producing measurable quantities of stabilized Criegee intermediates in the laboratory paved the way for the development of new experimental techniques to study their chemical properties and predict their importance in the atmosphere. Our lab uses transient UV absorption spectroscopy to measure the formation and decay of Criegee intermediates in a flow cell, using 8-pass absorption of a bright plasma light source combined with sensitive balanced photodiode detection. Here we measured the transient absorption of CH2OO and obtained rate coefficients for its reaction with water dimer from 283 to 324 K. The fast reaction of CH2OO with water dimer is thought to dominate CH2OO removal in the atmosphere, but reaction rates can vary considerably under different conditions of temperature, humidity, and pressure. The rate of the reaction of CH2OO with water dimer was found to exhibit a strong negative temperature dependence. Due to the strong temperature dependence, and shifting competition between water dimer and water monomer (which has a positive temperature dependence), the effective loss rate of CH2OO by reaction with water vapor is highly sensitive to atmospheric conditions. We also present the first measurements of the reaction rate between CH2OO and hydrogen sulfide, which is analogous to the water molecule and may have significance in areas with volcanic activity.

  11. 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.

  12. Rate of mixing controls rate and outcome of autocatalytic processes: theory and microfluidic experiments with chemical reactions and blood coagulation.

    PubMed

    Pompano, Rebecca R; Li, Hung-Wing; Ismagilov, Rustem F

    2008-08-01

    This article demonstrates that the rate of mixing can regulate the rate and outcome of both biological and nonbiological autocatalytic reaction systems that display a threshold response to the concentration of an activator. Plug-based microfluidics was used to control the timing of reactions, the rate of mixing, and surface chemistry in blood clotting and its chemical model. Initiation of clotting of human blood plasma required addition of a critical concentration of thrombin. Clotting could be prevented by rapid mixing when thrombin was added near the critical concentration, and mixing also affected the rate of clotting when thrombin was added at concentrations far above the critical concentration in two clinical clotting assays for human plasma. This phenomenon was modeled by a simple mechanism--local and global competition between the clotting reaction, which autocatalytically produces an activator, and mixing, which removes the activator. Numerical simulations showed that the Damköhler number, which describes this competition, predicts the effects of mixing. Many biological systems are controlled by thresholds, and these results shed light on the dynamics of these systems in the presence of spatial heterogeneities and provide simple guidelines for designing and interpreting experiments with such systems.

  13. Reevaluating Reaction Rates from Diffusion Profiles in Minerals and Effects on Trace Element Thermometers.

    NASA Astrophysics Data System (ADS)

    Kohn, M. J.; Penniston-Dorland, S.

    2016-12-01

    The overgrowth of one mineral upon another (corona) can be associated with a diffusion profile in the reactant (core) crystal. In principle, these profiles can be used to infer reaction rates using a steady state reaction model (constant velocity movement of the reactant/product grain boundary). In practice, however, natural data do not conform to these models. Assuming mass conservation and equilibrium partitioning between the two reactant and product minerals, steady state reaction predicts an exponential profile. Rutile that was overgrown by titanite sometimes show quasi-exponentially decreasing profiles in trace elements, suggesting reaction rates might be inferred. However, the steady-state reaction model also predicts that: (1) The mass excess in the diffusion profile in rutile should be balanced by a mass deficit in titanite, (2) Titanite should be zoned and exhibit a compositional trend complementary to the profile in rutile, and (3) Trace element partitioning between titanite and rutile should be maintained as the corona develops and should be preserved at the rutile-titanite interface. None of these three predictions are observed in natural titanite overgrowths on rutile, rather titanite is generally unzoned and significant trace element mass deficits or excesses indicate partial to complete interaction with other matrix minerals. Reaction rates might still be obtainable if titanite and rutile rim compositions continuously equilibrate with the matrix during reaction. If so, however, temperatures from Zr-in-titanite (ZiT) and Zr-in-rutile (ZiR) should be identical. Yet commonly they are not, even accounting for potentially low activities of zircon and quartz at the reaction interface, rather T(ZiT) > T(ZiR). Explanations for the diffusion profiles in rutile range from steadily increasing or decreasing reaction rates, or even post-reaction development of a diffusion profile with a fixed boundary condition. While reaction rates cannot be quantified, the

  14. A variable reaction rate model for chlorine decay in drinking water due to the reaction with dissolved organic matter.

    PubMed

    Hua, Pei; Vasyukova, Ekaterina; Uhl, Wolfgang

    2015-05-15

    A second order kinetic model for simulating chlorine decay in bulk water due to the reaction with dissolved organic matter (DOM) was developed. It takes into account the decreasing reactivity of dissolved organic matter using a variable reaction rate coefficient (VRRC) which decreases with an increasing conversion. The concentration of reducing species is surrogated by the maximum chlorine demand. Temperature dependency, respectively, is described by the Arrhenius-relationship. The accuracy and adequacy of the proposed model to describe chlorine decay in bulk water were evaluated and shown for very different waters and different conditions such as water mixing or rechlorination by applying statistical tests. It is thus very well suited for application in water quality modeling for distribution systems.

  15. 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.

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

    PubMed

    Szymańska, Paulina; Kochańczyk, Marek; Miękisz, 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.

  17. Quantitative rate constants for radical reactions in the nanopores of cotton.

    PubMed

    Hunt, Paula; Worrall, David R; Wilkinson, Frank; Batchelor, Stephen N

    2002-07-24

    The understanding of radical reactions in nanostructured materials is important for developing new synthetic procedures and controlling degradation reactions. To develop this area, an easy method for measuring quantitative rate constants of some radical reactions in nanostructures is required. A simple method for measuring the rate constant of dye bleaching, kdye, by organic radicals in such materials is introduced, involving the measurement of microsecond bleaching kinetics by diffuse reflectance spectroscopy, following laser flash creation of the radicals. Using wet and dry cotton as model substrates, we obtained kdye of 2-hydroxy-2-propyl and 1-hydroxy-1-cyclohexyl radicals with reactive red 3 and reactive orange 4 and compared them to solution-phase values. Surprisingly, the reactions in cotton follow simple liquid-phase kinetics and are diffusion-controlled. A cage effect in cotton is also found.

  18. 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

  19. The rate of the reaction between CN and C2H2 at interstellar temperatures.

    PubMed

    Woon, D E; Herbst, E

    1997-03-01

    The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

  20. 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):

  1. Kinetics of the benzyl + O(3P) reaction: a quantum chemical/statistical reaction rate theory study.

    PubMed

    da Silva, Gabriel; Bozzelli, Joseph W

    2012-12-14

    The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O(2). In this study the reaction of benzyl with ground-state atomic oxygen, O((3)P), is examined using quantum chemistry and statistical reaction rate theory. C(7)H(7)O energy surfaces are generated at the G3SX level, and include several novel pathways. Transition state theory is used to describe elementary reaction kinetics, with canonical variational transition state theory applied for barrierless O atom association with benzyl. Apparent rate constants and branching ratios to different product sets are obtained as a function of temperature and pressure from solving the time-dependent master equation, with RRKM theory for microcanonical k(E). These simulations indicate that the benzyl + O reaction predominantly forms the phenyl radical (C(6)H(5)) plus formaldehyde (HCHO), with lesser quantities of the C(7)H(6)O products benzaldehyde, ortho-quinone methide, and para-quinone methide (+H), along with minor amounts of the formyl radical (HCO) + benzene. Addition of O((3)P) to the methylene site in benzyl produces a highly vibrationally excited C(7)H(7)O* adduct, the benzoxyl radical, which can β-scission to benzaldehyde + H and phenyl + HCHO. In order to account for the experimental observation of benzene as the major reaction product, a roaming radical mechanism is proposed that converts the nascent products phenyl and HCHO to benzene + HCO. Oxygen atom addition at the ortho and para ring sites in benzyl, which has not been previously considered, is shown to lead to the quinone methides + H; these species are less-stable isomers of benzaldehyde that are proposed as important combustion intermediates, but

  2. Depletion: A Game with Natural Rules for Teaching Reaction Rate Theory

    NASA Astrophysics Data System (ADS)

    Olbris, Donald J.; Herzfeld, Judith

    2002-10-01

    Depletion is a game that reinforces central concepts of reaction rate theory through simulation. Each player buys chemicals and guides them through a series of reactions, thereby earning money to buy more chemicals. The reactions occur when players roll a high enough value on two dice to overcome an activation barrier. The reactions may be accelerated by buying heat (which allows the player to roll three dice instead of two) or catalysts (which lower the activation barrier). The value of acceleration derives from the increasing price of fresh chemicals as resources are depleted and waste products accumulate. The player who nets the most money wins the game. The details of the game are presented, with a set of follow-up questions suitable for either a quiz or discussion. Student reaction to the game is also described.

