Protein labeling reactions in electrochemical microchannel flow: Numerical simulation and uncertainty propagation

NASA Astrophysics Data System (ADS)

Debusschere, Bert J.; Najm, Habib N.; Matta, Alain; Knio, Omar M.; Ghanem, Roger G.; Le Maître, Olivier P.

2003-08-01

This paper presents a model for two-dimensional electrochemical microchannel flow including the propagation of uncertainty from model parameters to the simulation results. For a detailed representation of electroosmotic and pressure-driven microchannel flow, the model considers the coupled momentum, species transport, and electrostatic field equations, including variable zeta potential. The chemistry model accounts for pH-dependent protein labeling reactions as well as detailed buffer electrochemistry in a mixed finite-rate/equilibrium formulation. Uncertainty from the model parameters and boundary conditions is propagated to the model predictions using a pseudo-spectral stochastic formulation with polynomial chaos (PC) representations for parameters and field quantities. Using a Galerkin approach, the governing equations are reformulated into equations for the coefficients in the PC expansion. The implementation of the physical model with the stochastic uncertainty propagation is applied to protein-labeling in a homogeneous buffer, as well as in two-dimensional electrochemical microchannel flow. The results for the two-dimensional channel show strong distortion of sample profiles due to ion movement and consequent buffer disturbances. The uncertainty in these results is dominated by the uncertainty in the applied voltage across the channel.

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.

Reactions and reaction rates in the regional aquifer beneath the Pajarito Plateau, north-central New Mexico, USA

NASA Astrophysics Data System (ADS)

Hereford, Anne G.; Keating, Elizabeth H.; Guthrie, George D.; Zhu, Chen

2007-05-01

Reactions and reaction rates within aquifers are fundamental components of critical hydrological processes. However, reactions simulated in laboratory experiments typically demonstrate rates that are much faster than those observed in the field. Therefore, it is necessary to conduct more reaction rate analyses in natural settings. This study of geochemical reactions in the regional aquifer in the Pajarito Plateau near Los Alamos, New Mexico combines modeling with petrographic assessment to further knowledge and understanding of complex natural hydrologic systems. Groundwater geochemistry shows marked evolution along assumed flow paths. The flow path chosen for this study was evaluated using inverse mass balance modeling to calculate the mass transfer. X-ray diffraction and field emission gun scanning electron microscopy were used to identify possible reactants and products. Considering the mineralogy of the aquifer and saturation indices for the regional water refined initial interpretations. Calculations yielded dissolution rates for plagioclase on the order of 10-15 mol s-1 m-2 and for K-feldspar on the order of 10-17 mol s-1 m-2, orders of magnitude slower than laboratory rates. While these rates agree with other aquifer studies, they must be considered in the light of the uncertainty associated with geometric surface area estimates, 14C ages, and aquifer properties.

Radiologist Uncertainty and the Interpretation of Screening

PubMed Central

Carney, Patricia A.; Elmore, Joann G.; Abraham, Linn A.; Gerrity, Martha S.; Hendrick, R. Edward; Taplin, Stephen H.; Barlow, William E.; Cutter, Gary R.; Poplack, Steven P.; D’Orsi, Carl J.

2011-01-01

Objective To determine radiologists’ reactions to uncertainty when interpreting mammography and the extent to which radiologist uncertainty explains variability in interpretive performance. Methods The authors used a mailed survey to assess demographic and clinical characteristics of radiologists and reactions to uncertainty associated with practice. Responses were linked to radiologists’ actual interpretive performance data obtained from 3 regionally located mammography registries. Results More than 180 radiologists were eligible to participate, and 139 consented for a response rate of 76.8%. Radiologist gender, more years interpreting, and higher volume were associated with lower uncertainty scores. Positive predictive value, recall rates, and specificity were more affected by reactions to uncertainty than sensitivity or negative predictive value; however, none of these relationships was statistically significant. Conclusion Certain practice factors, such as gender and years of interpretive experience, affect uncertainty scores. Radiologists’ reactions to uncertainty do not appear to affect interpretive performance. PMID:15155014

Photochemical parameters of atmospheric source gases: accurate determination of OH reaction rate constants over atmospheric temperatures, UV and IR absorption spectra

NASA Astrophysics Data System (ADS)

Orkin, V. L.; Khamaganov, V. G.; Martynova, L. E.; Kurylo, M. J.

2012-12-01

The emissions of halogenated (Cl, Br containing) organics of both natural and anthropogenic origin contribute to the balance of and changes in the stratospheric ozone concentration. The associated chemical cycles are initiated by the photochemical decomposition of the portion of source gases that reaches the stratosphere. Reactions with hydroxyl radicals and photolysis are the main processes dictating the compound lifetime in the troposphere and release of active halogen in the stratosphere for a majority of halogen source gases. Therefore, the accuracy of photochemical data is of primary importance for the purpose of comprehensive atmospheric modeling and for simplified kinetic estimations of global impacts on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP). The sources of critically evaluated photochemical data for atmospheric modeling, NASA/JPL Publications and IUPAC Publications, recommend uncertainties within 10%-60% for the majority of OH reaction rate constants with only a few cases where uncertainties lie at the low end of this range. These uncertainties can be somewhat conservative because evaluations are based on the data from various laboratories obtained during the last few decades. Nevertheless, even the authors of the original experimental works rarely estimate the total combined uncertainties of the published OH reaction rate constants to be less than ca. 10%. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions still may constitute a major source of uncertainty in estimating the compound's environmental impact. One of the purposes of the presentation is to illustrate the potential for obtaining accurate laboratory measurements of the OH reaction rate constant over the temperature range of atmospheric interest. A detailed inventory of accountable sources of

Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

NASA Astrophysics Data System (ADS)

Newsome, Ben; Evans, Mat

2017-12-01

Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global, use these rate constants. Expert panels evaluate laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the Jet Propulsion Laboratory (JPL) and International Union of Pure and Applied Chemistry (IUPAC) evaluations we assess the influence of 50 mainly inorganic rate constants and 10 photolysis rates on tropospheric composition through the use of the GEOS-Chem chemistry transport model. We assess the impact on four standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH →M HNO3 and O3 + NO → NO2 + O2 are the two largest sources of uncertainty in these metrics. The absolute magnitude of the change in the metrics is similar if rate constants are increased or decreased by their σ values. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 10, 11, 16 and 16 %, respectively. These are larger than the spread between models

Inference of reaction rate parameters based on summary statistics from experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 H 2/O 2-mechanism chain branching reaction H + O 2 → 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 givenmore » 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-ignition computations to

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 H 2/O 2-mechanism chain branching reaction H + O 2 → 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 givenmore » 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-ignition computations to

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.

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…

The role of correlations in uncertainty quantification of transportation relevant fuel models

DOE PAGES

Fridlyand, Aleksandr; Johnson, Matthew S.; Goldsborough, S. Scott; ...

2017-02-03

Large reaction mechanisms are often used to describe the combustion behavior of transportation-relevant fuels like gasoline, where these are typically represented by surrogate blends, e.g., n-heptane/iso-octane/toluene. We describe efforts to quantify the uncertainty in the predictions of such mechanisms at realistic engine conditions, seeking to better understand the robustness of the model as well as the important reaction pathways and their impacts on combustion behavior. In this work, we examine the importance of taking into account correlations among reactions that utilize the same rate rules and those with multiple product channels on forward propagation of uncertainty by Monte Carlo simulations.more » Automated means are developed to generate the uncertainty factor assignment for a detailed chemical kinetic mechanism, by first uniquely identifying each reacting species, then sorting each of the reactions based on the rate rule utilized. Simulation results reveal that in the low temperature combustion regime for iso-octane, the majority of the uncertainty in the model predictions can be attributed to low temperature reactions of the fuel sub-mechanism. The foundational, or small-molecule chemistry (C 0-C 4) only contributes significantly to uncertainties in the predictions at the highest temperatures (Tc=900 K). Accounting for correlations between important reactions is shown to produce non-negligible differences in the estimates of uncertainty. Including correlations among reactions that use the same rate rules increases uncertainty in the model predictions, while accounting for correlations among reactions with multiple branches decreases uncertainty in some cases. Significant non-linear response is observed in the model predictions depending on how the probability distributions of the uncertain rate constants are defined.Finally, we concluded that care must be exercised in defining these probability distributions in order to reduce bias, and physically

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

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.

Alpha-capture reaction rates for 22Ne(alpha,n) via sub-Coulomb alpha-transfer

NASA Astrophysics Data System (ADS)

Jayatissa, Heshani; Rogachev, Grigory; Koshchiy, Yevgen; Goldberg, Vladilen; Bedoor, Shadi; Hooker, Joshua; Hunt, Curtis; Magana, Cordero; Roeder, Brian; Saastamoinen, Antti; Spiridon, Alexandria; Upadhyayula, Sriteja

2016-09-01

Direct measurements of α-capture reactions at energies relevant to astrophysics is extremely difficult to carry out due to the very small reaction cross section. The large uncertainties introduced when extrapolating direct measurements at high energies down to the Gamow energies can be overcome by measuring the Asymptotic Normalization Coefficients (ANC) of the relevant states using (6Li,d) α-transfer reactions at sub-Coulomb energies to reduce the model dependence. The study of the 22Ne(6Li,d) reaction was carried out at the Cyclotron Institute at Texas A&M University. The α-ANC measurements for the near α-threshold resonances of 26Mg will provide constraints for the reaction rate of the 22Ne(α,n) reaction.

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

NASA Astrophysics Data System (ADS)

Bravo, Eduardo; Martínez-Pinedo, Gabriel

2012-05-01

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

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.

Effects of uncertainty, transmission type, driver age and gender on brake reaction and movement time.

PubMed

Warshawsky-Livne, Lora; Shinar, David

2002-01-01

Braking time (BT) is a critical component in safe driving, and various approaches have been applied to minimize it. This study analyzed the components of BT in order to assess the effects of age, gender, vehicle transmission type, and event uncertainty, on its two primary components, perception-reaction time and brake-movement time. Perception-reaction time and brake-movement time were measured at the onset of lights for 72 subjects in a simulator. The six experimental conditions were three levels of uncertainty conditions (none, some, and some + false alarms) and two types of transmission (manual and automatic). The 72 subjects, half male and half female, were further divided into three age groups (mean of 23, 30, and 62 years). Each subject had 10 trials in each of the three levels of uncertainty conditions. Transmission type did not significantly affect either perception-reaction time or brake-movement time. Perception-reaction time increased significantly from 0.32 to 0.42 s (P < .05) as uncertainty increased but brake-movement time did not change. Perception-reaction time increased (from 0.35 to 0.43 s) with age but brake-movement time did not change with age. Gender did not affect perception-reaction time but did affect brake-movement time (males 0.19 s vs. females 0.16 s). At 90 km/h, a car travels 0.25 m in 0.01 s. Consequently, even such small effects multiplied by millions of vehicle-kilometers can contribute to significant savings in lives and damages.

Uncertainties in s-process nucleosynthesis in massive stars determined by Monte Carlo variations

NASA Astrophysics Data System (ADS)

Nishimura, N.; Hirschi, R.; Rauscher, T.; St. J. Murphy, A.; Cescutti, G.

2017-08-01

The s-process in massive stars produces the weak component of the s-process (nuclei up to A ˜ 90), in amounts that match solar abundances. For heavier isotopes, such as barium, production through neutron capture is significantly enhanced in very metal-poor stars with fast rotation. However, detailed theoretical predictions for the resulting final s-process abundances have important uncertainties caused both by the underlying uncertainties in the nuclear physics (principally neutron-capture reaction and β-decay rates) as well as by the stellar evolution modelling. In this work, we investigated the impact of nuclear-physics uncertainties relevant to the s-process in massive stars. Using a Monte Carlo based approach, we performed extensive nuclear reaction network calculations that include newly evaluated upper and lower limits for the individual temperature-dependent reaction rates. We found that most of the uncertainty in the final abundances is caused by uncertainties in the neutron-capture rates, while β-decay rate uncertainties affect only a few nuclei near s-process branchings. The s-process in rotating metal-poor stars shows quantitatively different uncertainties and key reactions, although the qualitative characteristics are similar. We confirmed that our results do not significantly change at different metallicities for fast rotating massive stars in the very low metallicity regime. We highlight which of the identified key reactions are realistic candidates for improved measurement by future experiments.

Uncertainties in s -process nucleosynthesis in low mass stars determined from Monte Carlo variations

NASA Astrophysics Data System (ADS)

Cescutti, G.; Hirschi, R.; Nishimura, N.; den Hartogh, J. W.; Rauscher, T.; Murphy, A. St J.; Cristallo, S.

2018-05-01

The main s-process taking place in low mass stars produces about half of the elements heavier than iron. It is therefore very important to determine the importance and impact of nuclear physics uncertainties on this process. We have performed extensive nuclear reaction network calculations using individual and temperature-dependent uncertainties for reactions involving elements heavier than iron, within a Monte Carlo framework. Using this technique, we determined the uncertainty in the main s-process abundance predictions due to nuclear uncertainties link to weak interactions and neutron captures on elements heavier than iron. We also identified the key nuclear reactions dominating these uncertainties. We found that β-decay rate uncertainties affect only a few nuclides near s-process branchings, whereas most of the uncertainty in the final abundances is caused by uncertainties in neutron capture rates, either directly producing or destroying the nuclide of interest. Combined total nuclear uncertainties due to reactions on heavy elements are in general small (less than 50%). Three key reactions, nevertheless, stand out because they significantly affect the uncertainties of a large number of nuclides. These are 56Fe(n,γ), 64Ni(n,γ), and 138Ba(n,γ). We discuss the prospect of reducing uncertainties in the key reactions identified in this study with future experiments.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lam, Y. H.; He, J. J.; Wang, M.

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 themore » 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.« less

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.

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.

Measurements of fusion neutron yields by neutron activation technique: Uncertainty due to the uncertainty on activation cross-sections

NASA Astrophysics Data System (ADS)

Stankunas, Gediminas; Batistoni, Paola; Sjöstrand, Henrik; Conroy, Sean; JET Contributors

2015-07-01

The neutron activation technique is routinely used in fusion experiments to measure the neutron yields. This paper investigates the uncertainty on these measurements as due to the uncertainties on dosimetry and activation reactions. For this purpose, activation cross-sections were taken from the International Reactor Dosimetry and Fusion File (IRDFF-v1.05) in 640 groups ENDF-6 format for several reactions of interest for both 2.5 and 14 MeV neutrons. Activation coefficients (reaction rates) have been calculated using the neutron flux spectra at JET vacuum vessel, both for DD and DT plasmas, calculated by MCNP in the required 640-energy group format. The related uncertainties for the JET neutron spectra are evaluated as well using the covariance data available in the library. These uncertainties are in general small, but not negligible when high accuracy is required in the determination of the fusion neutron yields.

Impact of measurement uncertainty from experimental load distribution factors on bridge load rating

NASA Astrophysics Data System (ADS)

Gangone, Michael V.; Whelan, Matthew J.

2018-03-01

Load rating and testing of highway bridges is important in determining the capacity of the structure. Experimental load rating utilizes strain transducers placed at critical locations of the superstructure to measure normal strains. These strains are then used in computing diagnostic performance measures (neutral axis of bending, load distribution factor) and ultimately a load rating. However, it has been shown that experimentally obtained strain measurements contain uncertainties associated with the accuracy and precision of the sensor and sensing system. These uncertainties propagate through to the diagnostic indicators that in turn transmit into the load rating calculation. This paper will analyze the effect that measurement uncertainties have on the experimental load rating results of a 3 span multi-girder/stringer steel and concrete bridge. The focus of this paper will be limited to the uncertainty associated with the experimental distribution factor estimate. For the testing discussed, strain readings were gathered at the midspan of each span of both exterior girders and the center girder. Test vehicles of known weight were positioned at specified locations on each span to generate maximum strain response for each of the five girders. The strain uncertainties were used in conjunction with a propagation formula developed by the authors to determine the standard uncertainty in the distribution factor estimates. This distribution factor uncertainty is then introduced into the load rating computation to determine the possible range of the load rating. The results show the importance of understanding measurement uncertainty in experimental load testing.

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.

Calculations on the rate of the ion-molecule reaction between NH3(+) and H2

NASA Technical Reports Server (NTRS)

Herbst, Eric; Defrees, D. J.; Talbi, D.; Pauzat, F.; Koch, W.

1991-01-01

The rate coefficient for the ion-molecule reaction NH3(+) + H2 yields NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He yields NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.

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

Reaction rates for mesoscopic reaction-diffusion kinetics

PubMed Central

Hellander, Stefan; Hellander, Andreas; Petzold, Linda

2016-01-01

The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results. PMID:25768640

Impact of Pitot tube calibration on the uncertainty of water flow rate measurement

NASA Astrophysics Data System (ADS)

de Oliveira Buscarini, Icaro; Costa Barsaglini, Andre; Saiz Jabardo, Paulo Jose; Massami Taira, Nilson; Nader, Gilder

2015-10-01

Water utility companies often use Cole type Pitot tubes to map velocity profiles and thus measure flow rate. Frequent monitoring and measurement of flow rate is an important step in identifying leaks and other types of losses. In Brazil losses as high as 42% are common and in some places even higher values are found. When using Cole type Pitot tubes to measure the flow rate, the uncertainty of the calibration coefficient (Cd) is a major component of the overall flow rate measurement uncertainty. A common practice is to employ the usual value Cd = 0.869, in use since Cole proposed his Pitot tube in 1896. Analysis of 414 calibrations of Cole type Pitot tubes show that Cd varies considerably and values as high 0.020 for the expanded uncertainty are common. Combined with other uncertainty sources, the overall velocity measurement uncertainty is 0.02, increasing flowrate measurement uncertainty by 1.5% which, for the Sao Paulo metropolitan area (Brazil) corresponds to 3.5 × 107 m3/year.

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.

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.

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…

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.

Capture and photonuclear reaction rates involving charged-particles: Impacts of nuclear ingredients and future measurement on ELI-NP

NASA Astrophysics Data System (ADS)

Xu, Y.; Goriely, S.; Balabanski, D. L.; Chesnevskaya, S.; Guardo, G. L.; La Cognata, M.; Lan, H. Y.; Lattuada, D.; Luo, W.; Matei, C.