  3. Analyzing Reaction Rates with the Distortion/Interaction‐Activation Strain Model

    PubMed Central

    2017-01-01

    Abstract The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction energies between the two distorted molecules. The energy required to distort the molecules is called the activation strain or distortion energy. This energy is the principal contributor to the activation barrier. The transition state occurs when this activation strain is overcome by the stabilizing interaction energy. Following the changes in these energies along the reaction coordinate gives insights into the factors controlling reactivity. This model has been applied to reactions of all types in both organic and inorganic chemistry, including substitutions and eliminations, cycloadditions, and several types of organometallic reactions. PMID:28447369

  4. Development of a group contribution method to predict aqueous phase hydroxyl radical (HO*) reaction rate constants.

    PubMed

    Minakata, Daisuke; Li, Ke; Westerhoff, Paul; Crittenden, John

    2009-08-15

    The hydroxyl radical (HO*) is a strong oxidant that reacts with electron-rich sites of organic compounds and initiates complex chain mechanisms. In order to help understand the reaction mechanisms, a rule-based model was previously developed to predict the reaction pathways. For a kinetic model, there is a need to develop a rate constant estimator that predicts the rate constants for a variety of organic compounds. In this study, a group contribution method (GCM) is developed to predict the aqueous phase HO* rate constants for the following reaction mechanisms: (1) H-atom abstraction, (2) HO* addition to alkenes, (3) HO* addition to aromatic compounds, and (4) HO* interaction with sulfur (S)-, nitrogen (N)-, or phosphorus (P)-atom-containing compounds. The GCM hypothesizes that an observed experimental rate constant for a given organic compound is the combined rate of all elementary reactions involving HO*, which can be estimated using the Arrhenius activation energy, E(a), and temperature. Each E(a) for those elementary reactions can be comprised of two parts: (1) a base part that includes a reactive bond in each reaction mechanism and (2) contributions from its neighboring functional groups. The GCM includes 66 group rate constants and 80 group contribution factors, which characterize each HO* reaction mechanism with steric effects of the chemical structure groups and impacts of the neighboring functional groups, respectively. Literature-reported experimental HO* rate constants for 310 and 124 compounds were used for calibration and prediction, respectively. The genetic algorithms were used to determine the group rate constants and group contribution factors. The group contribution factors for H-atom abstraction and HO* addition to the aromatic compounds were found to linearly correlate with the Taft constants, sigma*, and electrophilic substituent parameters, sigma+, respectively. The best calibrations for 83% (257 rate constants) and predictions for 62% (77

  5. An investigation of the reaction kinetics of luciferase and the effect of ionizing radiation on the reaction rate.

    PubMed

    Berovic, Nikolas; Parker, David J; Smith, Michael D

    2009-04-01

    The bioluminescence produced by luciferase, a firefly enzyme, requires three substrates: luciferin, ATP and oxygen. We find that ionizing radiation, in the form of a proton beam from a cyclotron, will eliminate dissolved oxygen prior to any damage to other substrates or to the protein. The dose constant for removal of oxygen is 70 +/- 20 Gy, a much smaller dose than required to cause damage to protein. Removal of oxygen, which is initially in excess, leads to a sigmoidal response of bioluminescence to radiation dose, consistent with a Michaelis-Menten relationship to substrate concentration. When excess oxygen is exhausted, the response becomes exponential. Following the irradiation, bioluminescence recovers due to a slow leak of oxygen into the solution. This may also explain previous observations on the response of bioluminescent bacteria to radiation. We have studied the dependence of the reaction rate on enzyme and substrate concentration and propose a model for the reaction pathway consistent with this data. The light output from unirradiated samples decreases significantly with time due to product inhibition. We observe that this inhibition rate changes dramatically immediately after a sample is exposed to the beam. This sudden change of the inhibition rate is unexplained but shows that enzyme regulatory function responds to ionizing radiation at a dose level less than 0.6 Gy.

  6. 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.

  7. Systematic analysis of astrophysical S-factors and thermonuclear reaction rates

    SciTech Connect

    Katsuma, M.

    2008-05-12

    The astrophysical S-factors of the {sup 13}C({alpha},n){sup 16}O, {sup 17}O({alpha},n){sup 20}Ne, {sup 21}Ne({alpha},n){sup 24}Mg and {sup 25}Mg({alpha},n){sup 28}Si reactions are analyzed with DWBA. The gross structures of the experimental data are reproduced by the DWBA calculations. The resulting reaction rates are compared with those in the CF88 and NACRE compilations.

  8. 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.

  9. Perturbation theory in the catalytic rate constant of the Henri-Michaelis-Menten enzymatic reaction.

    PubMed

    Bakalis, Evangelos; Kosmas, Marios; Papamichael, Emmanouel M

    2012-11-01

    The Henry-Michaelis-Menten (HMM) mechanism of enzymatic reaction is studied by means of perturbation theory in the reaction rate constant k (2) of product formation. We present analytical solutions that provide the concentrations of the enzyme (E), the substrate (S), as well as those of the enzyme-substrate complex (C), and the product (P) as functions of time. For k (2) small compared to k (-1), we properly describe the entire enzymatic activity from the beginning of the reaction up to longer times without imposing extra conditions on the initial concentrations E ( o ) and S ( o ), which can be comparable or much different.

  10. A simple recipe for modeling reaction-rate in flows with turbulent-combustion

    NASA Technical Reports Server (NTRS)

    Girimaji, Sharath S.

    1991-01-01

    A computationally viable scheme to account for chemical reaction in turbulent flows is presented. The multivariate beta-pdf model for multiple scalar mixing forms the basis of this scheme. Using the model scalar joint pdf and a general form of the instantaneous reaction-rate, the unclosed chemical reaction terms are expressed as simple functions of scalar means and the turbulent scalar energy. The calculation procedure requires that the mean scalar equations and only one other transport equation - for the turbulent scalar energy - be solved.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. New empirical rate expression for reactions without a barrier: Analysis of the reaction of CN with O[sub 2

    SciTech Connect

    Hessler, J.P. )

    1999-09-01

    The rate coefficients of reactions that occur on potential energy surfaces without a barrier often exhibit a negative temperature dependence at low temperatures. Generally, this behavior is modeled with either the Harcourt[endash] Essen equation, k(T)=AT[sup [minus] m], or a [open quotes] negative[close quotes] activation energy, k(T)=AT[sup m] [l brace] [Delta] E/k[sub B] T[r brace]. Neither of these expressions is consistent with the Wigner threshold law. The general expression k(T)=(1+T/T[sub W]) [sup [minus]m] [summation] [sub l=0] [sup [infinity

  16. Simulation study of the influence of PEB reaction rates on resist LER

    NASA Astrophysics Data System (ADS)

    Bhattarai, Suchit; Neureuther, Andrew R.; Naulleau, Patrick P.

    2015-03-01

    A stochastic resist simulator has first been calibrated to experimental results performed on a commercially available EUV resist, and subsequently has been used to study the influence of acid/base quenching rate and the polymer deprotection rate on resist LER for 22 nm half-pitch lines/spaces. Results indicate that larger quenching rates and smaller deprotection rates result in improved LER performance by causing an increase in the dose to size. With nominal quenching rate determined from literature, halving the deprotection rate relative to nominal value reduces the LER by 33%, while the dose to size increases by 2x. With nominal deprotection rate determined from literature, results indicate a low sensitivity of LER to quenching rate. Expected noise at the line edge calculated by using a shot noise model accounting for absorbed photons, acid, and base count, provides a good explanation for the LER trends calculated for several reaction rate scenarios.

  17. 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).

  18. 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.

  19. Correlation analysis of the progesterone-induced sperm acrosome reaction rate and the fertilisation rate in vitro.

    PubMed

    Jiang, T; Qin, Y; Ye, T; Wang, Y; Pan, J; Zhu, Y; Duan, L; Li, K; Teng, X

    2015-10-01

    In this study, we aimed to investigate whether progesterone-induced acrosome reaction (AR) rate could be an indicator for fertilisation rate in vitro. Twenty-six couples with unexplained infertility and undergoing in vitro fertilisation (IVF) treatment were involved. On the oocytes retrieval day after routine IVF, residual sperm samples were collected to receive progesterone induction (progesterone group) or not (control group). AR rate was calculated and fertilisation rate was recorded. The correlation between progesterone-induced AR and fertilisation rate and between sperm normal morphology and 3PN (tripronuclear) were analysed using the Spearman correlation analysis. The AR rate of progesterone group was statistically higher than that of the control group (15.6 ± 5.88% versus 9.66 ± 5.771%, P < 0.05), but not significantly correlated with fertilisation rate (r = -0.053, P > 0.01) or rate of high-quality embryo development (r = -0.055, P > 0.01). Normal sperm morphology also showed no significant correlation with the amount of 3PN zygotes (r = 0.029, P > 0.01), rate of 3PN zygotes production (r = 0.20, P > 0.01), rate of 3PN embryo development (r = -0.406, P > 0.01), fertilisation rate (r = -0.148, P > 0.01) or progesterone-induced AR rate (r = 0.214, P > 0.01). Progesterone can induce AR in vitro significantly; however, the progesterone-induced AR may not be used to indicate fertilisation rate.

  20. An accurate analytic representation of the temperature dependence of nonresonant nuclear reaction rate coefficients

    NASA Astrophysics Data System (ADS)

    Shizgal, Bernie D.

    2016-12-01

    There has been intense interest for several decades by different research groups to accurately model the temperature dependence of a large number of nuclear reaction rate coefficients for both light and heavy nuclides. The rate coefficient, k(T) , is given by the Maxwellian average of the reactive cross section expressed in terms of the astrophysical factor, S(E) , which for nonresonant reactions is generally written as a power series in the relative energy E. A computationally efficient algorithm for the temperature dependence of nuclear reaction rate coefficients is required for fusion reactor research and for models of nucleosynthesis and stellar evolution. In this paper, an accurate analytical expression for the temperature dependence of nuclear reaction rate coefficients is provided in terms of τ = 3(b / 2) 2/3 or equivalently, T - 1/3 , where b = B /√{kB T }, B is the Gamow factor and kB is the Boltzmann constant. The methodology is appropriate for all nonresonant nuclear reactions for which S(E) can be represented as a power series in E. The explicit expression for the rate coefficient versus temperature is derived with the asymptotic expansions of the moments of w(E) = exp(- E /kB T - B /√{ E }) in terms of τ. The zeroth order moment is the familiar Gaussian approximation to the rate coefficient. Results are reported for the representative reactions D(d, p)T, D(d, n)3He and 7Li(p, α) α and compared with several different fitting procedures reported in the literature.

  1. Effect of Superposition Location of Ultrasonic Fields on Sonochemical Reaction Rate

    NASA Astrophysics Data System (ADS)

    Yasuda, Keiji; Matsuura, Kazumasa

    2013-07-01

    The effect of the superposition location of ultrasonic fields on the sonochemical reaction rate was investigated using a sonochemical reactor with four transducers at 486 kHz. The transducers were attached at the bottom, upper side middle side, and lower side of a vessel. The reaction rate of potassium iodide in aqueous solution was measured. In the cases of the upper and bottom transducers, and the lower and bottom transducers, the synergy effect of sonochemical efficiency was observed. The amount of synergy effect for the upper and bottom transducers increased with increasing electric power.