2018-05-01

The astrophysical p-process is an important way of nucleosynthesis to produce the stable and proton-rich nuclei beyond Fe which can not be reached by the s- and r-processes. In the present study, the impact of nuclear ingredients, especially the nuclear potential, level density and strength function, to the astrophysical re-action rates of (p,γ), (α,γ), (γ,p), and (γ,α) reactions are systematically studied. The calculations are performed basad on the modern reaction code TALYS for about 3000 stable and proton-rich nuclei with 12≤Z≤110. In particular, both of the Wood-Saxon potential and the microscopic folding potential are taken into account. It is found that both the capture and photonuclear reaction rates are very sensitive to the nuclear potential, thus the better determination of nuclear potential would be important to reduce the uncertainties of reaction rates. Meanwhile, the Extreme Light Infrastructure-Nuclear Physics (ELI-NP) facility is being developed, which will provide the great opportunity to experimentally study the photonuclear reactions in p-process. Simulations of the experimental setup for the measurements of the photonuclear reactions 96Ru(γ,p) and 96Ru(γ,α) are performed. It is shown that the experiments of photonuclear reactions in p-process based on ELI-NP are quite promising.

Typewriting rate as a function of reaction time.

PubMed

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

1977-12-01

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

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…

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.

Non-equilibrium reaction rates in chemical kinetic equations

NASA Astrophysics Data System (ADS)

Gorbachev, Yuriy

2018-05-01

Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

Temperature-dependent rate coefficients and theoretical calculations for the OH+Cl2O reaction.

PubMed

Riffault, Véronique; Clark, Jared M; Hansen, Jaron C; Ravishankara, A R; Burkholder, James B

2010-12-17

Rate coefficients k for the OH+Cl(2)O reaction are measured as a function of temperature (230-370 K) and pressure by using pulsed laser photolysis to produce OH radicals and laser-induced fluorescence to monitor their loss under pseudo-first-order conditions in OH. The reaction rate coefficient is found to be independent of pressure, within the precision of our measurements at 30-100 Torr (He) and 100 Torr (N(2)). The rate coefficients obtained at 100 Torr (He) showed a negative temperature dependence with a weak non-Arrhenius behavior. A room-temperature rate coefficient of k(1)(297 K)=(7.5±1.1)×10(-12) cm(3) molecule(-1) s(-1) is obtained, where the quoted uncertainties are 2σ and include estimated systematic errors. Theoretical methods are used to examine OH···OCl(2) and OH···ClOCl adduct formation and the potential-energy surfaces leading to the HOCl+ClO (1a) and Cl+HOOCl (1d) products in reaction (1) at the hybrid density functional UMPW1K/6-311++G(2df,p) level of theory. The OH···OCl(2) and OH···ClOCl adducts are found to have binding energies of about 0.2 kcal mol(-1). The reaction is calculated to proceed through weak pre-reactive complexes. Transition-state energies for channels (1a) and (1d) are calculated to be about 1.4 and about 3.3 kcal mol(-1) above the energy of the reactants. The results from the present study are compared with previously reported rate coefficients, and the interpretation of the possible non-Arrhenius behavior is discussed.

Lognormal Uncertainty Estimation for Failure Rates

NASA Technical Reports Server (NTRS)

Britton, Paul T.; Al Hassan, Mohammad; Ring, Robert W.

2017-01-01

"Uncertainty analysis itself is uncertain, therefore, you cannot evaluate it exactly," Source Uncertain. Quantitative results for aerospace engineering problems are influenced by many sources of uncertainty. Uncertainty analysis aims to make a technical contribution to decision-making through the quantification of uncertainties in the relevant variables as well as through the propagation of these uncertainties up to the result. Uncertainty can be thought of as a measure of the 'goodness' of a result and is typically represented as statistical dispersion. This presentation will explain common measures of centrality and dispersion; and-with examples-will provide guidelines for how they may be estimated to ensure effective technical contributions to decision-making.

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

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

NASA Astrophysics Data System (ADS)

Mansanarez, Valentin; Le Coz, Jérôme; Renard, Benjamin; Lang, Michel; Pierrefeu, Gilles; Le Boursicaud, Raphaël; Pobanz, Karine

2016-04-01

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. Building on existing Bayesian approaches, we introduce an original hydraulics-based method for developing SFD rating curves used at twin gauge stations and estimating their uncertainties. Conventional power functions for channel and section controls are used, and transition to a backwater-affected channel control is computed based on a continuity condition, solved either analytically or numerically. The difference between the reference levels at the two stations is estimated as another uncertain parameter of the SFD model. The method proposed in this presentation incorporates information from both the hydraulic knowledge (equations of channel or section controls) and the information available in the stage-fall-discharge observations (gauging data). The obtained total uncertainty combines the parametric uncertainty and the remnant uncertainty related to the model of rating curve. This method provides a direct estimation of the physical inputs of the rating curve (roughness, width, slope bed, distance between twin gauges, etc.). The performance of the new method is tested using an application case affected by the variable backwater of a run-of-the-river dam: the Rhône river at Valence, France. In particular, a sensitivity analysis to the prior information and to the gauging dataset is performed. At that site, the stage-fall-discharge domain is well documented with gaugings conducted over a range of backwater affected and unaffected conditions. The performance of the new model was deemed to be satisfactory. Notably, transition to uniform flow when the overall range of the auxiliary stage is gauged is correctly simulated. The resulting curves are in good agreement with the observations (gaugings) and their uncertainty envelopes are acceptable for computing streamflow records. Similar

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.

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.

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

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

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.

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.

SU-F-T-301: Planar Dose Pass Rate Inflation Due to the MapCHECK Measurement Uncertainty Function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bailey, D; Spaans, J; Kumaraswamy, L

Purpose: To quantify the effect of the Measurement Uncertainty function on planar dosimetry pass rates, as analyzed with Sun Nuclear Corporation analytic software (“MapCHECK” or “SNC Patient”). This optional function is toggled on by default upon software installation, and automatically increases the user-defined dose percent difference (%Diff) tolerance for each planar dose comparison. Methods: Dose planes from 109 IMRT fields and 40 VMAT arcs were measured with the MapCHECK 2 diode array, and compared to calculated planes from a commercial treatment planning system. Pass rates were calculated within the SNC analytic software using varying calculation parameters, including Measurement Uncertainty onmore » and off. By varying the %Diff criterion for each dose comparison performed with Measurement Uncertainty turned off, an effective %Diff criterion was defined for each field/arc corresponding to the pass rate achieved with MapCHECK Uncertainty turned on. Results: For 3%/3mm analysis, the Measurement Uncertainty function increases the user-defined %Diff by 0.8–1.1% average, depending on plan type and calculation technique, for an average pass rate increase of 1.0–3.5% (maximum +8.7%). For 2%, 2 mm analysis, the Measurement Uncertainty function increases the user-defined %Diff by 0.7–1.2% average, for an average pass rate increase of 3.5–8.1% (maximum +14.2%). The largest increases in pass rate are generally seen with poorly-matched planar dose comparisons; the MapCHECK Uncertainty effect is markedly smaller as pass rates approach 100%. Conclusion: The Measurement Uncertainty function may substantially inflate planar dose comparison pass rates for typical IMRT and VMAT planes. The types of uncertainties incorporated into the function (and their associated quantitative estimates) as described in the software user’s manual may not accurately estimate realistic measurement uncertainty for the user’s measurement conditions. Pass rates listed in

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.

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 H 2/CO reaction model, assembled frommore » 73 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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 H 2/CO reaction model, assembled frommore » 73 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

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.

Analysis of mean seismic ground motion and its uncertainty based on the UCERF3 geologic slip rate model with uncertainty for California

USGS Publications Warehouse

Zeng, Yuehua

2018-01-01

The Uniform California Earthquake Rupture Forecast v.3 (UCERF3) model (Field et al., 2014) considers epistemic uncertainty in fault‐slip rate via the inclusion of multiple rate models based on geologic and/or geodetic data. However, these slip rates are commonly clustered about their mean value and do not reflect the broader distribution of possible rates and associated probabilities. Here, we consider both a double‐truncated 2σ Gaussian and a boxcar distribution of slip rates and use a Monte Carlo simulation to sample the entire range of the distribution for California fault‐slip rates. We compute the seismic hazard following the methodology and logic‐tree branch weights applied to the 2014 national seismic hazard model (NSHM) for the western U.S. region (Petersen et al., 2014, 2015). By applying a new approach developed in this study to the probabilistic seismic hazard analysis (PSHA) using precomputed rates of exceedance from each fault as a Green’s function, we reduce the computer time by about 10^5‐fold and apply it to the mean PSHA estimates with 1000 Monte Carlo samples of fault‐slip rates to compare with results calculated using only the mean or preferred slip rates. The difference in the mean probabilistic peak ground motion corresponding to a 2% in 50‐yr probability of exceedance is less than 1% on average over all of California for both the Gaussian and boxcar probability distributions for slip‐rate uncertainty but reaches about 18% in areas near faults compared with that calculated using the mean or preferred slip rates. The average uncertainties in 1σ peak ground‐motion level are 5.5% and 7.3% of the mean with the relative maximum uncertainties of 53% and 63% for the Gaussian and boxcar probability density function (PDF), respectively.

Sensitivity of tropospheric ozone to chemical kinetic uncertainties in air masses influenced by anthropogenic and biomass burning emissions

NASA Astrophysics Data System (ADS)

Ridley, D. A.; Cain, M.; Methven, J.; Arnold, S. R.

2017-07-01

We use a Lagrangian chemical transport model with a Monte Carlo approach to determine impacts of kinetic rate uncertainties on simulated concentrations of ozone, NOy and OH in a high-altitude biomass burning plume and a low-level industrial pollution plume undergoing long-range transport. Uncertainties in kinetic rate constants yield 10-12 ppbv (5th to 95th percentile) uncertainty in the ozone concentration, dominated by reactions that cycle NO and NO2, control NOx conversion to NOy reservoir species, and key reactions contributing to O3 loss (O(1D) + H2O, HO2 + O3). Our results imply that better understanding of the peroxyacetylnitrate (PAN) thermal decomposition constant is key to predicting large-scale O3 production from fire emissions and uncertainty in the reaction of NO + O3 at low temperatures is particularly important for both the anthropogenic and biomass burning plumes. The highlighted reactions serve as a useful template for targeting new laboratory experiments aimed at reducing uncertainties in our understanding of tropospheric O3 photochemistry.

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.

Uncertainty estimation with bias-correction for flow series based on rating curve

NASA Astrophysics Data System (ADS)

Shao, Quanxi; Lerat, Julien; Podger, Geoff; Dutta, Dushmanta

2014-03-01

Streamflow discharge constitutes one of the fundamental data required to perform water balance studies and develop hydrological models. A rating curve, designed based on a series of concurrent stage and discharge measurements at a gauging location, provides a way to generate complete discharge time series with a reasonable quality if sufficient measurement points are available. However, the associated uncertainty is frequently not available even though it has a significant impact on hydrological modelling. In this paper, we identify the discrepancy of the hydrographers' rating curves used to derive the historical discharge data series and proposed a modification by bias correction which is also in the form of power function as the traditional rating curve. In order to obtain the uncertainty estimation, we propose a further both-side Box-Cox transformation to stabilize the regression residuals as close to the normal distribution as possible, so that a proper uncertainty can be attached for the whole discharge series in the ensemble generation. We demonstrate the proposed method by applying it to the gauging stations in the Flinders and Gilbert rivers in north-west Queensland, Australia.

Raman Spectral Determination of Chemical Reaction Rate Characteristics

NASA Astrophysics Data System (ADS)

Balakhnina, I. A.; Brandt, N. N.; Mankova, A. A.; Chikishev, A. Yu.; Shpachenko, I. G.

2017-09-01

The feasibility of using Raman spectroscopy to determine chemical reaction rates and activation energies has been demonstrated for the saponification of ethyl acetate. The temperature dependence of the reaction rate was found in the range from 15 to 45°C.

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.

Rate coefficient measurements for the ClO radical self-reaction as a function of pressure and temperature

NASA Astrophysics Data System (ADS)

Burkholder, J. B.; Feierabend, K.

2010-12-01

Halogen chemistry plays an important role in polar stratospheric ozone loss. The ClO dimer (Cl2O2) catalytic ozone destruction cycle accounts for the vast majority of winter/spring polar stratospheric ozone loss. A key step in the dimer catalytic cycle is the pressure and temperature dependent self-reaction of the ClO radical. The rate coefficient for the ClO self-reaction has been measured in previous laboratory studies but uncertainties persist, particularly at atmospherically relevant temperatures and pressures. In this laboratory study, rate coefficients for the ClO self-reaction were measured over a range of temperature (200 - 296 K) and pressure (50 - 600 Torr, He and N2 bath gases). ClO radicals were produced by pulsed laser photolysis of Cl2O at 248 nm. The ClO radical temporal profile was measured using dual wavelength cavity ring-down spectroscopy (CRDS) near 280 nm. The absolute ClO radical concentration was determined using the ClO UV absorption cross sections and their temperature dependence measured as part of this work. The results from this work will be compared with previous studies and the discrepancies discussed. Possible explanations for deviations of the reaction rate coefficient from the simple Falloff kinetic behavior currently recommended for use in atmospheric model calculations will be discussed.

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…

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

NASA Astrophysics Data System (ADS)

Rajaram, Harihar; Arshadi, Masoud

2015-04-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 howmore » 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« less

Alpha-capture reaction rates for 22 Ne (α , n) via sub-Coulomb alpha-transfer and its effect on final abundances of s-process isotopes

NASA Astrophysics Data System (ADS)

Jayatissa, Heshani; Rogachev, Grigory; Koshchiy, Yevgeny; Goldberg, Vladilen; Hooker, Joshua; Hunt, Curtis; Magana, Cordero; Roeder, Brian; Saastamoinen, Antti; Spiridon, Alexandria; Upadhyayula, Sriteja; Trippella, Oscar

2017-09-01

The 22 Ne (α , n) reaction is a very important neutron source reaction for the slow neutron capture process (s-process) in asymptotic giant branch stars. These direct measurements are very difficult to carry out at the energy regimes of interest for astrophysics (Gamow energies) due to the extremely small reaction cross section. The large uncertainties introduced when extrapolating direct measurements at high energies down to the Gamow energies can be overcome by measuring the Asymptotic Normalization Coefficients (ANC) of the relevant states using α-transfer reactions at sub-Coulomb energies to reduce the optical model dependence. The study of the 22Ne(6Li,d) and 22Ne(7Li,t) reaction was carried out at the Cyclotron Institute at Texas A&M University. The α-ANC measurements for the near α-threshold resonances of 26Mg provide constraints for the 22Ne(α,n) reaction rate. The effect of this reaction rate on the final abundances of the s-process isotopes will be discussed.

Uncertainties in the production of p nuclides in thermonuclear supernovae determined by Monte Carlo variations

NASA Astrophysics Data System (ADS)

Nishimura, N.; Rauscher, T.; Hirschi, R.; Murphy, A. St J.; Cescutti, G.; Travaglio, C.

2018-03-01

Thermonuclear supernovae originating from the explosion of a white dwarf accreting mass from a companion star have been suggested as a site for the production of p nuclides. Such nuclei are produced during the explosion, in layers enriched with seed nuclei coming from prior strong s processing. These seeds are transformed into proton-richer isotopes mainly by photodisintegration reactions. Several thousand trajectories from a 2D explosion model were used in a Monte Carlo approach. Temperature-dependent uncertainties were assigned individually to thousands of rates varied simultaneously in post-processing in an extended nuclear reaction network. The uncertainties in the final nuclear abundances originating from uncertainties in the astrophysical reaction rates were determined. In addition to the 35 classical p nuclides, abundance uncertainties were also determined for the radioactive nuclides 92Nb, 97, 98Tc, 146Sm, and for the abundance ratios Y(92Mo)/Y(94Mo), Y(92Nb)/Y(92Mo), Y(97Tc)/Y(98Ru), Y(98Tc)/Y(98Ru), and Y(146Sm)/Y(144Sm), important for Galactic Chemical Evolution studies. Uncertainties found were generally lower than a factor of 2, although most nucleosynthesis flows mainly involve predicted rates with larger uncertainties. The main contribution to the total uncertainties comes from a group of trajectories with high peak density originating from the interior of the exploding white dwarf. The distinction between low-density and high-density trajectories allows more general conclusions to be drawn, also applicable to other simulations of white dwarf explosions.

Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling

NASA Astrophysics Data System (ADS)

Sutton, Jonathan E.; Guo, Wei; Katsoulakis, Markos A.; Vlachos, Dionisios G.

2016-04-01

Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells.

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.

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

Reaction rates for a generalized reaction-diffusion master equation

PubMed Central

Hellander, Stefan; Petzold, Linda

2016-01-01

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

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.

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.

A review of reaction rates in high temperature air

NASA Technical Reports Server (NTRS)

Park, Chul

1989-01-01

The existing experimental data on the rate coefficients for the chemical reactions in nonequilibrium high temperature air are reviewed and collated, and a selected set of such values is recommended for use in hypersonic flow calculations. For the reactions of neutral species, the recommended values are chosen from the experimental data that existed mostly prior to 1970, and are slightly different from those used previously. For the reactions involving ions, the recommended rate coefficients are newly chosen from the experimental data obtained more recently. The reacting environment is assumed to lack thermal equilibrium, and the rate coefficients are expressed as a function of the controlling temperature, incorporating the recent multitemperature reaction concept.

Rate Coefficient Measurements and Theoretical Analysis of the OH + ( E)-CF3CH═CHCF3 Reaction.