  2. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Atmospheric Lifetimes of Very Short Lived Substances: OH Reaction Rate Constants of Stereoisomers and Pressure Dependent Reactions.

    NASA Astrophysics Data System (ADS)

    Orkin, Vladimir; Khamaganov, Victor; Kurylo, Michael

    2017-04-01

    The accuracy of OH kinetic data is of primary importance for the comprehensive modeling of any compound's atmospheric behavior and of its environmental impacts, such as its atmospheric residence time and its potential roles in stratospheric ozone depletion, global warming, and local pollution. Rate constants of OH reactions with hydrocarbons and halogenated hydrocarbons can now be determined with an accuracy of 2-3% over the temperature range 220 K to 370 K. This has been demonstrated in studies of OH reactions with various halogenated and non-substituted organics including alkanes, alkenes, alcohols, and ethers. Lower data scattering and higher measurement accuracy allow for rigorous statistical analysis of the results and can reveal often-missing details about the reactivity, such as the weak dependencies of the rate constant on the temperature, pressure dependences, and the effect of molecular geometry on the reactivity. This presentation will provide examples of several of these measurement results that were recently obtained in our laboratory. The estimated atmospheric lifetimes and global warming potentials will be reported.

  4. Confirmation of high flow rate chaos in the Belousov-Zhabotindy reaction

    SciTech Connect

    Gyoergyi, L. |; Field, R.J.; McCormick, W.D.

    1992-02-06

    Past experiments and simulations on the Belousov-Zhabotinsky (BZ) reaction clearly demonstrated the existence of chaos in stirred flow reactors at low flow rates. However, the existence of chaos at high flow rates has remained the subject of controversy. The controversy is resolved by the present experiments at high flow rates, which accurately reproduce the complex sequence of periodic, complex periodic, and chaotic states observed by Hudson and co-workers; the flow rates observed here for the different dynamical regimes agree with those of Hudson et al. within a few percent. This striking reproducibility of the complex periodic and chaotic dynamics is found to be insensitive to stirring rate, size of the reactor, purity of the reagents, temperature, and type of pumping (peristaltic or piston pumps, premixed or nonpremixed feeds). Moreover, the observed sequence is reproduced qualitatively by a four-variable model of the BZ reaction. Thus, this work provides definitive evidence for the existence of deterministic chaos in the BZ reaction at high flow rates. The authors conclude that past descriptions of aperiodic behavior at high flow rates in terms of various stochastic mechanisms including incomplete mixing or switching between adjacent periodic states, are inappropriate for the conditions of the Hudson`s experiments. 24 refs., 5 figs., 2 tabs.

  5. Reaction rate of H atoms with N2O in hot water

    NASA Astrophysics Data System (ADS)

    Sargent, Leanne; Sterniczuk, Marcin; Bartels, David M.

    2017-06-01

    The rate constant of H• atoms with N2O in water has been measured by a competition method up to 300 °C. Radiolysis with 2.5 MeV electrons generated H• atoms, and the HD product from their reaction with deuterated tetrahydrofuran (THF-d8) was measured with mass spectroscopy. The concentration of THF-d8 was changed by an order of magnitude in the presence of 25 mM N2O to obtain the ratio of rate constants. To determine the rate constant of H• with THF-d8, a similar competition vs. 0.2 mM OH- ion was also measured. The reaction rate of H• with OH- has been accurately determined vs. temperature in previous work, allowing the two unknown rate constants to be deduced. Rate constant of H• with THF-d8 follows the Arrhenius law ln(k/M-1s-1)=27.33 - (32.30 kJ/mol)/RT. Rate constant of H• with N2O follows the Arrhenius law ln(k/M-1s-1)=24.50 - (30.42 kJ/mol)/RT. In all likelihood, the N2O reaction proceeds via cis-HNNO• radical intermediate as in the gas phase, but with participation of a bridging water molecule in the 1,3 hydrogen shift to form N2 and •OH products.

  6. Uncertainty in MR tracer kinetic parameters and water exchange rates estimated from T1-weighted dynamic contrast enhanced MRI

    PubMed Central

    Zhang, Jin; Kim, Sungheon

    2014-01-01

    Purpose The aim of this study was to assess the uncertainty in estimation of MR tracer kinetic parameters and water exchange rates in T1-weighted dynamic contrast enhanced (DCE)-MRI. Methods Simulated DCE-MRI data were used to assess four kinetic models; general kinetic model with a vascular compartment (GKM2), GKM2 combined with the 3S2X model (SSM2), adiabatic approximation of the tissue homogeneity model (ATH), and ATH combined 3S2X model (ATHX). Results In GKM2 and SSM2, increase in transfer constant (Ktrans) led to underestimation of vascular volume fraction (vb), and increase in vb led to overestimation of Ktrans. Such coupling between Ktrans and vb was not observed in ATH and ATHX. The precision of estimated intracellular water lifetime (τi) was substantially improved in both SSM2 and ATHX when Ktrans > 0.3 min−1. Ktrans and vb from ATHX model had significantly smaller errors than those from ATH model (p<0.05). Conclusion The results of this study demonstrated the feasibility of measuring τi from DCE-MRI data albeit low precision. While the inclusion of the water exchange model improved the accuracy of Ktrans, vb, and the interstitial volume fraction estimation (ve), it lowered the precision of other kinetic model parameters within the conditions investigated in this study. PMID:24006341

  7. Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach

    NASA Astrophysics Data System (ADS)

    Manogaran, Lavaneesvari; Sek, Siok Kun

    2017-04-01

    Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.

  8. Measuring kinetic rate constants of multiple-component reactions with optical biosensors.

    PubMed

    Edwards, David A; Evans, Ryan M; Li, Wenbin

    2017-09-15

    One may measure the kinetic rate constants associated with biochemical reactions using an optical biosensor: an instrument in which ligand molecules are convected through a flow cell over a surface to which receptors are immobilized. If there are multiple reactants, one is faced with the problem of fitting multiple kinetic rate constants to one signal, since data from all of the reacting species is lumped together. Even in the presence of ambiguous data, one may use a series of experiments to accurately determine the rate constants. Moreover, the true set of rate constants may be identified by either postprocessing the signals or adjusting the ligand inflow concentrations. Published by Elsevier Inc.

  9. 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.

  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.

  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. Controlling the rate of organic reactions: rational design of allosteric Diels-Alderase ribozymes.

    PubMed

    Amontov, Sergey; Jäschke, Andres

    2006-01-01

    Allosteric mechanisms are widely used in nature to control the rates of enzymatic reactions, but little is known about RNA catalysts controlled by these principles. The only natural allosteric ribozyme reported to date catalyzes an RNA cleavage reaction, and so do almost all artificial systems. RNA has, however, been shown to accelerate a much wider range of chemical reactions. Here we report that RNA catalysts for organic reactions can be put under the stringent control of effector molecules by straight-forward rational design. This approach uses known RNA sequences with catalytic and ligand-binding properties, and exploits weakly conserved sequence elements and available structural information to induce the formation of alternative, catalytically inactive structures. The potential and general applicability is demonstrated by the design of three different systems in which the rate of a catalytic carbon-carbon bond forming reaction is positively regulated up to 2100-fold by theophylline, tobramycin and a specific mRNA sequence, respectively. Although smaller in size than a tRNA, all three ribozymes show typical features of allosteric metabolic enzymes, namely high rate acceleration and tight allosteric regulation. Not only do these findings demonstrate RNA's power as a catalyst, but also highlight on RNA's capabilities as signaling components in regulatory networks.

  13. Controlling the rate of organic reactions: rational design of allosteric Diels-Alderase ribozymes

    PubMed Central

    Amontov, Sergey; Jäschke, Andres

    2006-01-01

    Allosteric mechanisms are widely used in nature to control the rates of enzymatic reactions, but little is known about RNA catalysts controlled by these principles. The only natural allosteric ribozyme reported to date catalyzes an RNA cleavage reaction, and so do almost all artificial systems. RNA has, however, been shown to accelerate a much wider range of chemical reactions. Here we report that RNA catalysts for organic reactions can be put under the stringent control of effector molecules by straight-forward rational design. This approach uses known RNA sequences with catalytic and ligand-binding properties, and exploits weakly conserved sequence elements and available structural information to induce the formation of alternative, catalytically inactive structures. The potential and general applicability is demonstrated by the design of three different systems in which the rate of a catalytic carbon–carbon bond forming reaction is positively regulated up to 2100-fold by theophylline, tobramycin and a specific mRNA sequence, respectively. Although smaller in size than a tRNA, all three ribozymes show typical features of allosteric metabolic enzymes, namely high rate acceleration and tight allosteric regulation. Not only do these findings demonstrate RNA's power as a catalyst, but also highlight on RNA's capabilities as signaling components in regulatory networks. PMID:16990253

  14. Derivation of a valid momentary first-order rate constant for kinetic and energetic analyses of enzymatic reactions.

    PubMed

    Imoto, Taiji

    2016-12-01

    To analyze enzymatic reactions energetically for comparison with non-enzymatic reactions (first order) under the same dimension, a method to derive valid momentary first-order rate constants for enzymatic reactions was developed. The momentary first-order rate constant, k enz0 = k cat[E'S']e,0/[S]0, was derived for an enzymatic reaction under a certain condition. It was shown that this rate constant is applicable for a wide range of enzymatic reactions. Utilizing this constant, one can conduct reliable kinetic and energetic analyses of enzymatic reactions.

  15. The influence of the sequence of nanoparticles injection to solution on the rate of fibrinogen-thrombin reaction

    NASA Astrophysics Data System (ADS)

    Kirichenko, M. N.; Krivokhiza, S. V.; Chaikov, L. L.; Bulychev, N. A.

    2017-01-01

    The influence of Fe2O3 nanoparticles on the rate of fibrinogen-thrombin reaction is studied. The nanoparticles were obtained in acoustoplasma discharge with cavitation. The sequence of nanoparticles injection appeared to change dramatically the rate and result of enzymatic reaction. In case of nanoparticles injection to fibrinogen before thrombin addition, enzymatic reaction practically stopped at the first stage. The mixing of nanoparticles with thrombin before its addition to fibrinogen leads to acceleration of gel formation in comparison with reaction without nanoparticles. We believe that Fe2O3 nanoparticles can modify the rate of enzymatic reaction, in one case acting as inhibitors of the reaction and as activators in other.

  16. Upper limit of a tunneling reaction rate for D-+H2 →HD+H-

    NASA Astrophysics Data System (ADS)

    Endres, Eric S.; Lakhamanskaya, Olga; Simpson, Malcolm; Spieler, Steffen; Wester, Roland

    2017-02-01

    The exothermic proton transfer reaction D-+H2→ HD+H- is known to proceed over a barrier of about 0.33 eV. Here we investigate whether this reaction may occur at low temperatures via tunneling through this barrier. The experiments were carried out in a cryogenic 22-pole ion trap, which provides a high sensitivity for slow ion-molecule reactions. Our experiments show no sign of the tunneling reaction with an upper limit to the rate coefficient of 2.6 ×10-18 cm3/s obtained from the decrease of the D- signal and 9 ×10-19 cm3/s from the absence of an increase of H-. Background impurities were identified to be the main limitation of the sensitivity.

  17. 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.

  18. Study of the ammonia (gas)-sulfuric acid (aerosol) reaction rate

    SciTech Connect

    McMurry, P.H.; Takano, H.; Anderson, G.R.

    1983-06-01

    An experimental study of the reaction rate between monodisperse sulfuric acid aerosols and ammonia gas is described. Reactions took place in a laminar flow reactor at 24/sup 0/C and 6% relative humidity, and reaction products were sampled from the core of the flow so that reaction times were well defined. For the data reported here, the reaction time was 5.0 +/- 0.5 s, ammonia concentrations ranged from 13 to 63 ppb, and particle sizes ranged from 0.03 to 0.2 ..mu..m. The extent of reaction was determined by comparing the hygroscopic and deliquescent properties of the product aerosols with known properties of aerosols consisting of internal mixtures of sulfuric acid and ammonium sulfate. It was found that the average fraction of ammonia-aerosol collisions that resulted in chemical reaction during neutralization decreased from 0.40 +/- 0.10 for 0.058-..mu..m particles to 0.18 +/- 0.03 for 0.10-..mu..m particles. Differential mobility analyzers were used for generating the monodisperse aerosols and also for measuring the hygroscopic and deliquescent properties of the product aerosols.

  19. Relative rate studies of the reactions of chlorine atoms with simple alkanes and the chlorinated methanes

    SciTech Connect

    Wingen, L.; Lee, J.J.; Neavyn, R.

    1995-12-01

    The reactions of chlorine atoms with organics are of interest because atomic chlorine is a potential tropospheric oxidant. Relative rate constants for the reaction of pairs of simple alkanes (ethane/propane, ethane/n-butane, and isobutane/n-butane) and the chlorinated methanes (chloromethane, dichloromethane, and chloroform relative to methane) were measured, using the photolysis of Cl{sub 2} as the source of chlorine atoms and following the loss of the organics by GC-FID. The ratios of the relative rate constants were in excellent agreement with the literature except for ethane/n-butane, where our results are approximately 20% lower than recently published values, and for chloroform/methane, where our value is approximately 50% higher than the values recommended by JPL and JPCRD. Our results will be compard to previously published relative rate studies as well as to the results of absolute rate constant studies, and the differences will be discussed.

  20. Dosimetric impact of source-positioning uncertainty in high-dose-rate balloon brachytherapy of breast cancer

    PubMed Central

    2015-01-01

    Purpose To evaluate the dosimetric impact of source-positioning uncertainty in high-dose-rate (HDR) balloon brachytherapy of breast cancer. Material and methods For 49 HDR balloon patients, each dwell position of catheter(s) was manually shifted distally (+) and proximally (–) with a magnitude from 1 to 4 mm. Total 392 plans were retrospectively generated and compared to corresponding clinical plans using 7 dosimetric parameters: dose (D95) to 95% of planning target volume for evaluation (PTV_EVAL), and volume covered by 100% and 90% of the prescribed dose (PD) (V100 and V90); skin and rib maximum point dose (Dmax); normal breast tissue volume receiving 150% and 200% of PD (V150 and V200). Results PTV_EVAL dosimetry deteriorated with larger average/maximum reduction (from ± 1 mm to ± 4 mm) for larger source position uncertainty (p value < 0.0001): from 1.0%/2.5%, 3.3%/5.9%, 6.3%/10.0% to 9.8%/14.5% for D95; from 1.0%/2.6%, 3.1%/5.7%, 5.8%/8.9% to 8.7%/12.3% for V100; from 0.2%/1.5%, 1.0%/4.0%, 2.7%/6.8% to 5.1%/10.3% for V90. ≥ ± 3 mm shift reduced average D95 to < 95% and average V100 to < 90%. While skin and rib Dmax change was case-specific, its absolute change (∣Δ(Value)∣) showed that larger shift and high dose group had larger variation compared to smaller and lower dose group (p value < 0.0001), respectively. Normal breast tissue V150 variation was case-specific and small. Average ∣Δ(V150)∣ was 0.2 cc for the largest shift (± 4 mm) with maximum < 1.7 cc. V200 was increased with higher elevation for larger shift: from 6.4 cc/9.8 cc, 7.0 cc/10.1 cc, 8.0 cc/11.3 cc to 9.2 cc/ 13.0 cc. Conclusions The tolerance of ± 2 mm recommended by AAPM TG 56 is clinically acceptable in most clinical cases. However, special attention should be paid to a case where both skin and rib are located proximally to balloon, and the orientation of balloon catheter(s) is vertical to these critical structures. In this case, sufficient dosimetric planning margins are

  1. Consistency between kinetics and thermodynamics: general scaling conditions for reaction rates of nonlinear chemical systems without constraints far from equilibrium.

    PubMed

    Vlad, Marcel O; Popa, Vlad T; Ross, John

    2011-02-03

    We examine the problem of consistency between the kinetic and thermodynamic descriptions of reaction networks. We focus on reaction networks with linearly dependent (but generally kinetically independent) reactions for which only some of the stoichiometric vectors attached to the different reactions are linearly independent. We show that for elementary reactions without constraints preventing the system from approaching equilibrium there are general scaling relations for nonequilibrium rates, one for each linearly dependent reaction. These scaling relations express the ratios of the forward and backward rates of the linearly dependent reactions in terms of products of the ratios of the forward and backward rates of the linearly independent reactions raised to different scaling powers; the scaling powers are elements of the transformation matrix, which relates the linearly dependent stoichiometric vectors to the linearly independent stoichiometric vectors. These relations are valid for any network of elementary reactions without constraints, linear or nonlinear kinetics, far from equilibrium or close to equilibrium. We show that similar scaling relations for the reaction routes exist for networks of nonelementary reactions described by the Horiuti-Temkin theory of reaction routes where the linear dependence of the mechanistic (elementary) reactions is transferred to the overall (route) reactions. However, in this case, the scaling conditions are valid only at the steady state. General relationships between reaction rates of the two levels of description are presented. These relationships are illustrated for a specific complex reaction: radical chlorination of ethylene.

  2. 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.

  3. 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

  4. 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.

  5. The effect of flow rate on the oscillatory activation energy of an oscillating reaction

    NASA Astrophysics Data System (ADS)

    Monteiro, Emily V.; Varela, Hamilton; Faria, Roberto B.

    2017-09-01

    The simultaneous influence of temperature and flow rate (k0) in the oscillatory regime of the bromate-oxalic acid-acetone-Ce(III) oscillating reaction was investigated. The influence of temperature was evaluated in terms of the oscillatory activation energy (Eω), which was determined at different flow rates. Increasing k0, the oscillatory activation energy is decreased, tending to a limit value, Eω∞. The sensitivity of Eω with k0 is described by the parameter η = dEω/d(1/k0). Eω∞ and η are global properties of any particular oscillating reaction and describes a correlation between the dynamical behavior and temperature, and should be used when comparing different oscillating reactions.

  6. Rate constants of the reactions of ozone with nitriles, acrylates and terpenes in gas phase

    NASA Astrophysics Data System (ADS)

    Munshi, Hushider B.; Rao, K. V. S. Rama; Iyer, R. Mahadeva

    Rate constants for the reactions of acrylonitrile, methacrylonitrile, methyl and ethyl acrylate with O 3 have been determined with the help of a flow system coupled to an u.v. spectrophotometer. The rate constants obtained have enabled an estimation of the tropospheric lifetimes with respect to O 3 and have also offered a clue to the nature of the initial ozone attack on the unsaturates. Non-stoichiometry observed in the case of acrylonitrile and ethyl acrylate has been rationalized by secondary free radical reactions. Absorptivities of the four unsaturates in vapour as well as in the solution phase have been reported. A brief attempt to study ozone-terpene reactions is also described.

  7. Rate constant for the reaction of O(3P) with diacetylene from 210 to 423 K

    NASA Technical Reports Server (NTRS)

    Mitchell, M. B.; Nava, D. F.; Stief, L. J.

    1986-01-01

    The absolute rate constant for the reaction of O(3P) with diacetylene (C4H2) has been measured as a function of pressure and temperature by the flash-photolysis/resonance-fluorescence method. At 298 K and below, no pressure dependence of the rate constant was observed, but at 423 K a moderate (factor-of-2) increase was detected in the range 3 to 75 torr Ar.Results at or near the high-pressure limit are represented by an Arrhenius expression over the temperature range 210 to 423 K. The results are compared with previous determinations, all of which employed the discharge-flow/mass-spectrometry technique. The mechanism of the reaction is considered, including both primary and secondary processes. The heats of formation of the reactants, adducts, and products for the O(3P) + C4H2 reaction are discussed and contrasted with those for O(3P) + C2H2.

  8. 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.