PubMed

Baasandorj, Munkhbayar; Marshall, Paul; Waterland, Robert L; Ravishankara, A R; Burkholder, James B

2018-05-04

Rate coefficients, k, for the gas-phase reaction of the OH radical with ( E)-CF 3 CH═CHCF 3 (( E)-1,1,1,4,4,4-hexafluoro-2-butene, HFO-1336mzz(E)) were measured over a range of temperatures (211-374 K) and bath gas pressures (20-300 Torr; He, N 2 ) using a pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) technique. k 1 ( T) was independent of pressure over this range of conditions with k 1 (296 K) = (1.31 ± 0.15) × 10 -13 cm 3 molecule -1 s -1 and k 1 ( T) = (6.94 ± 0.80) × 10 -13 exp[-(496 ± 10)/ T] cm 3 molecule -1 s -1 , where the uncertainties are 2σ, and the pre-exponential term includes estimated systematic error. Rate coefficients for the OD reaction were also determined over a range of temperatures (262-374 K) at 100 Torr (He). The OD rate coefficients were ∼15% greater than the OH values and showed similar temperature dependent behavior with k 2 ( T) = (7.52 ± 0.44) × 10 -13 exp[-(476 ± 20)/ T] and k 2 (296 K) = (1.53 ± 0.15) × 10 -13 cm 3 molecule -1 s -1 . The rate coefficients for reaction 1 were also measured using a relative rate technique between 296 and 375 K with k 1 (296 K) measured to be (1.22 ± 0.1) × 10 -13 cm 3 molecule -1 s -1 , in agreement with the PLP-LIF results. In addition, the 296 K rate coefficient for the O 3 + ( E)-CF 3 CH═CHCF 3 reaction was determined to be <5.2 × 10 -22 cm 3 molecule -1 s -1 . A theoretical computational analysis is presented to interpret the observed positive temperature dependence for the addition reaction and the significant decrease in OH reactivity compared to the ( Z)-CF 3 CH═CHCF 3 stereoisomer reaction. The estimated atmospheric lifetime of ( E)-CF 3 CH═CHCF 3 , due to loss by reaction with OH, is estimated to be ∼90 days, while the actual lifetime will depend on the location and season of its emission. Infrared absorption spectra of ( E)-CF 3 CH═CHCF 3 were measured and used to estimate the 100 year time horizon global warming potentials (GWP) of 32

Neutron Thermal Cross Sections, Westcott Factors, Resonance Integrals, Maxwellian Averaged Cross Sections and Astrophysical Reaction Rates Calculated from the ENDF/B-VII.1, JEFF-3.1.2, JENDL-4.0, ROSFOND-2010, CENDL-3.1 and EAF-2010 Evaluated Data Libraries

NASA Astrophysics Data System (ADS)

Pritychenko, B.; Mughabghab, S. F.

2012-12-01

We present calculations of neutron thermal cross sections, Westcott factors, resonance integrals, Maxwellian-averaged cross sections and astrophysical reaction rates for 843 ENDF materials using data from the major evaluated nuclear libraries and European activation file. Extensive analysis of newly-evaluated neutron reaction cross sections, neutron covariances, and improvements in data processing techniques motivated us to calculate nuclear industry and neutron physics quantities, produce s-process Maxwellian-averaged cross sections and astrophysical reaction rates, systematically calculate uncertainties, and provide additional insights on currently available neutron-induced reaction data. Nuclear reaction calculations are discussed and new results are presented. Due to space limitations, the present paper contains only calculated Maxwellian-averaged cross sections and their uncertainties. The complete data sets for all results are published in the Brookhaven National Laboratory report.

Mergers in ΛCDM: Uncertainties in Theoretical Predictions and Interpretations of the Merger Rate

NASA Astrophysics Data System (ADS)

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

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 ~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 ~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 (~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 ~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 ~2 uncertainties stemming from the uncertainty in those

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.

Psychophsyiological reactivity during uncertainty and ambiguity processing in high and low worriers.

PubMed

Kirschner, Hans; Hilbert, Kevin; Hoyer, Jana; Lueken, Ulrike; Beesdo-Baum, Katja

2016-03-01

Intolerance of uncertainty (IU) has been linked to Generalized Anxiety Disorder (GAD), but studies experimentally manipulating uncertainty have mostly failed to find differences between GAD patients and controls, possible due to a lack of distinction between uncertainty and ambiguity. This study therefore investigated reactivity to ambiguity in addition to uncertainty in high worriers (HW) and low worriers (LW). We hypothesized an interpretation bias between the groups during ambiguity tasks, while uncertainty would facilitate threat processing of subsequent aversive stimuli. HW (N = 23) and LW (N = 23) completed a paradigm comprising the anticipation and perception of pictures with dangerous, safe, or ambiguous content. Anticipatory cues were certain (always correct information about the following picture) or uncertain (no information). Subjective ratings, reaction times and skin conductance responses (SCRs) were recorded. HW rated particularly ambiguous pictures as more aversive and showed longer reaction times to all picture conditions compared to LW. SCRs were also larger in HW compared to LW, particularly during uncertain but also safe anticipation. No group differences were observed during perception of stimuli. All participants were female. HW was used as subclinical phenotype of GAD. Intolerance of ambiguity seems to be related to individual differences in worry and possibly to the development of GAD. Threat-related interpretations differentiating HW and LW occurred particularly for ambiguous pictures but were not accompanied by increased autonomic arousal during the picture viewing. This disparity between subjective rating and arousal may be the result of worrying in response to intolerance of uncertainty, restraining physiological responses. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 hasmore » 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« less

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

Quantifying chemical uncertainties in simulations of the ISM

NASA Astrophysics Data System (ADS)

Glover, Simon

2018-06-01

The ever-increasing power of large parallel computers now makes it possible to include increasingly sophisticated chemical models in three-dimensional simulations of the interstellar medium (ISM). This allows us to study the role that chemistry plays in the thermal balance of a realistically-structured, turbulent ISM, as well as enabling us to generated detailed synthetic observations of important atomic or molecular tracers. However, one major constraint on the accuracy of these models is the accuracy with which the input chemical rate coefficients are known. Uncertainties in these chemical rate coefficients inevitably introduce uncertainties into the model predictions. In this talk, I will review some of the methods we can use to quantify these uncertainties and to identify the key reactions where improved chemical data is most urgently required. I will also discuss a few examples, ranging from the local ISM to the high-redshift universe.

Modular rate laws for enzymatic reactions: thermodynamics, elasticities and implementation.

PubMed

Liebermeister, Wolfram; Uhlendorf, Jannis; Klipp, Edda

2010-06-15

Standard rate laws are a key requisite for systematically turning metabolic networks into kinetic models. They should provide simple, general and biochemically plausible formulae for reaction velocities and reaction elasticities. At the same time, they need to respect thermodynamic relations between the kinetic constants and the metabolic fluxes and concentrations. We present a family of reversible rate laws for reactions with arbitrary stoichiometries and various types of regulation, including mass-action, Michaelis-Menten and uni-uni reversible Hill kinetics as special cases. With a thermodynamically safe parameterization of these rate laws, parameter sets obtained by model fitting, sampling or optimization are guaranteed to lead to consistent chemical equilibrium states. A reformulation using saturation values yields simple formulae for rates and elasticities, which can be easily adjusted to the given stationary flux distributions. Furthermore, this formulation highlights the role of chemical potential differences as thermodynamic driving forces. We compare the modular rate laws to the thermodynamic-kinetic modelling formalism and discuss a simplified rate law in which the reaction rate directly depends on the reaction affinity. For automatic handling of modular rate laws, we propose a standard syntax and semantic annotations for the Systems Biology Markup Language. An online tool for inserting the rate laws into SBML models is freely available at www.semanticsbml.org. Supplementary data are available at Bioinformatics online.

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.

Astrophysical Nuclear Reaction Rates in the Dense Metallic Environments

NASA Astrophysics Data System (ADS)

Kilic, Ali Ihsan

2017-09-01

Nuclear reaction rates can be enhanced by many orders of magnitude in dense and relatively cold astrophysical plasmas such as in white dwarfs, brown dwarfs, and giant planets. Similar conditions are also present in supernova explosions where the ignition conditions are vital for cosmological models. White dwarfs are compact objects that have both extremely high interior densities and very strong local magnetic fields. For the first time, a new formula has been developed to explain cross section and reaction rate quantities for light elements that includes not only the nuclear component but also the material dependence, magnetic field, and crystal structure dependency in dense metallic environments. I will present the impact of the developed formula on the cross section and reaction rates for light elements. This could have possible technological applications in energy production using nuclear fusion reactions.

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

Reaction rate for carbon burning in massive stars

NASA Astrophysics Data System (ADS)

Jiang, C. L.; Santiago-Gonzalez, D.; Almaraz-Calderon, S.; Rehm, K. E.; Back, B. B.; Auranen, K.; Avila, M. L.; Ayangeakaa, A. D.; Bottoni, S.; Carpenter, M. P.; Dickerson, C.; DiGiovine, B.; Greene, J. P.; Hoffman, C. R.; Janssens, R. V. F.; Kay, B. P.; Kuvin, S. A.; Lauritsen, T.; Pardo, R. C.; Sethi, J.; Seweryniak, D.; Talwar, R.; Ugalde, C.; Zhu, S.; Bourgin, D.; Courtin, S.; Haas, F.; Heine, M.; Fruet, G.; Montanari, D.; Jenkins, D. G.; Morris, L.; Lefebvre-Schuhl, A.; Alcorta, M.; Fang, X.; Tang, X. D.; Bucher, B.; Deibel, C. M.; Marley, S. T.

2018-01-01

Carbon burning is a critical phase for nucleosynthesis in massive stars. The conditions for igniting this burning stage, and the subsequent isotope composition of the resulting ashes, depend strongly on the reaction rate for 12C+12C fusion at very low energies. Results for the cross sections for this reaction are influenced by various backgrounds encountered in measurements at such energies. In this paper, we report on a new measurement of 12C+12C fusion cross sections where these backgrounds have been minimized. It is found that the astrophysical S factor exhibits a maximum around Ecm=3.5 -4.0 MeV, which leads to a reduction of the previously predicted astrophysical reaction rate.

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, r max,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of r max,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 r max,i can be used to predict themore » 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. 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

Nuclear data uncertainty propagation by the XSUSA method in the HELIOS2 lattice code

NASA Astrophysics Data System (ADS)

Wemple, Charles; Zwermann, Winfried

2017-09-01

Uncertainty quantification has been extensively applied to nuclear criticality analyses for many years and has recently begun to be applied to depletion calculations. However, regulatory bodies worldwide are trending toward requiring such analyses for reactor fuel cycle calculations, which also requires uncertainty propagation for isotopics and nuclear reaction rates. XSUSA is a proven methodology for cross section uncertainty propagation based on random sampling of the nuclear data according to covariance data in multi-group representation; HELIOS2 is a lattice code widely used for commercial and research reactor fuel cycle calculations. This work describes a technique to automatically propagate the nuclear data uncertainties via the XSUSA approach through fuel lattice calculations in HELIOS2. Application of the XSUSA methodology in HELIOS2 presented some unusual challenges because of the highly-processed multi-group cross section data used in commercial lattice codes. Currently, uncertainties based on the SCALE 6.1 covariance data file are being used, but the implementation can be adapted to other covariance data in multi-group structure. Pin-cell and assembly depletion calculations, based on models described in the UAM-LWR Phase I and II benchmarks, are performed and uncertainties in multiplication factor, reaction rates, isotope concentrations, and delayed-neutron data are calculated. With this extension, it will be possible for HELIOS2 users to propagate nuclear data uncertainties directly from the microscopic cross sections to subsequent core simulations.

Robust Rate Maximization for Heterogeneous Wireless Networks under Channel Uncertainties

PubMed Central

Xu, Yongjun; Hu, Yuan; Li, Guoquan

2018-01-01

Heterogeneous wireless networks are a promising technology in next generation wireless communication networks, which has been shown to efficiently reduce the blind area of mobile communication and improve network coverage compared with the traditional wireless communication networks. In this paper, a robust power allocation problem for a two-tier heterogeneous wireless networks is formulated based on orthogonal frequency-division multiplexing technology. Under the consideration of imperfect channel state information (CSI), the robust sum-rate maximization problem is built while avoiding sever cross-tier interference to macrocell user and maintaining the minimum rate requirement of each femtocell user. To be practical, both of channel estimation errors from the femtocells to the macrocell and link uncertainties of each femtocell user are simultaneously considered in terms of outage probabilities of users. The optimization problem is analyzed under no CSI feedback with some cumulative distribution function and partial CSI with Gaussian distribution of channel estimation error. The robust optimization problem is converted into the convex optimization problem which is solved by using Lagrange dual theory and subgradient algorithm. Simulation results demonstrate the effectiveness of the proposed algorithm by the impact of channel uncertainties on the system performance. PMID:29466315

Uncertainty Quantification Techniques of SCALE/TSUNAMI

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rearden, Bradley T; Mueller, Don

2011-01-01

The Standardized Computer Analysis for Licensing Evaluation (SCALE) code system developed at Oak Ridge National Laboratory (ORNL) includes Tools for Sensitivity and Uncertainty Analysis Methodology Implementation (TSUNAMI). The TSUNAMI code suite can quantify the predicted change in system responses, such as k{sub eff}, reactivity differences, or ratios of fluxes or reaction rates, due to changes in the energy-dependent, nuclide-reaction-specific cross-section data. Where uncertainties in the neutron cross-section data are available, the sensitivity of the system to the cross-section data can be applied to propagate the uncertainties in the cross-section data to an uncertainty in the system response. Uncertainty quantification ismore » useful for identifying potential sources of computational biases and highlighting parameters important to code validation. Traditional validation techniques often examine one or more average physical parameters to characterize a system and identify applicable benchmark experiments. However, with TSUNAMI correlation coefficients are developed by propagating the uncertainties in neutron cross-section data to uncertainties in the computed responses for experiments and safety applications through sensitivity coefficients. The bias in the experiments, as a function of their correlation coefficient with the intended application, is extrapolated to predict the bias and bias uncertainty in the application through trending analysis or generalized linear least squares techniques, often referred to as 'data adjustment.' Even with advanced tools to identify benchmark experiments, analysts occasionally find that the application models include some feature or material for which adequately similar benchmark experiments do not exist to support validation. For example, a criticality safety analyst may want to take credit for the presence of fission products in spent nuclear fuel. In such cases, analysts sometimes rely on 'expert judgment' to select

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.

Treatment of uncertainties in atmospheric chemical systems: A combined modeling and experimental approach

NASA Astrophysics Data System (ADS)

Pun, Betty Kong-Ling

1998-12-01

Uncertainty is endemic in modeling. This thesis is a two- phase program to understand the uncertainties in urban air pollution model predictions and in field data used to validate them. Part I demonstrates how to improve atmospheric models by analyzing the uncertainties in these models and using the results to guide new experimentation endeavors. Part II presents an experiment designed to characterize atmospheric fluctuations, which have significant implications towards the model validation process. A systematic study was undertaken to investigate the effects of uncertainties in the SAPRC mechanism for gas- phase chemistry in polluted atmospheres. The uncertainties of more than 500 parameters were compiled, including reaction rate constants, product coefficients, organic composition, and initial conditions. Uncertainty propagation using the Deterministic Equivalent Modeling Method (DEMM) revealed that the uncertainties in ozone predictions can be up to 45% based on these parametric uncertainties. The key parameters found to dominate the uncertainties of the predictions include photolysis rates of NO2, O3, and formaldehyde; the rate constant for nitric acid formation; and initial amounts of NOx and VOC. Similar uncertainty analysis procedures applied to two other mechanisms used in regional air quality models led to the conclusion that in the presence of parametric uncertainties, the mechanisms cannot be discriminated. Research efforts should focus on reducing parametric uncertainties in photolysis rates, reaction rate constants, and source terms. A new tunable diode laser (TDL) infrared spectrometer was designed and constructed to measure multiple pollutants simultaneously in the same ambient air parcels. The sensitivities of the one hertz measurements were 2 ppb for ozone, 1 ppb for NO, and 0.5 ppb for NO2. Meteorological data were also collected for wind, temperature, and UV intensity. The field data showed clear correlations between ozone, NO, and NO2 in the one

Effects of directional uncertainty on visually-guided joystick pointing.

PubMed

Berryhill, Marian; Kveraga, Kestutis; Hughes, Howard C

2005-02-01

Reaction times generally follow the predictions of Hick's law as stimulus-response uncertainty increases, although notable exceptions include the oculomotor system. Saccadic and smooth pursuit eye movement reaction times are independent of stimulus-response uncertainty. Previous research showed that joystick pointing to targets, a motor analog of saccadic eye movements, is only modestly affected by increased stimulus-response uncertainty; however, a no-uncertainty condition (simple reaction time to 1 possible target) was not included. Here, we re-evaluate manual joystick pointing including a no-uncertainty condition. Analysis indicated simple joystick pointing reaction times were significantly faster than choice reaction times. Choice reaction times (2, 4, or 8 possible target locations) only slightly increased as the number of possible targets increased. These data suggest that, as with joystick tracking (a motor analog of smooth pursuit eye movements), joystick pointing is more closely approximated by a simple/choice step function than the log function predicted by Hick's law.

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

Reaction rate for carbon burning in massive stars

DOE PAGES

Jiang, C. L.; Santiago-Gonzalez, D.; Almaraz-Calderon, S.; ...