  9. Biochemistry on a leash: Confinement as a regulatory mechanism for bimolecular reaction rates

    NASA Astrophysics Data System (ADS)

    Reeves, Daniel; Cheveralls, Keith; Kondev, Jane

    2009-03-01

    We describe two mechanisms by which confinement regulates diffusion-limited bimolecular reaction rates. The first mechanism, illustrated by the actin capping protein formin, uses a flexible polymer to tether ligand binding sites, which serve as intermediaries, to the reactive site. The second mechanism uses a potential (e.g. hard wall potential), to constrain the motion of a ligand receptor within a confining volume. We analyze both mechanisms theoretically, using a combination of analytic and numerical techniques, to obtain the steady state binding kinetics. We explore how the reaction rates are regulated by parameters of the model such as the length of the polymer tether, and use our findings to explain the key features of the formin system. Finally, we suggest other systems, both synthetic and biological, in which these mechanisms for regulating bimolecular reactions might be at play.

  10. 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.

  11. Investigating rare events with nonequilibrium work measurements. II. Transition and reaction rates.

    PubMed

    Moradi, Mahmoud; Sagui, Celeste; Roland, Christopher

    2014-01-21

    We present a formalism for investigating transition pathways and transition probabilities for rare events in biomolecular systems. The formalism is based on combining Transition Path Theory with the results of nonequilibrium work relations, and shows that the equilibrium and nonequilibrium transition rates are in fact related. Aside from its fundamental importance, this allows for the calculation of relative equilibrium reaction rates with driven nonequilibrium simulations such as Steered Molecular Dynamics. The workings of the formalism are illustrated with a few typical numerical examples.

  12. SENSMG: First-Order Sensitivities of Neutron Reaction Rates, Reaction-Rate Ratios, Leakage, keff, and α Using PARTISN

    SciTech Connect

    Favorite, Jeffrey A.

    2016-11-21

    SENSMG is a tool for computing first-order sensitivities of neutron reaction rates, reaction-rate ratios, leakage, keff, and α using the PARTISN multigroup discrete-ordinates code. SENSMG computes sensitivities to all of the transport cross sections and data (total, fission, nu, chi, and all scattering moments), two edit cross sections (absorption and capture), and the density for every isotope and energy group. It also computes sensitivities to the mass density for every material and derivatives with respect to all interface locations. The tool can be used for one-dimensional spherical (r) and two-dimensional cylindrical (r-z) geometries. The tool can be used for fixed-source and eigenvalue problems. The tool implements Generalized Perturbation Theory (GPT) as discussed by Williams and Stacey. Section II of this report describes the theory behind adjoint-based sensitivities, gives the equations that SENSMG solves, and defines the sensitivities that are output. Section III describes the user interface, including the input file and command line options. Section IV describes the output. Section V gives some notes about the coding that may be of interest. Section VI discusses verification, which is ongoing. Section VII lists needs and ideas for future work. Appendix A lists all of the input files whose results are presented in Sec. VI.

  13. 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

  14. Acid-base chemical reaction model for nucleation rates in the polluted atmospheric boundary layer.

    PubMed

    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

    2012-11-13

    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.

  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. The Effect of Conceptual Change Pedagogy on Students' Conceptions of Rate of Reaction

    ERIC Educational Resources Information Center

    Calik, Muammer; Kolomuc, Ali; Karagolge, Zafer

    2010-01-01

    This paper reports on an investigation of the effect of conceptual change pedagogy on students' conceptions of "rate of reaction" concepts. The study used a pre-test/post-test non-equivalent comparison group design approach and the sample consisted of 72 Turkish grade-11 students (aged 16-18 years) selected from two intact classrooms.…

  17. 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.

  18. Reaction rate of beryllium with fluorine ion for Flibe redox control

    NASA Astrophysics Data System (ADS)

    Fukada, S.; Simpson, M. F.; Anderl, R. A.; Sharpe, J. P.; Katayama, K.; Smolik, G. R.; Oya, Y.; Terai, T.; Okuno, K.; Hara, M.; Petti, D. A.; Tanaka, S.; Sze, D.-K.; Sagara, A.

    2007-08-01

    An experimental effort to apply Flibe (a mixed molten salt of 2LiF + BeF 2) to a self-cooled liquid blanket of a fusion reactor was carried out under a Japan-US collaboration called JUPITER-II. Maintaining Flibe under a reducing atmosphere is a key issue to transform TF to T 2 with a faster reaction rate compared with the residence time in blanket. One of the tasks was to clarify whether or not the redox control of Flibe can be achieved with Be. The dissolution rate of a Be rod and the reaction rate of Be + 2HF = BeF 2 + H 2 in Flibe were experimentally determined. Sufficiently fast rates of the Be dissolution and the reduction reaction of HF to H 2 were clarified by our redox control experiment. Close agreement was obtained between experiments and our simplified complete-mixing model. In particular, the reaction between Be and a F - ion immediately after their contact was found to be limited by diffusion of the F - ion.

  19. 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.

  20. 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…

  1. 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.

  2. Interpretation of biological ion channel flux data--reaction-rate versus continuum theory.

    PubMed

    Levitt, D G

    1986-01-01

    Although the reaction-rate theory may provide a useful mathematical description of the channel flux, it presents a misleading physical picture of the channel structure. There is a tendency to regard the barriers in the model as actual physical structures, whereas they are actually only mathematical artifacts that allow one to reduce a complicated differential equation with an infinite number of states to a finite difference equation with a minimum number of states. I argue that the energy profile in the permeation pathway of most biological channels should vary relatively smoothly with only a few localized energy barriers or wells. In these smoothly varying regions, the resistance to ion movement is similar to bulk diffusion and cannot be accurately modeled by one or two energy barriers. For the one-ion channel, the continuum approach is as general and at least as simple as the reaction-rate theory and may provide a more physical interpretation of the data. Thus for the SR K+ channel, the structure suggested by the reaction-rate theory seems inconsistent with some experimental data, while the continuum-theory model is not only consistent with, but complements, the structure suggested by other data. Multi-ion channels have such complicated kinetics that one can only expect the theories to provide a qualitative description of the experimental data. They can be modeled by either the reaction-rate model or a finite difference approximation to the continuum model.

  3. 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.

  4. 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…

  5. 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.

  6. An Improved Reaction Rate Formulation for Charged-Particle Induced Thermonuclear Reaction of {sup 2}H(d,{gamma}){sup 4}He

    SciTech Connect

    Aziz, Azni Abdul; Yusof, Norhasliza; Idris, Mahirah; Kassim, Hasan Abu

    2011-03-30

    The reaction rate formula utilized in compilations such as the Nuclear Astrophysics Compilation of Reaction Rates (NACRE) uses low energy approximation due to temperatures in stars are in the region of a few keVs. Most nuclear reaction experiments were done in MeV range and the interior temperatures of massive stars are {approx}10{sup 9} K. Hence an improved formulation for calculating the nuclear reaction rate that is applicable to high temperatures is discussed in this work. The exact tunneling probability that is applicable for all energies is obtained by solving the Schroedinger equation. This yields an enhanced expression for the astrophysical S-factor for calculating the thermonuclear reaction rate at high temperature. The thermonuclear reaction rate from this work is applied to the {sup 2}H(d,{gamma}){sup 4}He reaction and is compared with the NACRE compilation. This improved reaction rate can be included in the nuclear reaction network in a Big Bang nucleosynthesis (BBN) code or a stellar nuclear network code.

  7. 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.

  8. 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.

  9. Effect of a mind-body therapeutic program for infertile women repeating in vitro fertilization treatment on uncertainty, anxiety, and implantation rate.

    PubMed

    Kim, Miok; Kim, Sue; Chang, Soon-bok; Yoo, Ji-Soo; Kim, Hee Kyung; Cho, Jung Hyun

    2014-03-01

    The study aimed to develop a mind-body therapeutic program and evaluate its effects on mitigating uncertainty, anxiety, and implantation rate of second-trial in vitro fertilization (IVF) women. This study employed a nonequivalent control group nonsynchronized design. The conceptual framework and program content were developed from a preliminary survey of eight infertile women and the extensive review of the literature. Program focuses on three uncertainty-induced anxieties in infertile women: cognitive, emotional, and biological responses. To evaluate the effect of the intervention, the infertile women with unknown cause preparing for a second IVF treatment were sampled at convenience (26 experimental and 24 control). The experimental group in the study showed greater decrease in uncertainty and anxiety in premeasurements and postmeasurements than the control group did. However, no statistically significant differences in the implantation rate between groups were observed. This study is meaningful as the first intervention program for alleviating uncertainty and anxiety provided during the IVF treatment process. The positive effects of the mind-body therapeutic program in alleviating both uncertainty and anxiety have direct meaning for clinical applications. Copyright © 2014. Published by Elsevier B.V.

  10. Estimating reaction rate coefficients within a travel-time modeling framework.

    PubMed

    Gong, R; Lu, C; Wu, W-M; Cheng, H; Gu, B; Watson, D; Jardine, P M; Brooks, S C; Criddle, C S; Kitanidis, P K; Luo, J

    2011-01-01

    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.

  11. Design of experiments for zeroth and first-order reaction rates.

    PubMed

    Amo-Salas, Mariano; Martín-Martín, Raúl; Rodríguez-Aragón, Licesio J

    2014-09-01

    This work presents optimum designs for reaction rates experiments. In these experiments, time at which observations are to be made and temperatures at which reactions are to be run need to be designed. Observations are performed along time under isothermal conditions. Each experiment needs a fixed temperature and so the reaction can be measured at the designed times. For these observations under isothermal conditions over the same reaction a correlation structure has been considered. D-optimum designs are the aim of our work for zeroth and first-order reaction rates. Temperatures for the isothermal experiments and observation times, to obtain the most accurate estimates of the unknown parameters, are provided in these designs. D-optimum designs for a single observation in each isothermal experiment or for several correlated observations have been obtained. Robustness of the optimum designs for ranges of the correlation parameter and comparisons of the information gathered by different designs are also shown. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Quantifying plyometric intensity via rate of force development, knee joint, and ground reaction forces.

    PubMed

    Jensen, Randall L; Ebben, William P

    2007-08-01

    Because the intensity of plyometric exercises usually is based simply upon anecdotal recommendations rather than empirical evidence, this study sought to quantify a variety of these exercises based on forces placed upon the knee. Six National Collegiate Athletic Association Division I athletes who routinely trained with plyometric exercises performed depth jumps from 46 and 61 cm, a pike jump, tuck jump, single-leg jump, countermovement jump, squat jump, and a squat jump holding dumbbells equal to 30% of 1 repetition maximum (RM). Ground reaction forces obtained via an AMTI force plate and video analysis of markers placed on the left hip, knee, lateral malleolus, and fifth metatarsal were used to estimate rate of eccentric force development (E-RFD), peak ground reaction forces (GRF), ground reaction forces relative to body weight (GRF/BW), knee joint reaction forces (K-JRF), and knee joint reaction forces relative to body weight (K-JRF/BW) for each plyometric exercise. One-way repeated measures analysis of variance indicated that E-RFD, K-JRF, and K-JRF/BW were different across the conditions (p < 0.05), but peak GRF and GRF/BW were not (p > 0.05). Results indicate that there are quantitative differences between plyometric exercises in the rate of force development during landing and the forces placed on the knee, though peak GRF forces associated with landing may not differ.

  13. 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.

  14. Using a detailed uncertainty analysis to adjust mapped rates of forest disturbance derived from Landsat time series data (Invited)

    NASA Astrophysics Data System (ADS)

    Cohen, W. B.; Yang, Z.; Stehman, S.; Huang, C.; Healey, S. P.

    2013-12-01

    Forest ecosystem process models require spatially and temporally detailed disturbance data to accurately predict fluxes of carbon or changes in biodiversity over time. A variety of new mapping algorithms using dense Landsat time series show great promise for providing disturbance characterizations at an annual time step. These algorithms provide unprecedented detail with respect to timing, magnitude, and duration of individual disturbance events, and causal agent. But all maps have error and disturbance maps in particular can have significant omission error because many disturbances are relatively subtle. Because disturbance, although ubiquitous, can be a relatively rare event spatially in any given year, omission errors can have a great impact on mapped rates. Using a high quality reference disturbance dataset, it is possible to not only characterize map errors but also to adjust mapped disturbance rates to provide unbiased rate estimates with confidence intervals. We present results from a national-level disturbance mapping project (the North American Forest Dynamics project) based on the Vegetation Change Tracker (VCT) with annual Landsat time series and uncertainty analyses that consist of three basic components: response design, statistical design, and analyses. The response design describes the reference data collection, in terms of the tool used (TimeSync), a formal description of interpretations, and the approach for data collection. The statistical design defines the selection of plot samples to be interpreted, whether stratification is used, and the sample size. Analyses involve derivation of standard agreement matrices between the map and the reference data, and use of inclusion probabilities and post-stratification to adjust mapped disturbance rates. Because for NAFD we use annual time series, both mapped and adjusted rates are provided at an annual time step from ~1985-present. Preliminary evaluations indicate that VCT captures most of the higher

  15. α-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products

    NASA Astrophysics Data System (ADS)

    Jones, Brian T.; Ham, Jason E.

    The bimolecular rate constant of k rad +α-terpineol (16 ± 4) × 10 -12 cm 3 molecule -1 s -1 was measured using the relative rate technique for the reaction of the nitrate radical (NO 3rad ) with α-terpineol (2-(4-methyl-1-cyclohex-3-enyl)propan-2-ol) at 297 ± 3 K and 1 atmosphere total pressure. To more clearly define part of α-terpineol's indoor environment degradation mechanism, the products of α-terpineol + NO 3rad reaction were investigated. The identified reaction products were: acetone, glyoxal (HC( dbnd O)C( dbnd O)H), and methylglyoxal (CH 3C( dbnd O)C( dbnd O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose the other major reaction products: 6-hydroxyhept-5-en-2-one, 4-(1-hydroxy-1-methylethyl)-1-methyl-2-oxocyclohexyl nitrate, 5-(1-hydroxy-1-methylethyl)-2-oxocyclohexyl nitrate, 1-formyl-5-hydroxy-4-(hydroxymethyl)-1,5-dimethylhexyl nitrate, and 1,4-diformyl-5-hydroxy-1,5-dimethylhexyl nitrate. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible α-terpineol + NO 3rad reaction mechanisms based on previously published volatile organic compound + NO 3rad gas-phase mechanisms. The additional gas-phase products (2,6,6-trimethyltetrahydro-2 H-pyran-2,5-dicarbaldehyde and 2,2-dimethylcyclohexane-1,4-dicarbaldehyde) are proposed to be the result of cyclization through a reaction intermediate.

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

    PubMed Central

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

    2008-01-01

    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. PMID:18226939

  17. Helium Ignition on Accreting Neutron Stars with a New Triple-α Reaction Rate

    NASA Astrophysics Data System (ADS)

    Peng, Fang; Ott, Christian D.

    2010-12-01

    We investigate the effect of a new triple-α reaction rate from Ogata et al. on helium ignition conditions on accreting neutron stars and on the properties of the subsequent type I X-ray burst. We find that the new rate leads to significantly lower ignition column density for accreting neutron stars at low accretion rates. We compare the results of our ignition models for a pure helium accretor to observations of bursts in ultracompact X-ray binaries (UCXBs), which are believed to have nearly pure helium donors. For \\dot{m}> 0.001 \\dot{m}_{{Edd}}, the new triple-α reaction rate from Ogata et al. predicts a maximum helium ignition column of ~3 × 109 g cm-2, corresponding to a burst energy of ~4 × 1040 erg. For \\dot{m}˜ 0.01 \\dot{m}_{{Edd}} at which intermediate long bursts occur, the predicted burst energies are at least a factor of 10 too low to explain the observed energies of such bursts in UCXBs. This finding adds to the doubts cast on the triple-α reaction rate of Ogata et al. by the low-mass stellar evolution results of Dotter & Paxton.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Quantum three-body calculation of nonresonant triple-{alpha} reaction rate at low temperatures

    SciTech Connect

    Ogata, Kazuyuki; Kan, Masataka; Kamimura, Masayasu

    2010-08-12

    Triple-{alpha} reaction rate is re-evaluated by directly solving the three-body Schroedinger equation. The resonant and nonresonant processes are treated on the same footing using the continuum-discretized coupled-channels method for three-body scattering. An accurate description of the {alpha}-{alpha} nonresonant states significantly quenches the Coulomb barrier between the first two {alpha}-particles and the third {alpha}-particle. Consequently, the{alpha}-{alpha} nonresonant continuum states give a markedly larger contribution at low temperatures than that reported in previous studies. We show that Nomoto's method for three-body nonresonant capture processes, which is adopted in the NACRE compilation and many other studies, is a crude approximation of the accurate quantum three-body model calculation. We find an increase in triple-{alpha} reaction rate by about 20 orders of magnitude around 10{sup 7} K compared with the rate of NACRE.

  3. Quantum three-body calculation of nonresonant triple-alpha reaction rate at low temperatures

    SciTech Connect

    Ogata, Kazuyuki; Kan, Masataka; Kamimura, Masayasu

    2010-06-01

    Triple-alpha reaction rate is re-evaluated by directly solving the three-body Schroedinger equation. The resonant and nonresonant processes are treated on the same footing using the continuum-discretized coupled-channels method for three-body scattering. An accurate description of the alpha-alpha nonresonant states significantly quenches the Coulomb barrier between the first two alpha-particles and the third alpha-particle. Consequently, the alpha-alpha nonresonant continuum states give a markedly larger contribution at low temperatures than that reported in previous studies. We show that Nomoto's method for three-body nonresonant capture processes, which is adopted in the NACRE compilation and many other studies, is a crude approximation of the accurate quantum three-body model calculation. We find an increase in triple-alpha reaction rate by 26 orders of magnitude around 10{sup 7} K compared with the rate of NACRE.

  4. 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.

  5. Rapid heartbeat, but dry palms: reactions of heart rate and skin conductance levels to social rejection.

    PubMed

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

    2014-01-01

    Social rejection elicits negative mood, emotional distress, and neural activity in networks that are associated with physical pain. However, studies assessing physiological reactions to social rejection are rare and results of these studies were found to be ambiguous. Therefore, the present study aimed to examine and specify physiological effects of social rejection. Participants (n = 50) were assigned to either a social exclusion or inclusion condition of a virtual ball-tossing game (Cyberball). Immediate and delayed physiological [skin conductance level (SCL) and heart rate] reactions were recorded. In addition, subjects reported levels of affect, emotional states, and fundamental needs. Subjects who were socially rejected showed increased heart rates. However, social rejection had no effect on subjects' SCLs. Both conditions showed heightened arousal on this measurement. Furthermore, psychological consequences of social rejection indicated the validity of the paradigm. Our results reveal that social rejection evokes an immediate physiological reaction. Accelerated heart rates indicate that behavior activation rather than inhibition is associated with socially threatening events. In addition, results revealed gender-specific response patterns suggesting that sample characteristics such as differences in gender may account for ambiguous findings of physiological reactions to social rejection.

  6. Rapid heartbeat, but dry palms: reactions of heart rate and skin conductance levels to social rejection

    PubMed Central

    Iffland, Benjamin; Sansen, Lisa M.; Catani, Claudia; Neuner, Frank

    2014-01-01

    Background: Social rejection elicits negative mood, emotional distress, and neural activity in networks that are associated with physical pain. However, studies assessing physiological reactions to social rejection are rare and results of these studies were found to be ambiguous. Therefore, the present study aimed to examine and specify physiological effects of social rejection. Methods: Participants (n = 50) were assigned to either a social exclusion or inclusion condition of a virtual ball-tossing game (Cyberball). Immediate and delayed physiological [skin conductance level (SCL) and heart rate] reactions were recorded. In addition, subjects reported levels of affect, emotional states, and fundamental needs. Results: Subjects who were socially rejected showed increased heart rates. However, social rejection had no effect on subjects' SCLs. Both conditions showed heightened arousal on this measurement. Furthermore, psychological consequences of social rejection indicated the validity of the paradigm. Conclusions: Our results reveal that social rejection evokes an immediate physiological reaction. Accelerated heart rates indicate that behavior activation rather than inhibition is associated with socially threatening events. In addition, results revealed gender-specific response patterns suggesting that sample characteristics such as differences in gender may account for ambiguous findings of physiological reactions to social rejection. PMID:25221535

  7. 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.