2018-01-10

Carbon burning is a critical phase for nucleosynthesis in massive stars. The conditions for igniting this burning stage, and the subsequent isotope composition of the resulting ashes, depend strongly on the reaction rate for 12C+ 12C fusion at very low energies. Results for the cross sections for this reaction are influenced by various backgrounds encountered in measurements at such energies. In this paper, we report on a new measurement of 12C+ 12C fusion cross sections where these backgrounds have been minimized. In conclusion, it is found that the astrophysical S factor exhibits a maximum around E cm=3.5–4.0 MeV, which leadsmore » to a reduction of the previously predicted astrophysical reaction rate.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Reduction and Uncertainty Analysis of Chemical Mechanisms Based on Local and Global Sensitivities

NASA Astrophysics Data System (ADS)

Esposito, Gaetano

Numerical simulations of critical reacting flow phenomena in hypersonic propulsion devices require accurate representation of finite-rate chemical kinetics. The chemical kinetic models available for hydrocarbon fuel combustion are rather large, involving hundreds of species and thousands of reactions. As a consequence, they cannot be used in multi-dimensional computational fluid dynamic calculations in the foreseeable future due to the prohibitive computational cost. In addition to the computational difficulties, it is also known that some fundamental chemical kinetic parameters of detailed models have significant level of uncertainty due to limited experimental data available and to poor understanding of interactions among kinetic parameters. In the present investigation, local and global sensitivity analysis techniques are employed to develop a systematic approach of reducing and analyzing detailed chemical kinetic models. Unlike previous studies in which skeletal model reduction was based on the separate analysis of simple cases, in this work a novel strategy based on Principal Component Analysis of local sensitivity values is presented. This new approach is capable of simultaneously taking into account all the relevant canonical combustion configurations over different composition, temperature and pressure conditions. Moreover, the procedure developed in this work represents the first documented inclusion of non-premixed extinction phenomena, which is of great relevance in hypersonic combustors, in an automated reduction algorithm. The application of the skeletal reduction to a detailed kinetic model consisting of 111 species in 784 reactions is demonstrated. The resulting reduced skeletal model of 37--38 species showed that the global ignition/propagation/extinction phenomena of ethylene-air mixtures can be predicted within an accuracy of 2% of the full detailed model. The problems of both understanding non-linear interactions between kinetic parameters and

Constraints on the ^22Ne(α,n)^25Mg reaction rate from ^natMg+n Total and ^25Mg(n,γ ) Cross Sections

NASA Astrophysics Data System (ADS)

Koehler, Paul

2002-10-01

The ^22Ne(α,n)^25Mg reaction is the neutron source during the s process in massive and intermediate mass stars as well as a secondary neutron source during the s process in low mass stars. Therefore, an accurate determination of this rate is important for a better understanding of the origin of nuclides heavier than iron as well as for improving s-process models. Also, because the s process produces seed nuclides for a later p process in massive stars, an accurate value for this rate is important for a better understanding of the p process. Because the lowest observed resonance in direct ^22Ne(α,n)^25Mg measurements is considerably above the most important energy range for s-process temperatures, the uncertainty in this rate is dominated by the poorly known properties of states in ^26Mg between this resonance and threshold. Neutron measurements can observe these states with much better sensitivity and determine their parameters much more accurately than direct ^22Ne(α,n)^25Mg measurements. I have analyzed previously reported Mg+n total and ^25Mg(n,γ ) cross sections to obtain a much improved set of resonance parameters for states in ^26Mg in this region, and an improved estimate of the uncertainty in the ^22Ne(α,n)^25Mg reaction rate. This work was supported by the U.S. DOE under contract No. DE-AC05-00OR22725 with UT-Battell, LLC.

Dynamic rating curve assessment in hydrometric stations and calculation of the associated uncertainties : Quality and monitoring indicators

NASA Astrophysics Data System (ADS)

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

2013-04-01

Whether we talk about safety reasons, energy production or regulation, water resources management is one of EDF's (French hydropower company) main concerns. To meet these needs, since the fifties EDF-DTG operates a hydrometric network that includes more than 350 hydrometric stations. The data collected allow real time monitoring of rivers (hydro meteorological forecasts at points of interests), as well as hydrological studies and the sizing of structures. Ensuring the quality of stream flow data is a priority. A rating curve is an indirect method of estimating the discharge in rivers based on water level measurements. The value of discharge obtained thanks to the rating curve is not entirely accurate due to the constant changes of the river bed morphology, to the precision of the gaugings (direct and punctual discharge measurements) and to the quality of the tracing. As time goes on, the uncertainty of the estimated discharge from a rating curve « gets older » and increases: therefore the final level of uncertainty remains particularly difficult to assess. Moreover, the current EDF capacity to produce a rating curve is not suited to the frequency of change of the stage-discharge relationship. The actual method does not take into consideration the variation of the flow conditions and the modifications of the river bed which occur due to natural processes such as erosion, sedimentation and seasonal vegetation growth. In order to get the most accurate stream flow data and to improve their reliability, this study undertakes an original « dynamic» method to compute rating curves based on historical gaugings from a hydrometric station. A curve is computed for each new gauging and a model of uncertainty is adjusted for each of them. The model of uncertainty takes into account the inaccuracies in the measurement of the water height, the quality of the tracing, the uncertainty of the gaugings and the aging of the confidence intervals calculated with a variographic

Determination of the reference air kerma rate for 192Ir brachytherapy sources and the related uncertainty.

PubMed

van Dijk, Eduard; Kolkman-Deurloo, Inger-Karine K; Damen, Patricia M G

2004-10-01

Different methods exist to determine the air kerma calibration factor of an ionization chamber for the spectrum of a 192Ir high-dose-rate (HDR) or pulsed-dose-rate (PDR) source. An analysis of two methods to obtain such a calibration factor was performed: (i) the method recommended by [Goetsch et al., Med. Phys. 18, 462-467 (1991)] and (ii) the method employed by the Dutch national standards institute NMi [Petersen et al., Report S-EI-94.01 (NMi, Delft, The Netherlands, 1994)]. This analysis showed a systematic difference on the order of 1% in the determination of the strength of 192Ir HDR and PDR sources depending on the method used for determining the air kerma calibration factor. The definitive significance of the difference between these methods can only be addressed after performing an accurate analysis of the associated uncertainties. For an NE 2561 (or equivalent) ionization chamber and an in-air jig, a typical uncertainty budget of 0.94% was found with the NMi method. The largest contribution in the type-B uncertainty is the uncertainty in the air kerma calibration factor for isotope i, N(i)k, as determined by the primary or secondary standards laboratories. This uncertainty is dominated by the uncertainties in the physical constants for the average mass-energy absorption coefficient ratio and the stopping power ratios. This means that it is not foreseeable that the standards laboratories can decrease the uncertainty in the air kerma calibration factors for ionization chambers in the short term. When the results of the determination of the 192Ir reference air kerma rates in, e.g., different institutes are compared, the uncertainties in the physical constants are the same. To compare the applied techniques, the ratio of the results can be judged by leaving out the uncertainties due to these physical constants. In that case an uncertainty budget of 0.40% (coverage factor=2) should be taken into account. Due to the differences in approach between the method

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)

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

Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

NASA Astrophysics Data System (ADS)

Zhang, Hong; Zuo, Ran; Zhang, Guoyi

2017-11-01

In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

Incorporating reaction-rate dependence in reaction-front models of wellbore-cement/carbonated-brine systems

DOE PAGES

Iyer, Jaisree; Walsh, Stuart D. C.; Hao, Yue; ...

2017-03-08

Contact between wellbore cement and carbonated brine produces reaction zones that alter the cement's chemical composition and its mechanical properties. The reaction zones have profound implications on the ability of wellbore cement to serve as a seal to prevent the flow of carbonated brine. Under certain circumstances, the reactions may cause resealing of leakage pathways within the cement or at cement-interfaces; either due to fracture closure in response to mechanical weakening or due to the precipitation of calcium carbonate within the fracture. In prior work, we showed how mechanical sealing can be simulated using a diffusion-controlled reaction-front model that linksmore » the growth of the cement reaction zones to the mechanical response of the fracture. Here, we describe how such models may be extended to account for the effects of the calcite reaction-rate. We discuss how the relative rates of reaction and diffusion within the cement affect the precipitation of calcium carbonate within narrow leakage pathways, and how such behavior relates to the formation of characteristic reaction modes in the direction of flow. In addition, we compare the relative impact of precipitation and mechanical deformation on fracture sealing for a range of flow conditions and fracture apertures. Here, we conclude by considering how the prior leaching of calcium from cement may influence the sealing behavior of fractures, and the implication of prior leaching on the ability of laboratory tests to predict long-term sealing.« less

Incorporating reaction-rate dependence in reaction-front models of wellbore-cement/carbonated-brine systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iyer, Jaisree; Walsh, Stuart D. C.; Hao, Yue

Contact between wellbore cement and carbonated brine produces reaction zones that alter the cement's chemical composition and its mechanical properties. The reaction zones have profound implications on the ability of wellbore cement to serve as a seal to prevent the flow of carbonated brine. Under certain circumstances, the reactions may cause resealing of leakage pathways within the cement or at cement-interfaces; either due to fracture closure in response to mechanical weakening or due to the precipitation of calcium carbonate within the fracture. In prior work, we showed how mechanical sealing can be simulated using a diffusion-controlled reaction-front model that linksmore » the growth of the cement reaction zones to the mechanical response of the fracture. Here, we describe how such models may be extended to account for the effects of the calcite reaction-rate. We discuss how the relative rates of reaction and diffusion within the cement affect the precipitation of calcium carbonate within narrow leakage pathways, and how such behavior relates to the formation of characteristic reaction modes in the direction of flow. In addition, we compare the relative impact of precipitation and mechanical deformation on fracture sealing for a range of flow conditions and fracture apertures. Here, we conclude by considering how the prior leaching of calcium from cement may influence the sealing behavior of fractures, and the implication of prior leaching on the ability of laboratory tests to predict long-term sealing.« less

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.

Influence of reaction-induced fracturing on serpentinisation rate

NASA Astrophysics Data System (ADS)

Malvoisin, B.; Brantut, N.; Kaczmarek, M. A.

2017-12-01

The alteration of mantle rocks at mid-ocean ridges (i.e. serpentinisation) can lead to a solid volume increase responsible for stress build-up and cracking during reaction (reaction-induced fracturing). This mechanism has been proposed to play a key role for maintaining fluid pathways during reaction. However, its impact on the reaction rate is not yet quantified. We propose here a micromechanical model to quantify the influence of the crystallisation pressure generated during serpentine precipitation on crack propagation in olivine. This model is then coupled to a simple geometrical model to calculate the generation of reactive surface area during grain splitting, and thus bulk reaction rate. The model is able to reproduce experimental kinetic data as well as the mesh texture observed in natural samples. The model results are compared to olivine grain size distribution in serpentinised peridotites from the Marum ophiolite and the Papuan ultramafic belt (Papuan New Guinea). The observations and the model both indicate a decrease of the mean grain size by one order of magnitude as the reaction progresses from 5 to 40 %. Based on this good agreement, we use our model to predict that cracking reduces the characteristic time of serpentinisation by one order of magnitude, down to values comprised between 10 and 1,000 yr. The peak serpentinisation is also shifted 4 km above the previous predictions due to effective pressure increase with depth.

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.

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.

Estimating rate uncertainty with maximum likelihood: differences between power-law and flicker–random-walk models

USGS Publications Warehouse

Langbein, John O.

2012-01-01

Recent studies have documented that global positioning system (GPS) time series of position estimates have temporal correlations which have been modeled as a combination of power-law and white noise processes. When estimating quantities such as a constant rate from GPS time series data, the estimated uncertainties on these quantities are more realistic when using a noise model that includes temporal correlations than simply assuming temporally uncorrelated noise. However, the choice of the specific representation of correlated noise can affect the estimate of uncertainty. For many GPS time series, the background noise can be represented by either: (1) a sum of flicker and random-walk noise or, (2) as a power-law noise model that represents an average of the flicker and random-walk noise. For instance, if the underlying noise model is a combination of flicker and random-walk noise, then incorrectly choosing the power-law model could underestimate the rate uncertainty by a factor of two. Distinguishing between the two alternate noise models is difficult since the flicker component can dominate the assessment of the noise properties because it is spread over a significant portion of the measurable frequency band. But, although not necessarily detectable, the random-walk component can be a major constituent of the estimated rate uncertainty. None the less, it is possible to determine the upper bound on the random-walk noise.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Austin, Sam M.; West, Christopher; Heger, Alexander, E-mail: austin@nscl.msu.edu, E-mail: christopher.west@metrostate.edu, E-mail: Alexander.Heger@Monash.edu

2017-04-10

We have used effective reaction rates (ERRs) for the helium burning reactions to predict the yield of the gamma-emitting nuclei {sup 26}Al, {sup 44}Ti, and {sup 60}Fe 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 {sup 60}Fe/{supmore » 26}Al 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.« less

Estimation of uncertainty in tracer gas measurement of air change rates.

PubMed

Iizuka, Atsushi; Okuizumi, Yumiko; Yanagisawa, Yukio

2010-12-01

Simple and economical measurement of air change rates can be achieved with a passive-type tracer gas doser and sampler. However, this is made more complex by the fact many buildings are not a single fully mixed zone. This means many measurements are required to obtain information on ventilation conditions. In this study, we evaluated the uncertainty of tracer gas measurement of air change rate in n completely mixed zones. A single measurement with one tracer gas could be used to simply estimate the air change rate when n = 2. Accurate air change rates could not be obtained for n ≥ 2 due to a lack of information. However, the proposed method can be used to estimate an air change rate with an accuracy of <33%. Using this method, overestimation of air change rate can be avoided. The proposed estimation method will be useful in practical ventilation measurements.

Multiscale Investigation on Biofilm Distribution and Its Impact on Macroscopic Biogeochemical Reaction Rates: BIOFILM DISTRIBUTION AND RATE SCALING

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Zhifeng; Liu, Chongxuan; Liu, Yuanyuan

Biofilms are critical locations for biogeochemical reactions in the subsurface environment. The occurrence and distribution of biofilms at microscale as well as their impacts on macroscopic biogeochemical reaction rates are still poorly understood. This paper investigated the formation and distributions of biofilms in heterogeneous sediments using multiscale models, and evaluated the effects of biofilm heterogeneity on local and macroscopic biogeochemical reaction rates. Sediment pore structures derived from X-ray computed tomography were used to simulate the microscale flow dynamics and biofilm distribution in the sediment column. The response of biofilm formation and distribution to the variations in hydraulic and chemical propertiesmore » was first examined. One representative biofilm distribution was then utilized to evaluate its effects on macroscopic reaction rates using nitrate reduction as an example. The results revealed that microorganisms primarily grew on the surfaces of grains and aggregates near preferential flow paths where both electron donor and acceptor were readily accessible, leading to the heterogeneous distribution of biofilms in the sediments. The heterogeneous biofilm distribution decreased the macroscopic rate of biogeochemical reactions as compared with those in homogeneous cases. Operationally considering the heterogeneous biofilm distribution in macroscopic reactive transport models such as using dual porosity domain concept can significantly improve the prediction of biogeochemical reaction rates. Overall, this study provided important insights into the biofilm formation and distribution in soils and sediments as well as their impacts on the macroscopic manifestation of reaction rates.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGraw, David; Hershey, Ronald L.

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.more » 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

Chemical kinetic model uncertainty minimization through laminar flame speed measurements

PubMed Central

Park, Okjoo; Veloo, Peter S.; Sheen, David A.; Tao, Yujie; Egolfopoulos, Fokion N.; Wang, Hai

2016-01-01

Laminar flame speed measurements were carried for mixture of air with eight C3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358–2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C3 and C4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel. PMID:27890938

Chemical kinetic model uncertainty minimization through laminar flame speed measurements.

PubMed

Park, Okjoo; Veloo, Peter S; Sheen, David A; Tao, Yujie; Egolfopoulos, Fokion N; Wang, Hai

2016-10-01

Laminar flame speed measurements were carried for mixture of air with eight C 3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso -butene, n -butane, and iso -butane) at the room temperature and ambient pressure. Along with C 1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358-2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C 3 and C 4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C 3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C 4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C 4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel.

Chemical kinetic model uncertainty minimization through laminar flame speed measurements

DOE PAGES

Park, Okjoo; Veloo, Peter S.; Sheen, David A.; ...

2016-07-25

Laminar flame speed measurements were carried for mixture of air with eight C 3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C 1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011,more » 158, 2358–2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C 3 and C 4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C 3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C 4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C 4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel.« less

Chemical kinetic model uncertainty minimization through laminar flame speed measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Okjoo; Veloo, Peter S.; Sheen, David A.

Laminar flame speed measurements were carried for mixture of air with eight C 3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C 1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011,more » 158, 2358–2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C 3 and C 4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C 3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C 4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C 4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel.« less

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying thesemore » methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.« less

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

DOE PAGES

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; ...

2017-03-06

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying thesemore » methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.« less

Numerical Simulation and Quantitative Uncertainty Assessment of Microchannel Flow

NASA Astrophysics Data System (ADS)

Debusschere, Bert; Najm, Habib; Knio, Omar; Matta, Alain; Ghanem, Roger; Le Maitre, Olivier

2002-11-01

This study investigates the effect of uncertainty in physical model parameters on computed electrokinetic flow of proteins in a microchannel with a potassium phosphate buffer. The coupled momentum, species transport, and electrostatic field equations give a detailed representation of electroosmotic and pressure-driven flow, including sample dispersion mechanisms. The chemistry model accounts for pH-dependent protein labeling reactions as well as detailed buffer electrochemistry in a mixed finite-rate/equilibrium formulation. To quantify uncertainty, the governing equations are reformulated using a pseudo-spectral stochastic methodology, which uses polynomial chaos expansions to describe uncertain/stochastic model parameters, boundary conditions, and flow quantities. Integration of the resulting equations for the spectral mode strengths gives the evolution of all stochastic modes for all variables. Results show the spatiotemporal evolution of uncertainties in predicted quantities and highlight the dominant parameters contributing to these uncertainties during various flow phases. This work is supported by DARPA.

Global sensitivity analysis for identifying important parameters of nitrogen nitrification and denitrification under model uncertainty and scenario uncertainty

NASA Astrophysics Data System (ADS)

Chen, Zhuowei; Shi, Liangsheng; Ye, Ming; Zhu, Yan; Yang, Jinzhong

2018-06-01

Nitrogen reactive transport modeling is subject to uncertainty in model parameters, structures, and scenarios. By using a new variance-based global sensitivity analysis method, this paper identifies important parameters for nitrogen reactive transport with simultaneous consideration of these three uncertainties. A combination of three scenarios of soil temperature and two scenarios of soil moisture creates a total of six scenarios. Four alternative models describing the effect of soil temperature and moisture content are used to evaluate the reduction functions used for calculating actual reaction rates. The results show that for nitrogen reactive transport problem, parameter importance varies substantially among different models and scenarios. Denitrification and nitrification process is sensitive to soil moisture content status rather than to the moisture function parameter. Nitrification process becomes more important at low moisture content and low temperature. However, the changing importance of nitrification activity with respect to temperature change highly relies on the selected model. Model-averaging is suggested to assess the nitrification (or denitrification) contribution by reducing the possible model error. Despite the introduction of biochemical heterogeneity or not, fairly consistent parameter importance rank is obtained in this study: optimal denitrification rate (Kden) is the most important parameter; reference temperature (Tr) is more important than temperature coefficient (Q10); empirical constant in moisture response function (m) is the least important one. Vertical distribution of soil moisture but not temperature plays predominant role controlling nitrogen reaction. This study provides insight into the nitrogen reactive transport modeling and demonstrates an effective strategy of selecting the important parameters when future temperature and soil moisture carry uncertainties or when modelers face with multiple ways of establishing nitrogen

Astrophysical reaction rate for α(αn,γ)9Be by photodisintegration

NASA Astrophysics Data System (ADS)

Sumiyoshi, K.; Utsunomiya, H.; Goko, S.; Kajino, T.