  8. 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.

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

    SciTech Connect

    Scott C. Brooks; Wenming Dong; Sue Carroll; Jim Fredrickson; Ken Kemner; Shelly 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. ? Elucidate the controls on the rate and extent of contaminant reactivity. (2) Provide new insights into the aqueous and solid speciation of U(VI)/U(IV) under representative groundwater conditions.

  10. 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.

  11. The effect of heat conduction on the rate of chemical reaction in dilute gases

    NASA Astrophysics Data System (ADS)

    Fort, J.; Cukrowski, A. S.

    1997-09-01

    Information statistical theory is used to obtain the second-order terms (similar to those analyzed in the Burnett approximation to the solution of the Boltzmann equation) in the expansion of the nonequilibrium velocity distribution function. These terms are used for the evaluation of the effect of the heat flux on the rate of bimolecular chemical reactions. This effect is shown to be important for reactions characterized by high values of the activation energy. However, very large values of the heat flux would be necessary. The results are compared with those obtained earlier from the square terms calculated from the linearized Boltzmann equation and with recent results due to Nettleton.

  12. 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.

  13. 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.

  14. 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.

  15. Rate constant for the reaction SO + BrO yields SO2 + Br

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L.

    1986-01-01

    The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

  16. 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

  17. Determination of relative rate constants for in vitro RNA processing reactions by internal competition.

    PubMed

    Lin, Hsuan-Chun; Yandek, Lindsay E; Gjermeni, Ino; Harris, Michael E

    2014-12-15

    Studies of RNA recognition and catalysis typically involve measurement of rate constants for reactions of individual RNA sequence variants by fitting changes in substrate or product concentration to exponential or linear functions. A complementary approach is determination of relative rate constants by internal competition, which involves quantifying the time-dependent changes in substrate or product ratios in reactions containing multiple substrates. Here, we review approaches for determining relative rate constants by analysis of both substrate and product ratios and illustrate their application using the in vitro processing of precursor transfer RNA (tRNA) by ribonuclease P as a model system. The presence of inactive substrate populations is a common complicating factor in analysis of reactions involving RNA substrates, and approaches for quantitative correction of observed rate constants for these effects are illustrated. These results, together with recent applications in the literature, indicate that internal competition offers an alternate method for analyzing RNA processing kinetics using standard molecular biology methods that directly quantifies substrate specificity and may be extended to a range of applications. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

    PubMed

    Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

    2012-04-28

    The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction.

  19. Formulation of a universal first-order rate constant for enzymatic reactions.

    PubMed

    Imoto, Taiji

    2013-01-01

    It is a common practice to employ k(cat)[E]₀/K(m) as a first-order rate constant for the analysis of an enzymatic reaction, where [E]₀ is the total enzyme concentration. I describe in this report a serious shortcoming in analyzing enzymatic reactions when kcat[E]₀/K(m) is employed and show that k(cat)[E]₀/K(m) can only be applied under very limited conditions. I consequently propose the use of a more universal first-order rate constant, k(cat)[ES](K)/[S]₀, where [ES](K) is the initial equilibrium concentration of the ES-complex derived from [E]₀, [S]₀ and K(m). Employing k(cat)[ES](K)/[S]₀ as the first-order rate constant enables all enzymatic reactions to be reasonably simulated under a wide range of conditions, and the catalytic and binding contributions to the rate constant of any enzyme can be determined under any and all conditions.

  20. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate.

    PubMed

    Wu, Junjun; Khaled, Fethi; Ning, Hongbo; Ma, Liuhao; Farooq, Aamir; Ren, Wei

    2017-08-24

    We report a systematic chemical kinetics study of the H atom abstractions from ethyl formate (EF) by H, O((3)P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range 500-2500 K by the transition state theory (TST) in conjunction with the asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900-1321 K and 1.4-2.0 atm. Our theoretical rate constants of OH + EF → products agree well with the experimental results within 15% over the experimental temperature range of 900-1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  1. On OH and O3 Reaction Rates with Isoprene-Derived Hydroxy Nitrates

    NASA Astrophysics Data System (ADS)

    Lee, L.; Teng, A.; Crounse, J.; Wennberg, P. O.; Cohen, R. C.

    2013-12-01

    3 of the 8 primary isoprene hydroxy nitrate isomers ((E & Z)-2-methyl-4-nitrooxybut-2-ene-1-ol and 2-methyl-1-nitrooxybut-3-ene-2-ol) were synthesized. The purity of these isomers was confirmed with proton NMR spectroscopy. Oxidation of these unsaturated nitrates by OH and O3 were studied in an environmental chamber equipped with both Chemical Ionization Mass Spectrometer (CIMS) and Thermo-Dissociation Laser Induced Fluorescence (TD-LIF) instrument for continuous monitoring of reactants and products. The OH reaction rates of the individual isomers were measured relative to propene resulting in rate constants for each isomer, in the same order as above, of: 1.1×10-10, 1.1×10-10 and 4.2×10-11 cm3/s. For the O3 reaction rate constant of 2-methyl-1-nitrooxybut-3-ene-2-ol, we report an interval of (2.5~5)×10-19 cm3/s. The precision of our estimate on this very slow process was limited by the chamber wall loss. For (E) and (Z)-2-methyl-4-nitrooxybut-2-ene-1-ol the O3 rate constants are 2.7×10-17 and 2.9×10-17 cm3/s, respectively. Reaction pathways, product yields and implications for atmospheric chemistry are discussed.

  2. 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.

  3. Mathematical Formalism of Nonequilibrium Thermodynamics for Nonlinear Chemical Reaction Systems with General Rate Law

    NASA Astrophysics Data System (ADS)

    Ge, Hao; Qian, Hong

    2017-01-01

    This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with N species, M reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs' macroscopic chemical thermodynamics under G. N. Lewis' kinetic law of entire equilibrium (detailed balance in nonlinear chemical kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy function and its associated balance equation with nonnegative source and sink are the major discoveries. The proof is based on the large deviation principle of this type of Markov processes. A general fluctuation dissipation theorem for stochastic reaction kinetics is also proved. The mathematical theory illustrates how a novel macroscopic dynamic law can emerges from the mesoscopic kinetics in a multi-scale system.

  4. 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.

  5. Reaction Rates for H-burning in Stars from Experiments with Radioactive Nuclear Beams

    NASA Astrophysics Data System (ADS)

    Trache, Livius

    2008-01-01

    In this lecture some of the indirect methods for nuclear astrophysics that can be applied to extract reaction rates for H-burning in stars are treated. Instead of reviewing all methods, I chose for exemplification four different experiments of our Texas A&M group, each involving a different method, but all related to the study of the proton rich nucleus 23Al. They involve the use of radioactive nuclear beams. I will describe the use of one-nucleon transfer reactions (the ANC method), breakup reactions at intermediate energies, β-decay and β-delayed proton-decay to extract nuclear structure information that is then used for nuclear astrophysics. I will show the specificities of each method, talk about their complementarities and redundancies.

  6. Learned Cardiac Control with Heart Rate Biofeedback Transfers to Emotional Reactions

    PubMed Central

    Peira, Nathalie; Pourtois, Gilles; Fredrikson, Mats

    2013-01-01

    Emotions involve subjective feelings, action tendencies and physiological reactions. Earlier findings suggest that biofeedback might provide a way to regulate the physiological components of emotions. The present study investigates if learned heart rate regulation with biofeedback transfers to emotional situations without biofeedback. First, participants learned to decrease heart rate using biofeedback. Then, inter-individual differences in the acquired skill predicted how well they could decrease heart rate reactivity when later exposed to negative arousing pictures without biofeedback. These findings suggest that (i) short lasting biofeedback training improves heart rate regulation and (ii) the learned ability transfers to emotion challenging situations without biofeedback. Thus, heart rate biofeedback training may enable regulation of bodily aspects of emotion also when feedback is not available. PMID:23894574

  7. Learned cardiac control with heart rate biofeedback transfers to emotional reactions.

    PubMed

    Peira, Nathalie; Pourtois, Gilles; Fredrikson, Mats

    2013-01-01

    Emotions involve subjective feelings, action tendencies and physiological reactions. Earlier findings suggest that biofeedback might provide a way to regulate the physiological components of emotions. The present study investigates if learned heart rate regulation with biofeedback transfers to emotional situations without biofeedback. First, participants learned to decrease heart rate using biofeedback. Then, inter-individual differences in the acquired skill predicted how well they could decrease heart rate reactivity when later exposed to negative arousing pictures without biofeedback. These findings suggest that (i) short lasting biofeedback training improves heart rate regulation and (ii) the learned ability transfers to emotion challenging situations without biofeedback. Thus, heart rate biofeedback training may enable regulation of bodily aspects of emotion also when feedback is not available.

  8. 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.