2002-10-01

We study the astrophysical reaction rate for the formation of 9Be through the three body reaction α(αn,γ). This reaction is one of the key reactions which could bridge the mass gap at A=8 nuclear systems to produce intermediate-to-heavy mass elements in alpha- and neutron-rich environments such as r-process nucleosynthesis in supernova explosions, s-process nucleosynthesis in asymptotic giant branch (AGB) stars, and primordial nucleosynthesis in baryon inhomogeneous cosmological models. To calculate the thermonuclear reaction rate in a wide range of temperatures, we numerically integrate the thermal average of cross sections assuming a two-steps formation through a metastable 8Be, α+α⇌8Be(n,γ)9Be. Off-resonant and on-resonant contributions from the ground state in 8Be are taken into account. As input cross section, we adopt the latest experimental data by photodisintegration of 9Be with laser-electron photon beams, which covers all relevant resonances in 9Be. Experimental data near the neutron threshold are added with γ-ray flux corrections and a new least-squares analysis is made to deduce resonance parameters in the Breit-Wigner formulation. Based on the photodisintegration cross section, we provide the reaction rate for α(αn,γ)9Be in the temperature range from T9=10-3 to T9=101 (T9 is the temperature in units of 109 K) both in the tabular form and in the analytical form for potential usage in nuclear reaction network calculations. The calculated reaction rate is compared with the reaction rates of the CF88 and the NACRE compilations. The CF88 rate, which is based on the photoneutron cross section for the 1/2+ state in 9Be by Berman et al., is valid at T9>0.028 due to lack of the off-resonant contribution. The CF88 rate differs from the present rate by a factor of two in a temperature range T9⩾0.1. The NACRE rate, which adopted different sources of experimental information on resonance states in 9Be, is 4-12 times larger than the present rate at T9�

Uncertainty quantification in (α,n) neutron source calculations for an oxide matrix

DOE PAGES

Pigni, M. T.; Croft, S.; Gauld, I. C.

2016-04-25

Here we present a methodology to propagate nuclear data covariance information in neutron source calculations from (α,n) reactions. The approach is applied to estimate the uncertainty in the neutron generation rates for uranium oxide fuel types due to uncertainties on 1) 17,18O( α,n) reaction cross sections and 2) uranium and oxygen stopping power cross sections. The procedure to generate reaction cross section covariance information is based on the Bayesian fitting method implemented in the R-matrix SAMMY code. The evaluation methodology uses the Reich-Moore approximation to fit the 17,18O(α,n) reaction cross-sections in order to derive a set of resonance parameters andmore » a related covariance matrix that is then used to calculate the energydependent cross section covariance matrix. The stopping power cross sections and related covariance information for uranium and oxygen were obtained by the fit of stopping power data in the -energy range of 1 keV up to 12 MeV. Cross section perturbation factors based on the covariance information relative to the evaluated 17,18O( α,n) reaction cross sections, as well as uranium and oxygen stopping power cross sections, were used to generate a varied set of nuclear data libraries used in SOURCES4C and ORIGEN for inventory and source term calculations. The set of randomly perturbed output (α,n) source responses, provide the mean values and standard deviations of the calculated responses reflecting the uncertainties in nuclear data used in the calculations. Lastly, the results and related uncertainties are compared with experiment thick target (α,n) yields for uranium oxide.« less

Modelling of plasma-based dry reforming: how do uncertainties in the input data affect the calculation results?

NASA Astrophysics Data System (ADS)

Wang, Weizong; Berthelot, Antonin; Zhang, Quanzhi; Bogaerts, Annemie

2018-05-01

One of the main issues in plasma chemistry modeling is that the cross sections and rate coefficients are subject to uncertainties, which yields uncertainties in the modeling results and hence hinders the predictive capabilities. In this paper, we reveal the impact of these uncertainties on the model predictions of plasma-based dry reforming in a dielectric barrier discharge. For this purpose, we performed a detailed uncertainty analysis and sensitivity study. 2000 different combinations of rate coefficients, based on the uncertainty from a log-normal distribution, are used to predict the uncertainties in the model output. The uncertainties in the electron density and electron temperature are around 11% and 8% at the maximum of the power deposition for a 70% confidence level. Still, this can have a major effect on the electron impact rates and hence on the calculated conversions of CO2 and CH4, as well as on the selectivities of CO and H2. For the CO2 and CH4 conversion, we obtain uncertainties of 24% and 33%, respectively. For the CO and H2 selectivity, the corresponding uncertainties are 28% and 14%, respectively. We also identify which reactions contribute most to the uncertainty in the model predictions. In order to improve the accuracy and reliability of plasma chemistry models, we recommend using only verified rate coefficients, and we point out the need for dedicated verification experiments.

Measurement of Reactions on 30P for Nova Nucleosynthesis

NASA Astrophysics Data System (ADS)

Ma, Z.; Guidry, M. W.; Hix, W. R.; Smith, M. S.

2003-05-01

Replace these paragraphs with your abstract. We encourage you to include a sentence acknowledging your funding agency. In a recent study the 30P(p,gamma)31S rate played a crucial role in the synthesis of heavier nuclear species, from Si to Ca, in nova outbursts on ONe White Dwarfs [1]. The adopted rate of this reaction, based on a Hauser-Feshbach calculation [2], has a large uncertainty and could be as much as a factor of 100 too high or too low [3]. In their study, Jose et al.[1] varied the 30P(p,gamma)31S reaction rate within this uncertainty and found that, when rate is reduced by a factor of 100, the synthesis of elements above Si is lowered by a factor 10 with respect to the values found with the nominal rate. This has important consequences for nova nucleosynthesis, as overproduction of isotopes in the Si to Ca mass region has been observed in the ejecta from some nova explosions (e.g.,[4,5]). While generally valid at higher temperatures, Hauser-Feshbach calculations of the rates at nova temperatures can have large uncertainties. At these temperatures, the rate is more likely dominated by a few individual nuclear resonances. At present there are about 10 31S resonances known above the 30P + p threshold that may contribute to the 30P(p,gamma)31S reaction rate at nova temperatures. The excitation energies of these levels are known but spins and parities (for all but two) are not. We plan to measure the 30P(p,p)30P and 30P(p,gamma)31S reactions at HRIBF to better determine this reaction rate. A detailed description of the experiments will be given. We are also conducting a new nova nucleosynthesis simulation over multiple spatial zones of the exploding envelope to investigate the influence of the 30P(p,gamma)31S reaction rate on nova nucleosynthesis. The results of these calculations will be discussed. 1. Jose , J., Coc, A., Hernanz, M., Astrophys. J., 560, 897(2001). 2. Thielemann, F.-K et al., 1987, Advances in Nuclear Astrophysics, ed. E. Vangioni-Flam ( Gif

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.

Evaluating the combined effects of source zone mass release rates and aquifer heterogeneity on solute discharge uncertainty

NASA Astrophysics Data System (ADS)

de Barros, Felipe P. J.

2018-07-01

Quantifying the uncertainty in solute mass discharge at an environmentally sensitive location is key to assess the risks due to groundwater contamination. Solute mass fluxes are strongly affected by the spatial variability of hydrogeological properties as well as release conditions at the source zone. This paper provides a methodological framework to investigate the interaction between the ubiquitous heterogeneity of the hydraulic conductivity and the mass release rate at the source zone on the uncertainty of mass discharge. Through the use of perturbation theory, we derive analytical and semi-analytical expressions for the statistics of the solute mass discharge at a control plane in a three-dimensional aquifer while accounting for the solute mass release rates at the source. The derived solutions are limited to aquifers displaying low-to-mild heterogeneity. Results illustrate the significance of the source zone mass release rate in controlling the mass discharge uncertainty. The relative importance of the mass release rate on the mean solute discharge depends on the distance between the source and the control plane. On the other hand, we find that the solute release rate at the source zone has a strong impact on the variance of the mass discharge. Within a risk context, we also compute the peak mean discharge as a function of the parameters governing the spatial heterogeneity of the hydraulic conductivity field and mass release rates at the source zone. The proposed physically-based framework is application-oriented, computationally efficient and capable of propagating uncertainty from different parameters onto risk metrics. Furthermore, it can be used for preliminary screening purposes to guide site managers to perform system-level sensitivity analysis and better allocate resources.

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions.

PubMed

Zheng, Jingjing; Truhlar, Donald G

2012-01-01

Complex molecules often have many structures (conformations) of the reactants and the transition states, and these structures may be connected by coupled-mode torsions and pseudorotations; some but not all structures may have hydrogen bonds in the transition state or reagents. A quantitative theory of the reaction rates of complex molecules must take account of these structures, their coupled-mode nature, their qualitatively different character, and the possibility of merging reaction paths at high temperature. We have recently developed a coupled-mode theory called multi-structural variational transition state theory (MS-VTST) and an extension, called multi-path variational transition state theory (MP-VTST), that includes a treatment of the differences in the multi-dimensional tunneling paths and their contributions to the reaction rate. The MP-VTST method was presented for unimolecular reactions in the original paper and has now been extended to bimolecular reactions. The MS-VTST and MP-VTST formulations of variational transition state theory include multi-faceted configuration-space dividing surfaces to define the variational transition state. They occupy an intermediate position between single-conformation variational transition state theory (VTST), which has been used successfully for small molecules, and ensemble-averaged variational transition state theory (EA-VTST), which has been used successfully for enzyme kinetics. The theories are illustrated and compared here by application to three thermal rate constants for reactions of ethanol with hydroxyl radical--reactions with 4, 6, and 14 saddle points.

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.

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

Spectral optimization and uncertainty quantification in combustion modeling

NASA Astrophysics Data System (ADS)

Sheen, David Allan

become available, and it will be desirable to know the effect that inclusion of these data has on the optimized model. Two cases are considered here. In the first, a study of H2/CO mass burning rates has recently been published, wherein the experimentally-obtained results could not be reconciled with any extant H2/CO oxidation model. It is shown in that an optimized H2/CO model can be developed that will reproduce the results of the new experimental measurements. In addition, the high precision of the new experiments provide a strong constraint on the reaction rate parameters of the chemistry model, manifested in a significant improvement in the precision of simulations. In the second case, species time histories were measured during n-heptane oxidation behind reflected shock waves. The highly precise nature of these measurements is expected to impose critical constraints on chemical kinetic models of hydrocarbon combustion. The results show that while an as-compiled, prior reaction model of n-alkane combustion can be accurate in its prediction of the detailed species profiles, the kinetic parameter uncertainty in the model remains to be too large to obtain a precise prediction of the data. Constraining the prior model against the species time histories within the measurement uncertainties led to notable improvements in the precision of model predictions against the species data as well as the global combustion properties considered. Lastly, we show that while the capability of the multispecies measurement presents a step-change in our precise knowledge of the chemical processes in hydrocarbon combustion, accurate data of global combustion properties are still necessary to predict fuel combustion.

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.

Dissolution Rates and Reaction Products of Olivine Interaction with Ammonia-Rich Fluid

NASA Astrophysics Data System (ADS)

Zandanel, A. E.; Truche, L.; Hellmann, R.; Tobie, G.; Marrocchi, Y.

2018-05-01

Olivine dissolution rates and reaction products in NH3-rich fluids are determined from experiments simulating H2O-rock interaction on Enceladus. Kinetic rates are calculated from flow through experiments and reaction products from static experiments.

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.

Rate coefficients for the gas-phase reaction of the hydroxyl radical with CH2=CHF and CH2=CF2.

PubMed

Baasandorj, Munkhbayar; Knight, Gary; Papadimitriou, Vassileios C; Talukdar, Ranajit K; Ravishankara, A R; Burkholder, James B

2010-04-08

Rate coefficients, k, for the gas-phase reaction of the OH radical with CH(2)=CHF (k(1)) and CH(2)=CF(2) (k(2)) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH and laser-induced fluorescence (PLP-LIF) to detect it. Rate coefficients were measured over a range of temperature (220-373 K) and bath gas pressure (20-600 Torr; He, N(2)). The rate coefficients were found to be independent of pressure. The measured rate coefficient for reaction 1 at room temperature was k(1)(296 K) = (5.18 +/- 0.50) x 10(-12) cm(3) molecule(-1) s(-1), independent of pressure, and the temperature dependence is given by the Arrhenius expression k(1)(T) = (1.75 +/- 0.20) x 10(-12) exp[(316 +/- 25)/T] cm(3) molecule(-1) s(-1); the rate coefficients for reaction 2 were k(2)(296 K) = (2.79 +/- 0.25) x 10(-12) cm(3) molecule(-1) s(-1) and k(2)(T) = (1.75 +/- 0.20) x 10(-12) exp[(140 +/- 20)/T] cm(3) molecule(-1) s(-1). The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors. The fall-off parameters for reaction 2 of k(infinity) = 3 x 10(-12) cm(3) molecule(-1) s(-1) and k(0)(296 K) = 1.8 x 10(-28) cm(6) molecule(-2) s(-1) with F(c) = 0.6 reproduce the room temperature data obtained in this study combined with the low pressure rate coefficient data from Howard (J. Chem. Phys. 1976, 65, 4771). OH radical formation was observed for reactions 1 and 2 in the presence of O(2), and the mechanism was investigated using (18)OH and OD rate coefficient measurements with CH(2)=CHF and CH(2)=CF(2) over a range of temperature (260-373 K) and pressure (20-100 Torr, He). Quantum chemical calculations using density functional theory (DFT) were used to determine the geometries and energies of the reactants and adducts formed in reactions 1 and 2 and the peroxy radicals formed following the addition of O(2). The atmospheric lifetimes of CH(2)=CHF and CH(2)=CF(2) due to loss by reaction with OH are approximately 2 and 4

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

Triple-α reaction rate constrained by stellar evolution models

NASA Astrophysics Data System (ADS)

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

2012-11-01

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

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.

Measuring one nucleon transfer reaction 24Mg( p, d)23Mg for astrophysical reaction rates

NASA Astrophysics Data System (ADS)

Lee, E. J.; Chae, K. Y.

2017-12-01

The level structure of a radionuclide 23Mg has been studied by using the 24Mg( p, d)23Mg one nucleon transfer reaction measurement for the astrophysical 19Ne(α, γ)23Mg reaction rate. A 41 MeV proton beam was produced and accelerated at the 25 MV tandem accelerator of the Holifield Radioactive Ion Beam Facility of the Oak Ridge National Laboratory in the United States. The beam particles impinged on an isotopically-enriched 24Mg solid target. Angular distributions of recoiling deuterons were extracted by using a large area silicon strip detector array. By comparing the experimentally-obtained angular distributions with zero range distorted wave Born approximation calculations, spins and parities of three energy levels of 23Mg could be constrained for the first time, which is very important information needed to understand the 19Ne(α, γ)23Mg reaction rate.

Validation and cultural adaptation of a German version of the Physicians' Reactions to Uncertainty scales

PubMed Central

Schneider, Antonius; Szecsenyi, Joachim; Barie, Stefan; Joest, Katharina; Rosemann, Thomas

2007-01-01

Background The aim of the study was to examine the validity of a translated and culturally adapted version of the Physicians' Reaction to Uncertainty scales (PRU) in primary care physicians. Methods In a structured process, the original questionnaire was translated, culturally adapted and assessed after administering it to 93 GPs. Test-retest reliability was tested by sending the questionnaire to the GPs again after two weeks. Results The principal factor analysis confirmed the postulated four-factor structure underlying the 15 items. In contrast to the original version, item 5 achieved a higher loading on the 'concern about bad outcomes' scale. Consequently, we rearranged the scales. Good item-scale correlations were obtained, with Pearson's correlation coefficient ranging from 0.56–0.84. As regards the item-discriminant validity between the scales 'anxiety due to uncertainty' and 'concern about bad outcomes', partially high correlations (Pearson's correlation coefficient 0.02–0.69; p < 0.001) were found, indicating an overlap between both constructs. The assessment of internal consistency revealed satisfactory values; Cronbach's alpha of the rearranged version was 0.86 or higher for all scales. Test-retest-reliability, assessed by means of the intraclass-correlation-coefficient (ICC), exceeded 0.84, except for the 'reluctance to disclose mistakes to physicians' scale (ICC = 0.66). In this scale, some substantial floor effects occurred, with 29.3% of answers showing the lowest possible value. Conclusion Dealing with uncertainty is an important issue in daily practice. The psychometric properties of the rearranged German version of the PRU are satisfying. The revealed floor effects do not limit the significance of the questionnaire. Thus, the German version of the PRU could contribute to the further evaluation of the impact of uncertainty in primary care physicians. PMID:17562018

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.

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…

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

NASA Astrophysics Data System (ADS)

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

2005-07-01

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

Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.

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 themore » 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.« less

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.

Nuclear Reactions and the ν p-Process

NASA Astrophysics Data System (ADS)

Fröhlich, Carla; Hatcher, Daniel; Perdikakis, Georgios; Nikas, Stylianos

In understanding the origin of the heavy elements, the "light heavy elements" pose a particular challenge: The two neutron-capture processes, r- and s-process, cannot explain the abundances patterns seen in very old galactic halo stars. A proposed solution to this problem is the ν p-process, which takes place in the strong neutrino-driven winds of core-collapse supernovae. In the ν p-process, a sequence of (n, p) and (p, γ ) reactions allows for the synthesis of elements with atomic numbers A > 64, which includes Sr, Y, Zr, and others possibly up to Sn. The relevant reaction rates are all based on statistical model predictions and carry some uncertainty. Here, the sensitivity of the final ν p-process abundance pattern on modifications of (n, p), (p, γ ), and (n, γ ) reactions are characterized. Only few reactions affect the final abundance pattern and hence warrant a more detailed study of the reaction rate.