  9. The Effects of Tempur Insoles on Ground Reaction Forces and Loading Rates in Running

    PubMed Central

    RUANO, CRYSTAL; POWELL, DOUGLAS; CHALAMBAGA, ELIZABETH T.; RENSHAW, DOUG

    2009-01-01

    Runners often experience over-use injuries. Ground reaction force (GRFs) patterns have been associated with these over-use injuries; however, it is not solely the magnitude of GRFs, but also the rate at which they are applied that lead to lower extremity injury. Many recreational runners will use over-the-counter insoles as a method of treating or preventing injury. Therefore, the purpose of this study was to examine the efficacy of two insoles on peak GRFs and loading rates. It was hypothesized that no differences in peak GRFs or loading rates would exist with the addition of two insoles during running. Twelve subjects (7 females; 5 males) performed seven running trials in each of the following conditions: no insoles (NORM), over-the-counter insoles (OTC) and memory-foam insoles (TEMPUR). GRFs were recorded using a force plate (1440Hz; AMTI) while subjects ran across a 15 meter lab. A 2 x 3 (gender x insole) repeated measures ANOVA was used to compare the effects of insoles on loading rate and ground reaction forces. Alpha level was set at p <0.05. The current study found no statistical differences in loading rate or GRFs between the insole and no insole conditions. Furthermore, there was no gender effect in any condition. The findings of the current study suggest that insoles do not attenuate shock or decrease loading rate. The lack of shock attenuation associated with insoles suggests they do not protect the lower extremity from injury. PMID:27182316

  10. 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

  11. Site-specific rate coefficients for reaction of OH with ethanol from 298 to 900 K.

    PubMed

    Carr, Scott A; Blitz, Mark A; Seakins, Paul W

    2011-04-21

    The rate coefficients for reactions of OH with ethanol and partially deuterated ethanols have been measured by laser flash photolysis/laser-induced fluorescence over the temperature range 298-523 K and 5-100 Torr of helium bath gas. The rate coefficient, k(1.1), for reaction of OH with C(2)H(5)OH is given by the expression k(1.1) = 1.06 × 10(-22)T(3.58) exp(1126/T) cm(3) molecule(-1) s(-1), and the values are in good agreement with previous literature. Site-specific rate coefficients were determined from the measured kinetic isotope effects. Over the temperature region 298-523 K abstraction from the hydroxyl site is a minor channel. The reaction is dominated by abstraction of the α hydrogens (92 ± 8)% at 298 K decreasing to (76 ± 9)% with the balance being abstraction at the β position where the errors are 2σ. At higher temperatures decomposition of the CH(2)CH(2)OH product from β abstraction complicates the kinetics. From 575 to 650 K, biexponential decays were observed, allowing estimates to be made for k(1.1) and the fractional production of CH(2)CH(2)OH. Above 650 K, decomposition of the CH(2)CH(2)OH product was fast on the time scale of the measured kinetics and removal of OH corresponds to reaction at the α and OH sites. The kinetics agree (within ±20%) with previous measurements. Evidence suggests that reaction at the OH site is significant at our higher temperatures: 47-53% at 865 K.

  12. 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

  13. Laboratory Experiments and Investigations on the Reaction Rates of Mg-sulfates Under Mars Relevant Conditions

    NASA Astrophysics Data System (ADS)

    Wang, A.; Freeman, J. J.

    2009-12-01

    Large deposits of hydrous Mg-sulfates was identified on Mars by orbital remote sensing (OMEGA on Mars Express and CRISM on Mars Reconnaissance Orbiter). Kieserite (MgSO4.H2O) and a non-specific “polyhydrated sulfates” are among the most observed and widely distributed sulfates (Bibring et al., 2005, Murchie et al., 2007). They frequently co-exist (Gendrin et al., 2005) and sometimes occur in alternative stratigraphic layers (Roach et al., 2008). Mg-sulfates were suggested, by compositional correlations and mineral models, to exist in Meridiani outcrops (Clark et al., 2005) and in rocks and regolith at Gusev (Squyres et al., 2006, Haskin et al., 2005, Wang et al., 2006, 2008); but no information on the hydration state of these sulfates can be extracted. We have conducted 188 experiments to investigate the stability fields and phase transition pathways of hydrous Mg-sulfates (Wang et al., 2009). In addition, we can extract the information on the reaction rates of five important dehydration and rehydration processes involved in these experiments. Our experiments were done at four temperatures (50°C, 21°C, 5°C, and -10°C) and ten relative humidity levels, with five hydrous Mg-sulfate species as starting phases. The rate information was extracted from the mineral identifications of the intermediate reaction products, measured by non-invasive Raman spectroscopy at regular time intervals during the entire duration of experiments (tens’ thousands hours). The rates for five processes are all strongly controlled by temperatures. We found that the experimental results match Arrhenius equation very well, thus the rate constants for dehydration and rehydration processes of Mg-sulfates at lower temperatures (down to 180K) can be approximately estimated by using the experimentally derived pre-exponential factor(s) and activation energy(s). In this study, only the orders of magnitudes for reaction rate ratios at different temperatures were considered. The estimated

  14. Reaction rate modeling in cryoconcentrated solutions: alkaline phosphatase catalyzed DNPP hydrolysis.

    PubMed

    Champion, D; Blond, G; Le Meste, M; Simatos, D

    2000-10-01

    The hydrolysis of disodium p-nitrophenyl phosphate catalyzed by alkaline phosphatase was chosen as a model to study the kinetics of changes in frozen food products. The initial reaction rate was determined in concentrated sucrose solutions down to -24 degrees C, and the enzymatic characteristics K(M) and V(max) were calculated. The experimental data were compared to the kinetics predicted by assuming that the reaction was viscosity dependent. Indeed, an analysis of the enzymatic reaction demonstrated that both the diffusion of the substrate and the flexibility of the enzyme segments were controlled by the high viscosity of the media. When the temperature was too low for the viscosity to be measured simply, the Williams-Landel-Ferry equation was used to predict the viscosity, taking, as reference temperature, the glass transition temperature (T(g)) corresponding to the concentration of the freeze-concentrated phase at the test temperature. Predicted values of the reaction rate were very close to the experimental ones in the studied temperature range.

  15. Transition path sampling with quantum/classical mechanics for reaction rates.

    PubMed

    Gräter, Frauke; Li, Wenjin

    2015-01-01

    Predicting rates of biochemical reactions through molecular simulations poses a particular challenge for two reasons. First, the process involves bond formation and/or cleavage and thus requires a quantum mechanical (QM) treatment of the reaction center, which can be combined with a more efficient molecular mechanical (MM) description for the remainder of the system, resulting in a QM/MM approach. Second, reaction time scales are typically many orders of magnitude larger than the (sub-)nanosecond scale accessible by QM/MM simulations. Transition path sampling (TPS) allows to efficiently sample the space of dynamic trajectories from the reactant to the product state without an additional biasing potential. We outline here the application of TPS and QM/MM to calculate rates for biochemical reactions, by means of a simple toy system. In a step-by-step protocol, we specifically refer to our implementation within the MD suite Gromacs, which we have made available to the research community, and include practical advice on the choice of parameters.

  16. 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.

  17. Beyond transition state theory: Rigorous quantum approaches for determining chemical reaction rates

    SciTech Connect

    Miller, W.H.

    1995-01-01

    Transition state theory (TST) has historically been the most important and widely used theoretical approach for describing the rates of chemical reactions, and for qualitative pictures and order-of-magnitude estimates one does not expect this situation to change. However a rigorous, quantitative treatment of chemical reaction rates must go beyond TST. A rigorous description, for example, must be based on a quantum mechanical description of the molecular system, but the fundamental assumption on which TST is based - namely that the molecular dynamics is {open_quotes}direct,{close_quotes} i.e., that no trajectories re-cross a dividing surface which separates reactants and products (vide infra) - is couched inherently in the language of classical mechanics. There is no unambiguous way to quantize TST, for the various ways of trying to do so invariably require one to introduce additional assumptions about the reaction dynamics. As one tries to eliminate these {open_quotes}additional assumptions{close_quotes} one is driven ultimately to an exact quantum treatment of the reaction dynamics which is then no longer a transition state theory (i.e., approximation) but simply an exact formulation. It is such exact approaches, those without inherent approximations, that are the subject of this chapter.

  18. Rate parameters for the reaction of atomic hydrogen with dimethyl ether and dimethyl sulfide

    NASA Astrophysics Data System (ADS)

    Lee, J. H.; Machen, R. C.; Nava, D. F.; Stief, L. J.

    1981-03-01

    Absolute rate constants for the reaction of atomic hydrogen with dimethyl ether (DME) and dimethyl sulfide (DMS) were obtained using the flash photolysis-resonance fluorescence technique. Under conditions where secondary reactions are avoided, rate constants for the H+DME reaction over the temperature range 273-426 K are well represented by the Arrhenius expression k1=(4.38±0.59)×10-12 exp(-1956±43/T) cm3 molecule-1 s-1. The corresponding Arrhenius expression for the H+DMS reaction over the temperature range 212-500 K is k2=(1.30±0.43)×10-11exp(-1118±81/T) cm3 molecule-1 s-1. The Arrhenius plot for k2 shows signs of curvature, however, and separate Arrhenius expressions are derived for the data above and below room temperature. These results are discussed and comparisons are made with previous determinations which employed flow discharge and product analysis techniques.

  19. The rate of the deoxygenation reaction limits myoglobin- and hemoglobin-facilitated O₂ diffusion in cells.

    PubMed

    Endeward, Volker

    2012-05-01

    A mathematical model describing facilitation of O(2) diffusion by the diffusion of myoglobin and hemoglobin is presented. The equations are solved numerically by a finite-difference method for the conditions as they prevail in cardiac and skeletal muscle and in red cells without major simplifications. It is demonstrated that, in the range of intracellular diffusion distances, the degree of facilitation is limited by the rate of the chemical reaction between myglobin or hemoglobin and O(2). The results are presented in the form of relationships between the degree of facilitation and the length of the diffusion path on the basis of the known kinetics of the oxygenation-deoxygenation reactions. It is concluded that the limitation by reaction kinetics reduces the maximally possible facilitated oxygen diffusion in cardiomyoctes by ∼50% and in skeletal muscle fibers by ∼ 20%. For human red blood cells, a reduction of facilitated O(2) diffusion by 36% is obtained in agreement with previous reports. This indicates that, especially in cardiomyocytes and red cells, chemical equilibrium between myoglobin or hemoglobin and O(2) is far from being established, an assumption that previously has often been made. Although the "O(2) transport function" of myoglobin in cardiac muscle cells thus is severely limited by the chemical reaction kinetics, and to a lesser extent also in skeletal muscle, it is noteworthy that the speed of release of O(2) from MbO(2), the "storage function," is not limited by the reaction kinetics under physiological conditions.

  20. 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, alt