Phasic heart rate responses and cardiac cycle time in auditory choice reaction time.

PubMed

van der Molen, M W; Somsen, R J; Orlebeke, J F

1983-01-01

This study investigated the cardiovascular-behavioral interaction under short and long stimulus interval conditions. In addition, the cardiovascular-behavioral interaction was studied as affected by cardiac cycle duration. Fourteen subjects performed a choice reaction time (RT) task employing a mixed speed-accuracy tradeoff design in which reactions were paced to coincide with a signal that occurs randomly at either 200 or 500 msec after the reaction stimulus. The preparatory interval between a warning stimulus and a lead-reaction stimulus complex was also varied (2 vs. 4.5 sec). Anticipatory deceleration occurred within the 4.5 sec interval but not in the 2 sec interval. The depth of anticipatory deceleration did not discriminate between fast and slow reactions; but an earlier shift from deceleration to acceleration was associated with fast reactions. The effect of stimulus timing relative to the R-wave of the electrocardiogram was also analysed. Meaningful stimuli tended to produce cardiac slowing as previously described in the literature. Early occurring stimuli prolong the cycle of their occurrence more than late occurring stimuli. The later prolong the subsequent cycle. Cardiac cycle time effects were absent for unattended stimuli. The results of anticipatory deceleration suggested that the depth of deceleration was regulated by time-uncertainty and speed-accuracy criterion.

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.

Multiscale Investigation on Biofilm Distribution and Its Impact on Macroscopic Biogeochemical Reaction Rates

NASA Astrophysics Data System (ADS)

Yan, Zhifeng; Liu, Chongxuan; Liu, Yuanyuan; Bailey, Vanessa L.

2017-11-01

Biofilms are critical locations for biogeochemical reactions in the subsurface environment. The occurrence and distribution of biofilms at microscale as well as their impacts on macroscopic biogeochemical reaction rates are still poorly understood. This paper investigated the formation and distributions of biofilms in heterogeneous sediments using multiscale models and evaluated the effects of biofilm heterogeneity on local and macroscopic biogeochemical reaction rates. Sediment pore structures derived from X-ray computed tomography were used to simulate the microscale flow dynamics and biofilm distribution in the sediment column. The response of biofilm formation and distribution to the variations in hydraulic and chemical properties was first examined. One representative biofilm distribution was then utilized to evaluate its effects on macroscopic reaction rates using nitrate reduction as an example. The results revealed that microorganisms primarily grew on the surfaces of grains and aggregates near preferential flow paths where both electron donor and acceptor were readily accessible, leading to the heterogeneous distribution of biofilms in the sediments. The heterogeneous biofilm distribution decreased the macroscopic rate of biogeochemical reactions as compared with those in homogeneous cases. Operationally considering the heterogeneous biofilm distribution in macroscopic reactive transport models such as using dual porosity domain concept can significantly improve the prediction of biogeochemical reaction rates. Overall, this study provided important insights into the biofilm formation and distribution in soils and sediments as well as their impacts on the macroscopic manifestation of reaction rates.

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.

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.

Astrophysical Impact of the Updated 9Be(p,α)6Li and 10B(p,α)7Be Reaction Rates As Deduced By THM

NASA Astrophysics Data System (ADS)

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

2015-10-01

The complete understanding of the stellar abundances of lithium, beryllium, and boron represents one of the most interesting open problems in astrophysics. These elements are largely used to probe stellar structure and mixing phenomena in different astrophysical scenarios, such as pre-main-sequence or main-sequence stars. Their different fragility against (p,α) burning reactions allows one to investigate different depths of the stellar interior. Such fusion mechanisms are triggered at temperatures between T ≈ (2-5) × {10}6 K, thus defining a corresponding Gamow energy between ≈ 3-10 keV, where S(E)-factor measurements need to be performed to get reliable reaction rate evaluations. The Trojan Horse Method is a well defined procedure to measure cross sections at Gamow energies overcoming the uncertainties due to low-energy S(E)-factor extrapolation as well as electron screening effects. Taking advantage of the {\\mathtt{THM}} measure of the 9Be(p,α)6Li and 10B(p,α)7Be cross sections, the corresponding reaction rates have been calculated and compared with the evaluations by the NACRE collaboration, widely used in the literature. The impact on surface abundances of the updated 9Be and 10B (p,α) burning rates is discussed for pre-MS stars.

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.

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 reactions, TACO

EXPERIMENTAL PROTOCOL FOR DETERMINING PROTOLYSIS REACTION RATE CONSTANTS

EPA Science Inventory

An experimental protocol to determine photolysis rates of chemicals which photolyze relatively rapidly in the gas phase has been developed. This procedure provides a basis for evaluating the relative importance of one atmospheric reaction pathway (i.e., photolysis) for organic su...

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

Evaluation of incremental reactivity and its uncertainty in Southern California.

PubMed

Martien, Philip T; Harley, Robert A; Milford, Jana B; Russell, Armistead G

2003-04-15

The incremental reactivity (IR) and relative incremental reactivity (RIR) of carbon monoxide and 30 individual volatile organic compounds (VOC) were estimated for the South Coast Air Basin using two photochemical air quality models: a 3-D, grid-based model and a vertically resolved trajectory model. Both models include an extended version of the SAPRC99 chemical mechanism. For the 3-D modeling, the decoupled direct method (DDM-3D) was used to assess reactivities. The trajectory model was applied to estimate uncertainties in reactivities due to uncertainties in chemical rate parameters, deposition parameters, and emission rates using Monte Carlo analysis with Latin hypercube sampling. For most VOC, RIRs were found to be consistent in rankings with those produced by Carter using a box model. However, 3-D simulations show that coastal regions, upwind of most of the emissions, have comparatively low IR but higher RIR than predicted by box models for C4-C5 alkenes and carbonyls that initiate the production of HOx radicals. Biogenic VOC emissions were found to have a lower RIR than predicted by box model estimates, because emissions of these VOC were mostly downwind of the areas of primary ozone production. Uncertainties in RIR of individual VOC were found to be dominated by uncertainties in the rate parameters of their primary oxidation reactions. The coefficient of variation (COV) of most RIR values ranged from 20% to 30%, whereas the COV of absolute incremental reactivity ranged from about 30% to 40%. In general, uncertainty and variability both decreased when relative rather than absolute reactivity metrics were used.

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 CH 2 OO 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 CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

Impact of the uncertainty in α-captures on {sup 22}Ne on the weak s-process in massive stars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishimura, N.; Hirschi, R.; Pignatari, M.

2014-05-02

Massive stars at solar metallicity contribute to the production of heavy elements with atomic masses between A = 60 and A = 90 via the so-called weak s-process (which takes place during core He and shell C burning phases). Furthermore, recent studies have shown that rotation boosts the s-process production in massive stars at low metallicities, with a production that may reach the barium neutron-magic peak. These results are very sensitive to neutron source and neutron poison reaction rates. For the weak s-process, the main neutron source is the reaction {sup 22}Ne(α,n){sup 25}Mg, which is in competition with {sup 22}Ne(α,γ){supmore » 26}Mg. The uncertainty of both rates strongly affects the nucleosynthesis predictions from stellar model calculations. In this study, we investigate the impact of the uncertainty in α-captures on {sup 22}Ne on the s-process nucleosynthesis in massive stars both at solar and at very low metallicity. For this purpose, we post-process, with the Nugrid mppnp code, non-rotating and rotating evolutionary models 25M{sub ⊙} stars at two different metallicities: Z = Z{sub ⊙} and Z = 10{sup −5}Z{sub ⊙}, respectively. Our results show that uncertainty of {sup 22}Ne(α,n){sup 25}Mg and {sup 22}Ne(α,γ){sup 26}Mg rates have a significant impact on the final elemental production especially for metal poor rotating models. Beside uncertainties in the neutron source reactions, for fast rotating massive stars at low metallicity we revisit the impact of the neutron poisoning effect by the reaction chain {sup 16}O(n,γ){sup 17}O(α,γ){sup 21}Ne, in competition with the {sup 17}O(α,n){sup 20}Ne, recycling the neutrons captured by {sup 16}O.« less

Reactions of O- with D2 at temperatures below 300 K

NASA Astrophysics Data System (ADS)

Plašil, Radek; Tran, Thuy D.; Roučka, Štěpán; Rednyk, Serhiy; Kovalenko, Artem; Jusko, Pavol; Mulin, Dmytro; Zymak, Illia; Dohnal, Petr; Glosík, Juraj

2017-11-01

The reaction of O- anions with molecular deuterium D2 has been studied experimentally using a cryogenic 22-pole radiofrequency ion trap. Two reaction channels were observed. In the associative detachment D2O and an electron are formed and for atom transfer formation OD- + D was observed. The rate coefficients of the reactions have been determined at temperatures below 300 K. The reaction rate coefficient k 1 of the associative detachment increases with decreasing temperature from k 1(300 K) = 0.5 × 10-9 cm3 s-1 at 300 K up to k 1(70 K) = 1.2 × 10-9 cm3 s-1 at 70 K both with 30 % overall uncertainty.

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.

Energy diffusion controlled reaction rate of reacting particle driven by broad-band noise

NASA Astrophysics Data System (ADS)

Deng, M. L.; Zhu, W. Q.

2007-10-01

The energy diffusion controlled reaction rate of a reacting particle with linear weak damping and broad-band noise excitation is studied by using the stochastic averaging method. First, the stochastic averaging method for strongly nonlinear oscillators under broad-band noise excitation using generalized harmonic functions is briefly introduced. Then, the reaction rate of the classical Kramers' reacting model with linear weak damping and broad-band noise excitation is investigated by using the stochastic averaging method. The averaged Itô stochastic differential equation describing the energy diffusion and the Pontryagin equation governing the mean first-passage time (MFPT) are established. The energy diffusion controlled reaction rate is obtained as the inverse of the MFPT by solving the Pontryagin equation. The results of two special cases of broad-band noises, i.e. the harmonic noise and the exponentially corrected noise, are discussed in details. It is demonstrated that the general expression of reaction rate derived by the authors can be reduced to the classical ones via linear approximation and high potential barrier approximation. The good agreement with the results of the Monte Carlo simulation verifies that the reaction rate can be well predicted using the stochastic averaging method.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thanh, Vo Hong, E-mail: vo@cosbi.eu; Priami, Corrado, E-mail: priami@cosbi.eu; Department of Mathematics, University of Trento, Trento

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 reactionmore » 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.« less

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

ERIC Educational Resources Information Center

Olbris, Donald J.; Herzfeld, Judith

2002-01-01

Depletion is a game that reinforces central concepts of reaction rate theory through simulation. Presents the game with a set of follow-up questions suitable for either a quiz or discussion. Also describes student reaction to the game. (MM)

Uncertainty and Sensitivity Analysis of Afterbody Radiative Heating Predictions for Earth Entry

NASA Technical Reports Server (NTRS)

West, Thomas K., IV; Johnston, Christopher O.; Hosder, Serhat

2016-01-01

The objective of this work was to perform sensitivity analysis and uncertainty quantification for afterbody radiative heating predictions of Stardust capsule during Earth entry at peak afterbody radiation conditions. The radiation environment in the afterbody region poses significant challenges for accurate uncertainty quantification and sensitivity analysis due to the complexity of the flow physics, computational cost, and large number of un-certain variables. In this study, first a sparse collocation non-intrusive polynomial chaos approach along with global non-linear sensitivity analysis was used to identify the most significant uncertain variables and reduce the dimensions of the stochastic problem. Then, a total order stochastic expansion was constructed over only the important parameters for an efficient and accurate estimate of the uncertainty in radiation. Based on previous work, 388 uncertain parameters were considered in the radiation model, which came from the thermodynamics, flow field chemistry, and radiation modeling. The sensitivity analysis showed that only four of these variables contributed significantly to afterbody radiation uncertainty, accounting for almost 95% of the uncertainty. These included the electronic- impact excitation rate for N between level 2 and level 5 and rates of three chemical reactions in uencing N, N(+), O, and O(+) number densities in the flow field.

Estimating river discharge uncertainty by applying the Rating Curve Model

NASA Astrophysics Data System (ADS)

Barbetta, S.; Melone, F.; Franchini, M.; Moramarco, T.

2012-04-01

The knowledge of the flow discharge at a river site is necessary for planning and management of water resources as well as for monitoring and real-time forecasting purposes when significant flood events occur. In the hydrological practice, the operational discharge measurement in medium and large rivers is mostly based on indirect approaches by converting the observed stage into discharge values using steady-flow rating curves. However, the stage-discharge relationship can be unknown for hydrometric sections where flow velocity measurements, particularly during high floods, are not available. To overcome this issue, a simplified approach named Rating Curve Model (RCM) and proposed by Moramarco et al. (Moramarco, T., Barbetta, S., F. Melone, F. & Singh, V.P., Relating local stage and remote discharge with significant lateral inflow, J. Hydrol. Engng ASCE, 10[1], 58?69, 2005) can be conveniently used. RCM turned out able to assess, with a high level of accuracy, the discharge hydrograph at a river site where only the stage is monitored while the flow is recorded at a different section along the river, even when significant lateral flows occur. The simple structure of the model is depending on three parameters of which two can be considered characteristic of the river reach and one of the wave travel time of floods. Considering that RCM well lends itself to predict the stage-discharge relationship at a river site wherein only stages are recorded, an uncertainty analysis on river discharge estimate is of interest for the hydrological practice definitely. To this aim, the uncertainty characterizing the RCM outcomes is addressed in this work by considering two different procedures based on the Monte Carlo approach and the Generalized Likelihood Uncertainty Estimation (GLUE) method, respectively. The statistical distribution of parameters is found and a random re-sampling of parameters is done for assessing the 90% confidence interval (CI) of discharge estimates. In

A simple thermometric technique for reaction-rate determination of inorganic species, based on the iodide-catalysed cerium(IV)-arsenic(III) reaction.

PubMed

Grases, F; Forteza, R; March, J G; Cerda, V

1985-02-01

A very simple reaction-rate thermometric technique is used for determination of iodide (5-20 ng ml ), based on its catalytic action on the cerium(IV)-arsenic(III) reaction, and for determination of mercury(II) (1.5-10 ng ml ) and silver(I) (2-10 ng ml ), based on their inhibitory effect on this reaction. The reaction is followed by measuring the rate of temperature increase. The method suffers from very few interferences and is applied to determination of iodide in biological and inorganic samples, and Hg(II) and Ag(I) in pharmaceutical products.

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.

The rate constant of a quantum-diffusion-controlled bimolecular reaction

NASA Astrophysics Data System (ADS)

Bondarev, B. V.

1986-04-01

A quantum-mechanical equation is derived in the tight-bond approximation which describes the motion and chemical interaction of a pair of species A and B when their displacement in the matrix is caused by tunnelling. Within the framework of the discrete model of random walks, definitions are given of the probability and rate constant of a reaction A + B → P (products) proceeding in a condensed medium. A method is suggested for calculating the rate constant of a quantum-diffusion-controlled bimolecular reaction. By this method, an expression is obtained for the rate constant in the stationary spherically symmetrical case. An equation for the density matrix is also proposed which describes the motion and chemical interaction of a pair of species when the quantum and classical diffusion are competitive.

Determination of the rate constant for the NH2(X(2)B1) + NH2(X(2)B1) reaction at low pressure and 293 K.

PubMed

Bahng, Mi-Kyung; Macdonald, R Glen

2008-12-25

The rate constant for the reaction NH(2)(X(2)B(1)) + NH(2)(X(2)B(1)) --> products was measured in CF(4), N(2) and Ar carrier gases at 293 +/- 2 K over a pressure range from 2 to 10 Torr. The NH(2) radical was produced by the 193 nm photolysis of NH(3) dilute in the carrier gas. Both the loss of NH(3) and its subsequent recovery and the production of NH(2) and subsequent reaction were monitored simultaneously following the photolysis laser pulse. Both species were detected using quantitative time-resolved high-resolution absorption spectroscopy. The NH(3) molecule was monitored in the NIR using a rotation transition of the nu(1) + nu(3) first combination band near 1500 nm, and the NH(2) radical was monitored using the (1)2(21) <-- (1)3(31) rotational transition of the (0,7,0)A(2)A(1) <-- (0,0,0) X(2)B(1) band near 675 nm. The low-pressure rate constant showed a linear dependence on pressure. The slope of the pressure dependence was dominated by a recombination rate constant for NH(2) + NH(2) given by (8.0 +/- 0.5) x 10(-29), (5.7 +/- 0.7) x 10(-29), and (3.9 +/- 0.4) x 10(-29) cm(6) molecule(-2) s(-1) in CF(4), N(2), and Ar bath gases, respectively, where the uncertainties are +/-2sigma in the scatter of the measurements. The average of the three independent measurements of the sum of the disproportionation rate constants (the zero pressure rate constant) was (3.4 +/- 6) x 10(-13) cm(3) molecule(-1) s(-1), where the uncertainty is +/-2sigma in the scatter of the measurements.

The Influence of Particle Charge on Heterogeneous Reaction Rate Coefficients

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Pesnell, W. D.

2000-01-01

The effects of particle charge on heterogeneous reaction rates are presented. Many atmospheric particles, whether liquid or solid are charged. This surface charge causes a redistribution of charge within a liquid particle and as a consequence a perturbation in the gaseous uptake coefficient. The amount of perturbation is proportional to the external potential and the square of the ratio of debye length in the liquid to the particle radius. Previous modeling has shown how surface charge affects the uptake coefficient of charged aerosols. This effect is now included in the heterogeneous reaction rate of an aerosol ensemble. Extension of this analysis to ice particles will be discussed and examples presented.

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.

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

NASA Astrophysics Data System (ADS)

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

2012-07-01

In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011), 10.1063/1.3611400] various calculations of the rate coefficient for the Mu + H2 → 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 H2 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.

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

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

Impact of (α, n) reactions on weak r-process in neutrino-driven winds

NASA Astrophysics Data System (ADS)

Bliss, J.; Arcones, A.; Montes, F.; Pereira, J.

2017-05-01

After a successful core-collapse supernova, a neutrino-driven wind develops where it is possible to synthesize lighter heavy elements (30 < Z < 45). In the early galaxy, the origin of these elements is associated with the r-process and to an additional process. Here we assume that the additional process corresponds to the weak r-process (sometimes referred to as alpha-process) taking place in neutrino-driven winds. Based on a trajectory obtained from hydrodynamical simulations we study the astrophysics and nuclear physics uncertainties of a weak r-process with our main focus on the (α, n) reactions. These reactions are critical to redistribute the matter and allow it to move from light to heavy elements after nuclear statistical equilibrium freezes out. In this first sensitivity study, we vary all (α, n) reactions by given constant factors which are justified based on the uncertainties of the statistical model and its nuclear physics input, mainly alpha optical potentials for weak r-process conditions. Our results show that (α, n) rate uncertainties are indeed crucial to predict abundances. Therefore, further studies will follow to identify individual critical reactions. Since the nucleosynthesis path is close to stability, these reactions can be measured in the near future. Since much of the other nuclear data for the weak r-process are known, the reduction in nuclear physics uncertainties provided by these experiments will allow astronomical observations to directly constrain the astronomical conditions in the wind.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, R.L.; Glaeser, R.; Bush, D.

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.

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. Copyright © 2010 The Author(s). Journal compilation © 2010 National Ground Water Association.

Estimating Reaction Rate Coefficients Within a Travel-Time Modeling Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, R; Lu, C; Luo, Jian

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 transportmore » 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.« less

A Monte Carlo Uncertainty Analysis of Ozone Trend Predictions in a Two Dimensional Model. Revision

NASA Technical Reports Server (NTRS)

Considine, D. B.; Stolarski, R. S.; Hollandsworth, S. M.; Jackman, C. H.; Fleming, E. L.

1998-01-01

We use Monte Carlo analysis to estimate the uncertainty in predictions of total O3 trends between 1979 and 1995 made by the Goddard Space Flight Center (GSFC) two-dimensional (2D) model of stratospheric photochemistry and dynamics. The uncertainty is caused by gas-phase chemical reaction rates, photolysis coefficients, and heterogeneous reaction parameters which are model inputs. The uncertainty represents a lower bound to the total model uncertainty assuming the input parameter uncertainties are characterized correctly. Each of the Monte Carlo runs was initialized in 1970 and integrated for 26 model years through the end of 1995. This was repeated 419 times using input parameter sets generated by Latin Hypercube Sampling. The standard deviation (a) of the Monte Carlo ensemble of total 03 trend predictions is used to quantify the model uncertainty. The 34% difference between the model trend in globally and annually averaged total O3 using nominal inputs and atmospheric trends calculated from Nimbus 7 and Meteor 3 total ozone mapping spectrometer (TOMS) version 7 data is less than the 46% calculated 1 (sigma), model uncertainty, so there is no significant difference between the modeled and observed trends. In the northern hemisphere midlatitude spring the modeled and observed total 03 trends differ by more than 1(sigma) but less than 2(sigma), which we refer to as marginal significance. We perform a multiple linear regression analysis of the runs which suggests that only a few of the model reactions contribute significantly to the variance in the model predictions. The lack of significance in these comparisons suggests that they are of questionable use as guides for continuing model development. Large model/measurement differences which are many multiples of the input parameter uncertainty are seen in the meridional gradients of the trend and the peak-to-peak variations in the trends over an annual cycle. These discrepancies unambiguously indicate model formulation

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

PubMed Central

Juraszek, Jarek; Bolhuis, Peter G.

2008-01-01

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

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.

Design of long-term sludge-loading rates for forests under uncertainty

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crohn, D.M.

1995-09-01

A simple time series describing nitrate-nitrogen concentrations percolating form a sludge-amended forest is presented for the case where applications are made at several-year intervals. The time series converges to a quasi-steady-state solution that can be solved for an application rate limited by percolating nitrate-nitrogen concentrations. Excess nitrogen is commonly converted to nitrate, a form that leaches readily to pollute ground water. A chance constraint incorporates uncertainty associated with precipitation and evapotranspiration, the most important factors in determining the excess of water available for leaching. Design loading rates for eight New York state forest regions are discussed. If applications occur atmore » 3-year intervals, rates range form 0.2 to 5.3 Mg/ha dry weight depending on the design confidence level, local excess water patterns, forest nitrogen uptake, sludge type, and atmospheric nitrogen deposition rates. Results are compared to predictions made with FORSENTO, a comprehensive model for simulating sludge applications to northern hardwood forests. FORSENTO simulations suggest that mature hardwoods need only 12 kg/ha to support annually perennial material growth and that atmospheric nitrogen deposition may eventually meet or exceed needs of trees so that landspreading may not be sustainable indefinitely in some areas.« less

NaCl nucleation from brine in seeded simulations: Sources of uncertainty in rate estimates.

PubMed

Zimmermann, Nils E R; Vorselaars, Bart; Espinosa, Jorge R; Quigley, David; Smith, William R; Sanz, Eduardo; Vega, Carlos; Peters, Baron

2018-06-14

This work reexamines seeded simulation results for NaCl nucleation from a supersaturated aqueous solution at 298.15 K and 1 bar pressure. We present a linear regression approach for analyzing seeded simulation data that provides both nucleation rates and uncertainty estimates. Our results show that rates obtained from seeded simulations rely critically on a precise driving force for the model system. The driving force vs. solute concentration curve need not exactly reproduce that of the real system, but it should accurately describe the thermodynamic properties of the model system. We also show that rate estimates depend strongly on the nucleus size metric. We show that the rate estimates systematically increase as more stringent local order parameters are used to count members of a cluster and provide tentative suggestions for appropriate clustering criteria.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

NASA Technical Reports Server (NTRS)

Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C.

2000-01-01

The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

Self-optimized construction of transition rate matrices from accelerated atomistic simulations with Bayesian uncertainty quantification

NASA Astrophysics Data System (ADS)

Swinburne, Thomas D.; Perez, Danny

2018-05-01

A massively parallel method to build large transition rate matrices from temperature-accelerated molecular dynamics trajectories is presented. Bayesian Markov model analysis is used to estimate the expected residence time in the known state space, providing crucial uncertainty quantification for higher-scale simulation schemes such as kinetic Monte Carlo or cluster dynamics. The estimators are additionally used to optimize where exploration is performed and the degree of temperature acceleration on the fly, giving an autonomous, optimal procedure to explore the state space of complex systems. The method is tested against exactly solvable models and used to explore the dynamics of C15 interstitial defects in iron. Our uncertainty quantification scheme allows for accurate modeling of the evolution of these defects over timescales of several seconds.

Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

PubMed

Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

2017-12-21

Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

Minimum reaction network necessary to describe Ar/CF4 plasma etch

NASA Astrophysics Data System (ADS)

Helpert, Sofia; Chopra, Meghali; Bonnecaze, Roger T.

2018-03-01

Predicting the etch and deposition profiles created using plasma processes is challenging due to the complexity of plasma discharges and plasma-surface interactions. Volume-averaged global models allow for efficient prediction of important processing parameters and provide a means to quickly determine the effect of a variety of process inputs on the plasma discharge. However, global models are limited based on simplifying assumptions to describe the chemical reaction network. Here a database of 128 reactions is compiled and their corresponding rate constants collected from 24 sources for an Ar/CF4 plasma using the platform RODEo (Recipe Optimization for Deposition and Etching). Six different reaction sets were tested which employed anywhere from 12 to all 128 reactions to evaluate the impact of the reaction database on particle species densities and electron temperature. Because many the reactions used in our database had conflicting rate constants as reported in literature, we also present a method to deal with those uncertainties when constructing the model which includes weighting each reaction rate and filtering outliers. By analyzing the link between a reaction's rate constant and its impact on the predicted plasma densities and electron temperatures, we determine the conditions at which a reaction is deemed necessary to the plasma model. The results of this study provide a foundation for determining which minimal set of reactions must be included in the reaction set of the plasma model.

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.

Improving the {sup 33}S(p,{gamma}){sup 34}Cl Reaction Rate for Models of Classical Nova Explosions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parikh, A.; Faestermann, Th.; Kruecken, R.

2011-10-28

Reduced uncertainty in the thermonuclear rate of the {sup 33}S(p,{gamma}){sup 34}Cl 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 themore » solar abundance of {sup 33}S. 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 {sup 33}S(p,{gamma}){sup 34}Cl rate (the principal destruction mechanism for {sup 33}S in novae) would help to ensure a robust model prediction for the amount of {sup 33}S that may be produced. Finally, constraining this rate could confirm or rule out the decay of an isomeric state of {sup 34}Cl(E{sub x} = 146 keV, t{sub 1/2} = 32 m) as a source for observable gamma-rays from novae. We have performed several complementary experiments dedicated to improving our knowledge of the {sup 33}S(p,{gamma}){sup 34}Cl rate, using both indirect methods (measurement of the {sup 34}S({sup 3}He,t){sup 34}Cl and {sup 33}S({sup 3}He,d){sup 34}Cl 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.« less

Reaction Rate of Small Diffusing Molecules on a Cylindrical Membrane

NASA Astrophysics Data System (ADS)

Straube, Ronny; Ward, Michael J.; Falcke, Martin

2007-10-01

Biomembranes consist of a lipid bi-layer into which proteins are embedded to fulfill numerous tasks in localized regions of the membrane. Often, the proteins have to reach these regions by simple diffusion. Motivated by the observation that IP3 receptor channels (IP3R) form clusters on the surface of the endoplasmic reticulum (ER) during ATP-induced calcium release, the reaction rate of small diffusing molecules on a cylindrical membrane is calculated based on the Smoluchowski approach. In this way, the cylindrical topology of the tubular ER is explicitly taken into account. The problem can be reduced to the solution of the diffusion equation on a finite cylindrical surface containing a small absorbing hole. The solution is constructed by matching appropriate `inner' and `outer' asymptotic expansions. The asymptotic results are compared with those from numerical simulations and excellent agreement is obtained. For realistic parameter sets, we find reaction rates in the range of experimentally measured clustering rates of IP3R. This supports the idea that clusters are formed by a purely diffusion limited process.

Determination of astrophysical 7Be(p, γ)8B reaction rates from the 7Li(d, p)8Li reaction

NASA Astrophysics Data System (ADS)

Du, XianChao; Guo, Bing; Li, ZhiHong; Pang, DanYang; Li, ErTao; Liu, WeiPing

2015-06-01

The 7Be(p, γ)8B reaction plays a central role not only in the evaluation of solar neutrino fluxes but also in the evolution of the first stars. Study of this reaction requires the asymptotic normalization coefficient (ANC) for the virtual decay 8B g.s. → 7Be + p. By using the charge symmetry relation, we obtain this proton ANC with the single neutron ANC of 8Li g.s. →7Li + n, which is determined with the distorted wave Born approximation (DWBA) and adiabatic distorted wave approximation (ADWA) analysis of the 7Li(d, p)8Li angular distribution. The astrophysical S-factors and reaction rates of the direct capture process in the 7Be(p, γ)8B reaction are further deduced at energies of astrophysical relevance. The astrophysical S-factor at zero energy for direct capture, S 17(0), is derived to be (19.9 ± 3.5) eV b in good agreement with the most recent recommended value. The contributions of the 1+ and 3+ resonances to the S-factor and reaction rate are also evaluated. The present result demonstrates that the direct capture dominates the 7Be(p, γ)8B reaction in the whole temperature range. This work provides an independent examination to the current results of the 7Be(p, γ)8B reaction.

Inventory Uncertainty Quantification using TENDL Covariance Data in Fispact-II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eastwood, J.W.; Morgan, J.G.; Sublet, J.-Ch., E-mail: jean-christophe.sublet@ccfe.ac.uk

2015-01-15

The new inventory code Fispact-II provides predictions of inventory, radiological quantities and their uncertainties using nuclear data covariance information. Central to the method is a novel fast pathways search algorithm using directed graphs. The pathways output provides (1) an aid to identifying important reactions, (2) fast estimates of uncertainties, (3) reduced models that retain important nuclides and reactions for use in the code's Monte Carlo sensitivity analysis module. Described are the methods that are being implemented for improving uncertainty predictions, quantification and propagation using the covariance data that the recent nuclear data libraries contain. In the TENDL library, above themore » upper energy of the resolved resonance range, a Monte Carlo method in which the covariance data come from uncertainties of the nuclear model calculations is used. The nuclear data files are read directly by FISPACT-II without any further intermediate processing. Variance and covariance data are processed and used by FISPACT-II to compute uncertainties in collapsed cross sections, and these are in turn used to predict uncertainties in inventories and all derived radiological data.« less

Adjoint-Based Implicit Uncertainty Analysis for Figures of Merit in a Laser Inertial Fusion Engine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seifried, J E; Fratoni, M; Kramer, K J

A primary purpose of computational models is to inform design decisions and, in order to make those decisions reliably, the confidence in the results of such models must be estimated. Monte Carlo neutron transport models are common tools for reactor designers. These types of models contain several sources of uncertainty that propagate onto the model predictions. Two uncertainties worthy of note are (1) experimental and evaluation uncertainties of nuclear data that inform all neutron transport models and (2) statistical counting precision, which all results of a Monte Carlo codes contain. Adjoint-based implicit uncertainty analyses allow for the consideration of anymore » number of uncertain input quantities and their effects upon the confidence of figures of merit with only a handful of forward and adjoint transport calculations. When considering a rich set of uncertain inputs, adjoint-based methods remain hundreds of times more computationally efficient than Direct Monte-Carlo methods. The LIFE (Laser Inertial Fusion Energy) engine is a concept being developed at Lawrence Livermore National Laboratory. Various options exist for the LIFE blanket, depending on the mission of the design. The depleted uranium hybrid LIFE blanket design strives to close the fission fuel cycle without enrichment or reprocessing, while simultaneously achieving high discharge burnups with reduced proliferation concerns. Neutron transport results that are central to the operation of the design are tritium production for fusion fuel, fission of fissile isotopes for energy multiplication, and production of fissile isotopes for sustained power. In previous work, explicit cross-sectional uncertainty analyses were performed for reaction rates related to the figures of merit for the depleted uranium hybrid LIFE blanket. Counting precision was also quantified for both the figures of merit themselves and the cross-sectional uncertainty estimates to gauge the validity of the analysis. All cross

Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

PubMed

Minakata, Daisuke; Crittenden, John

2011-04-15

The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

A study of the photocatalytic effects of aqueous suspensions of platinized semiconductor materials on the reaction rates of candidate redox reactions

NASA Technical Reports Server (NTRS)

Miles, A. M.

1982-01-01

The effectiveness of powdered semiconductor materials in photocatalyzing candidate redox reactions was investigated. The rate of the photocatalyzed oxidation of cyanide at platinized TiO2 was studied. The extent of the cyanide reaction was followed directly using an electroanalytical method (i.e. differential pulse polarography). Experiments were performed in natural or artificial light. A comparison was made of kinetic data obtained for photocatalysis at platinized powders with rate data for nonplatinized powders.

Temperature dependence of the Cl atom reaction with deuterated methanes.

PubMed

Sauer, Frank; Portmann, Robert W; Ravishankara, A R; Burkholder, James B

2015-05-14

Kinetic isotope effect (KIE) and reaction rate coefficients, k1-k4, for the gas-phase reaction of Cl atoms with (12)CH3D (k1), (12)CH2D2 (k2), (12)CHD3 (k3), and (12)CD4 (k4) over the temperature range 223-343 K in 630 Torr of synthetic air are reported. Rate coefficients were measured using a relative rate technique with (12)CH4 as the primary reference compound. Fourier transform infrared spectroscopy was used to monitor the methane isotopologue loss. The obtained KIE values were (12)CH3D: KIE1(T) = (1.227 ± 0.004) exp((43 ± 5)/T); (12)CH2D2: KIE2(T) = (1.14 ± 0.20) exp((191 ± 60)/T); (12)CHD3: KIE3(T) = (1.73 ± 0.34) exp((229 ± 60)/T); and (12)CD4: KIE4(T) = (1.01 ± 0.3) exp((724 ± 19)/T), where KIEx(T) = kCl+(12)CH4(T)/kx(T). The quoted uncertainties are at the 2σ (95% confidence) level and represent the precision of our data. The following Arrhenius expressions and 295 K rate coefficient values (in units of cm(3) molecule(-1) s(-1)) were derived from the above KIE using a rate coefficient of 7.3 × 10(-12) exp(-1280/T) cm(3) molecule(-1) s(-1) for the reaction of Cl with (12)CH4: k1(T) = (5.95 ± 0.70) × 10(-12) exp(-(1323 ± 50)/T), k1(295 K) = (6.7 ± 0.8) × 10(-14); k2(T) = (6.4 ± 1.3) × 10(-12) exp(-(1471 ± 60)/T), k2(295 K) = (4.4 ± 0.9) × 10(-14); k3(T) = (4.2 ± 1.0) × 10(-12) exp(-(1509 ± 60)/T), k3(295 K) = (2.53 ± 0.6) × 10(-14); and k4(T) = (7.13 ± 2.3) × 10(-12) exp(-(2000 ± 120)/T), k4(295 K) = (0.81 ± 0.26) × 10(-14). The reported uncertainties in the pre-exponential factors are 2σ and include estimated systematic errors in our measurements and the uncertainty in the reference reaction rate coefficient. The results from this study are compared with previously reported room-temperature rate coefficients for each of the deuterated methanes as well as the available temperature dependent data for the Cl atom reactions with CH3D and CD4. A two-dimensional atmospheric chemistry model was used to examine the implications of the

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.

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.

Calculating the True and Observed Rates of Complex Heterogeneous Catalytic Reactions

NASA Astrophysics Data System (ADS)

Avetisov, A. K.; Zyskin, A. G.

2018-06-01

Equations of the theory of steady-state complex reactions are considered in matrix form. A set of stage stationarity equations is given, and an algorithm is described for deriving the canonic set of stationarity equations with appropriate corrections for the existence of fast stages in a mechanism. A formula for calculating the number of key compounds is presented. The applicability of the Gibbs rule to estimating the number of independent compounds in a complex reaction is analyzed. Some matrix equations relating the rates of dependent and key substances are derived. They are used as a basis to determine the general diffusion stoichiometry relationships between temperature, the concentrations of dependent reaction participants, and the concentrations of key reaction participants in a catalyst grain. An algorithm is described for calculating heat and mass transfer in a catalyst grain with respect to arbitrary complex heterogeneous catalytic reactions.

Propagating uncertainty from hydrology into human health risk assessment

NASA Astrophysics Data System (ADS)

Siirila, E. R.; Maxwell, R. M.

2013-12-01

Hydro-geologic modeling and uncertainty assessment of flow and transport parameters can be incorporated into human health risk (both cancer and non-cancer) assessment to better understand the associated uncertainties. This interdisciplinary approach is needed now more than ever as societal problems concerning water quality are increasingly interdisciplinary as well. For example, uncertainty can originate from environmental conditions such as a lack of information or measurement error, or can manifest as variability, such as differences in physiological and exposure parameters between individuals. To complicate the matter, traditional risk assessment methodologies are independent of time, virtually neglecting any temporal dependence. Here we present not only how uncertainty and variability can be incorporated into a risk assessment, but also how time dependent risk assessment (TDRA) allows for the calculation of risk as a function of time. The development of TDRA and the inclusion of quantitative risk analysis in this research provide a means to inform decision makers faced with water quality issues and challenges. The stochastic nature of this work also provides a means to address the question of uncertainty in management decisions, a component that is frequently difficult to quantify. To illustrate this new formulation and to investigate hydraulic mechanisms for sensitivity, an example of varying environmental concentration signals resulting from rate dependencies in geochemical reactions is used. Cancer risk is computed and compared using environmental concentration ensembles modeled with sorption as 1) a linear equilibrium assumption and 2) first order kinetics. Results show that the up scaling of these small-scale processes controls the distribution, magnitude, and associated uncertainty of cancer risk.

Estimation of parameters in rational reaction rates of molecular biological systems via weighted least squares

NASA Astrophysics Data System (ADS)

Wu, Fang-Xiang; Mu, Lei; Shi, Zhong-Ke

2010-01-01

The models of gene regulatory networks are often derived from statistical thermodynamics principle or Michaelis-Menten kinetics equation. As a result, the models contain rational reaction rates which are nonlinear in both parameters and states. It is challenging to estimate parameters nonlinear in a model although there have been many traditional nonlinear parameter estimation methods such as Gauss-Newton iteration method and its variants. In this article, we develop a two-step method to estimate the parameters in rational reaction rates of gene regulatory networks via weighted linear least squares. This method takes the special structure of rational reaction rates into consideration. That is, in the rational reaction rates, the numerator and the denominator are linear in parameters. By designing a special weight matrix for the linear least squares, parameters in the numerator and the denominator can be estimated by solving two linear least squares problems. The main advantage of the developed method is that it can produce the analytical solutions to the estimation of parameters in rational reaction rates which originally is nonlinear parameter estimation problem. The developed method is applied to a couple of gene regulatory networks. The simulation results show the superior performance over Gauss-Newton method.

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

PubMed

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

2007-04-01

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

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....

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.

Investigation of Solvent Effects on the Rate and Stereoselectivity of the Henry Reaction

PubMed Central

Kostal, Jakub; Voutchkova, Adelina M.; Jorgensen, William L.

2011-01-01

A combined computational and experimental kinetic study on the Henry reaction is reported. The effects of salvation on the transition structures and the rates of reaction between nitromethane and formaldehyde, and between nitropropane and benzaldehyde are elucidated with QM/MM calculations. PMID:22168236

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.

Uncertainties in the estimation of specific absorption rate during radiofrequency alternating magnetic field induced non-adiabatic heating of ferrofluids

NASA Astrophysics Data System (ADS)

Lahiri, B. B.; Ranoo, Surojit; Philip, John

2017-11-01

Magnetic fluid hyperthermia (MFH) is becoming a viable cancer treatment methodology where the alternating magnetic field induced heating of magnetic fluid is utilized for ablating the cancerous cells or making them more susceptible to the conventional treatments. The heating efficiency in MFH is quantified in terms of specific absorption rate (SAR), which is defined as the heating power generated per unit mass. In majority of the experimental studies, SAR is evaluated from the temperature rise curves, obtained under non-adiabatic experimental conditions, which is prone to various thermodynamic uncertainties. A proper understanding of the experimental uncertainties and its remedies is a prerequisite for obtaining accurate and reproducible SAR. Here, we study the thermodynamic uncertainties associated with peripheral heating, delayed heating, heat loss from the sample and spatial variation in the temperature profile within the sample. Using first order approximations, an adiabatic reconstruction protocol for the measured temperature rise curves is developed for SAR estimation, which is found to be in good agreement with those obtained from the computationally intense slope corrected method. Our experimental findings clearly show that the peripheral and delayed heating are due to radiation heat transfer from the heating coils and slower response time of the sensor, respectively. Our results suggest that the peripheral heating is linearly proportional to the sample area to volume ratio and coil temperature. It is also observed that peripheral heating decreases in presence of a non-magnetic insulating shielding. The delayed heating is found to contribute up to ~25% uncertainties in SAR values. As the SAR values are very sensitive to the initial slope determination method, explicit mention of the range of linear regression analysis is appropriate to reproduce the results. The effect of sample volume to area ratio on linear heat loss rate is systematically studied and the

Prediction of Chain Propagation Rate Constants of Polymerization Reactions in Aqueous NIPAM/BIS and VCL/BIS Systems.

PubMed

Kröger, Leif C; Kopp, Wassja A; Leonhard, Kai

2017-04-06

Microgels have a wide range of possible applications and are therefore studied with increasing interest. Nonetheless, the microgel synthesis process and some of the resulting properties of the microgels, such as the cross-linker distribution within the microgels, are not yet fully understood. An in-depth understanding of the synthesis process is crucial for designing tailored microgels with desired properties. In this work, rate constants and reaction enthalpies of chain propagation reactions in aqueous N-isopropylacrylamide/N,N'-methylenebisacrylamide and aqueous N-vinylcaprolactam/N,N'-methylenebisacrylamide systems are calculated to identify the possible sources of an inhomogeneous cross-linker distribution in the resulting microgels. Gas-phase reaction rate constants are calculated from B2PLYPD3/aug-cc-pVTZ energies and B3LYPD3/tzvp geometries and frequencies. Then, solvation effects based on COSMO-RS are incorporated into the rate constants to obtain the desired liquid-phase reaction rate constants. The rate constants agree with experiments within a factor of 2-10, and the reaction enthalpies deviate less than 5 kJ/mol. Further, the effect of rate constants on the microgel growth process is analyzed, and it is shown that differences in the magnitude of the reaction rate constants are a source of an inhomogeneous cross-linker distribution within the resulting microgel.

Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burke, Michael P.; Goldsmith, C. Franklin; Klippenstein, Stephen J.

2015-07-16

We have developed a multi-scale approach (Burke, M. P.; Klippenstein, S. J.; Harding, L. B. Proc. Combust. Inst. 2013, 34, 547–555.) to kinetic model formulation that directly incorporates elementary kinetic theories as a means to provide reliable, physics-based extrapolation to unexplored conditions. Here, we extend and generalize the multi-scale modeling strategy to treat systems of considerable complexity – involving multi-well reactions, potentially missing reactions, non-statistical product branching ratios, and non-Boltzmann (i.e. non-thermal) reactant distributions. The methodology is demonstrated here for a subsystem of low-temperature propane oxidation, as a representative system for low-temperature fuel oxidation. A multi-scale model is assembled andmore » informed by a wide variety of targets that include ab initio calculations of molecular properties, rate constant measurements of isolated reactions, and complex systems measurements. Active model parameters are chosen to accommodate both “parametric” and “structural” uncertainties. Theoretical parameters (e.g. barrier heights) are included as active model parameters to account for parametric uncertainties in the theoretical treatment; experimental parameters (e.g. initial temperatures) are included to account for parametric uncertainties in the physical models of the experiments. RMG software is used to assess potential structural uncertainties due to missing reactions. Additionally, branching ratios among product channels are included as active model parameters to account for structural uncertainties related to difficulties in modeling sequences of multiple chemically activated steps. The approach is demonstrated here for interpreting time-resolved measurements of OH, HO2, n-propyl, i-propyl, propene, oxetane, and methyloxirane from photolysis-initiated low-temperature oxidation of propane at pressures from 4 to 60 Torr and temperatures from 300 to 700 K. In particular, the multi

R-Matrix Analysis of the 13C(α,n)16O Reaction

NASA Astrophysics Data System (ADS)

Kock, Arthur; Rogachev, Grigory

2015-10-01

The 13C(α,n)16O reaction plays a crucial role in the main s-process occurring in low-mass thermally-pulsing asymptotic giant branch (TP-AGB) stars, which produces about half of all nuclei heavier than iron. However, direct measurements of this reaction cross section near the Gamow-peak energy are currently not possible due to very small reaction cross sections. Additionally, available cross-section data at higher energy have some inconsistencies, leading to significant uncertainties in low energy extrapolations. A global R-matrix fit was conducted, using all available data for the 13C(α,n)16O, 13C(α, α)13C, and 16O(n,n)16O reactions. Of particular importance was the inclusion of the fixed ANC for the 1 / 2 + state at 6 . 356 MeV in 17O, which was measured recently using the sub-Coulomb α-transfer reaction, as well as the new 13C+ α elastic-scattering data measured in the low-energy region 1 . 6 - 3 . 8 MeV. Important constraining information on various resonances was found, and the uncertainty for the astrophysical 13C(α,n)16O reaction rate was dramatically reduced. Much work on the analysis was done by A. K. Nurmukhanbetova from National Laboratory Astana in Astana, Kazakhstan.

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

Rate and reaction probability of the surface reaction between ozone and dihydromyrcenol measured in a bench scale reactor and a room-sized chamber

NASA Astrophysics Data System (ADS)

Shu, Shi; Morrison, Glenn C.

2012-02-01

Low volatility terpenoids emitted from consumer products can react with ozone on surfaces and may significantly alter concentrations of ozone, terpenoids and reaction products in indoor air. We measured the reaction probability and a second-order surface-specific reaction rate for the ozonation of dihydromyrcenol, a representative indoor terpenoid, adsorbed onto polyvinylchloride (PVC), glass, and latex paint coated spheres. The reaction probability ranged from (0.06-8.97) × 10 -5 and was very sensitive to humidity, substrate and mass adsorbed. The average surface reaction probability is about 10 times greater than that for the gas-phase reaction. The second-order surface-specific rate coefficient ranged from (0.32-7.05) × 10 -15 cm 4 s -1 molecule -1and was much less sensitive to humidity, substrate, or mass adsorbed. We also measured the ozone deposition velocity due to adsorbed dihydromyrcenol on painted drywall in a room-sized chamber, Based on that, we calculated the rate coefficient ((0.42-1.6) × 10 -15 cm 4 molecule -1 s -1), which was consistent with that derived from bench-scale experiments for the latex paint under similar conditions. We predict that more than 95% of dihydromyrcenol oxidation takes place on indoor surfaces, rather than in building air.

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.

Uncertainty as Knowledge: Constraints on Policy Choices Provided by Analysis of Uncertainty

NASA Astrophysics Data System (ADS)

Lewandowsky, S.; Risbey, J.; Smithson, M.; Newell, B. R.

2012-12-01

Uncertainty forms an integral part of climate science, and it is often cited in connection with arguments against mitigative action. We argue that an analysis of uncertainty must consider existing knowledge as well as uncertainty, and the two must be evaluated with respect to the outcomes and risks associated with possible policy options. Although risk judgments are inherently subjective, an analysis of the role of uncertainty within the climate system yields two constraints that are robust to a broad range of assumptions. Those constraints are that (a) greater uncertainty about the climate system is necessarily associated with greater expected damages from warming, and (b) greater uncertainty translates into a greater risk of the failure of mitigation efforts. These ordinal constraints are unaffected by subjective or cultural risk-perception factors, they are independent of the discount rate, and they are independent of the magnitude of the estimate for climate sensitivity. The constraints mean that any appeal to uncertainty must imply a stronger, rather than weaker, need to cut greenhouse gas emissions than in the absence of uncertainty.

Uncertainty in hydrological signatures

NASA Astrophysics Data System (ADS)

McMillan, Hilary; Westerberg, Ida

2015-04-01

Information that summarises the hydrological behaviour or flow regime of a catchment is essential for comparing responses of different catchments to understand catchment organisation and similarity, and for many other modelling and water-management applications. Such information types derived as an index value from observed data are known as hydrological signatures, and can include descriptors of high flows (e.g. mean annual flood), low flows (e.g. mean annual low flow, recession shape), the flow variability, flow duration curve, and runoff ratio. Because the hydrological signatures are calculated from observed data such as rainfall and flow records, they are affected by uncertainty in those data. Subjective choices in the method used to calculate the signatures create a further source of uncertainty. Uncertainties in the signatures may affect our ability to compare different locations, to detect changes, or to compare future water resource management scenarios. The aim of this study was to contribute to the hydrological community's awareness and knowledge of data uncertainty in hydrological signatures, including typical sources, magnitude and methods for its assessment. We proposed a generally applicable method to calculate these uncertainties based on Monte Carlo sampling and demonstrated it for a variety of commonly used signatures. The study was made for two data rich catchments, the 50 km2 Mahurangi catchment in New Zealand and the 135 km2 Brue catchment in the UK. For rainfall data the uncertainty sources included point measurement uncertainty, the number of gauges used in calculation of the catchment spatial average, and uncertainties relating to lack of quality control. For flow data the uncertainty sources included uncertainties in stage/discharge measurement and in the approximation of the true stage-discharge relation by a rating curve. The resulting uncertainties were compared across the different signatures and catchments, to quantify uncertainty

Consistent Modeling of GS 1826-24 X-Ray Bursts for Multiple Accretion Rates Demonstrates the Possibility of Constraining rp-process Reaction Rates

NASA Astrophysics Data System (ADS)

Meisel, Zach

2018-06-01

Type-I X-ray burst light curves encode unique information about the structure of accreting neutron stars and the nuclear reaction rates of the rp-process that powers bursts. Using the first model calculations of hydrogen/helium-burning bursts for a large range of astrophysical conditions performed with the code MESA, this work shows that simultaneous model–observation comparisons for bursts from several accretion rates \\dot{M} are required to remove degeneracies in astrophysical conditions that otherwise reproduce bursts for a single \\dot{M} and that such consistent multi-epoch modeling could possibly limit the 15O(α, γ)19Ne reaction rate. Comparisons to the 1998, 2000, and 2007 bursting epochs of the neutron star GS 1826-24 show that \\dot{M} must be larger than previously inferred and that the shallow heating in this source must be below 0.5 MeV/u, providing a new method to constrain the shallow heating mechanism in the outer layers of accreting neutron stars. Features of the light curve rise are used to demonstrate that a lower limit could likely be placed on the 15O(α, γ) reaction rate, demonstrating the possibility of constraining nuclear reaction rates with X-ray burst light curves.

Believable Statements of Uncertainty and Believable Science

PubMed Central

Lindstrom, Richard M.

2017-01-01

Nearly fifty years ago, two landmark papers appeared that should have cured the problem of ambiguous uncertainty statements in published data. Eisenhart’s paper in Science called for statistically meaningful numbers, and Currie’s Analytical Chemistry paper revealed the wide range in common definitions of detection limit. Confusion and worse can result when uncertainties are misinterpreted or ignored. The recent stories of cold fusion, variable radioactive decay, and piezonuclear reactions provide cautionary examples in which prior probability has been neglected. We show examples from our laboratory and others to illustrate the fact that uncertainty depends on both statistical and scientific judgment. PMID:28584391

Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

NASA Technical Reports Server (NTRS)

Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

1976-01-01

Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

Ab initio thermal rate calculations of HO + HO = O(3P) + H2O reaction and isotopologues.

PubMed

Nguyen, Thanh Lam; Stanton, John F

2013-04-04

The forward and reverse reactions, HO + HO ⇌ O((3)P) + H2O, which play roles in both combustion and laboratory studies, were theoretically characterized with a master equation approach to compute thermal reaction rate constants at both the low and high pressure limits. Our ab initio k(T) results for the title reaction and two isotopic variants agree very well with experiments (within 15%) over a wide temperature range. The calculated reaction rate shows a distinctly non-Arrhenius behavior and a strong curvature consistent with the experiment. This characteristic behavior is due to effects of positive barrier height and quantum mechanical tunneling. Tunneling is very important and contributes more than 70% of total reaction rate at room temperature. A prereactive complex is also important in the overall reaction scheme.

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

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

Uncertainty quantification for optical model parameters

DOE PAGES

Lovell, A. E.; Nunes, F. M.; Sarich, J.; ...

2017-02-21

Although uncertainty quantification has been making its way into nuclear theory, these methods have yet to be explored in the context of reaction theory. For example, it is well known that different parameterizations of the optical potential can result in different cross sections, but these differences have not been systematically studied and quantified. The purpose of our work is to investigate the uncertainties in nuclear reactions that result from fitting a given model to elastic-scattering data, as well as to study how these uncertainties propagate to the inelastic and transfer channels. We use statistical methods to determine a best fitmore » and create corresponding 95% confidence bands. A simple model of the process is fit to elastic-scattering data and used to predict either inelastic or transfer cross sections. In this initial work, we assume that our model is correct, and the only uncertainties come from the variation of the fit parameters. Here, we study a number of reactions involving neutron and deuteron projectiles with energies in the range of 5–25 MeV/u, on targets with mass A=12–208. We investigate the correlations between the parameters in the fit. The case of deuterons on 12C is discussed in detail: the elastic-scattering fit and the prediction of 12C(d,p) 13C transfer angular distributions, using both uncorrelated and correlated χ 2 minimization functions. The general features for all cases are compiled in a systematic manner to identify trends. This work shows that, in many cases, the correlated χ 2 functions (in comparison to the uncorrelated χ 2 functions) provide a more natural parameterization of the process. These correlated functions do, however, produce broader confidence bands. Further optimization may require improvement in the models themselves and/or more information included in the fit.« less

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.

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.

Our Sun IV: The Standard Model and Helioseismology: Consequences of Uncertainties in Input Physics and in Observed Solar Parameters

NASA Technical Reports Server (NTRS)

Boothroyd, Arnold I.; Sackmann, I.-Juliana

2001-01-01

Helioseismic frequency observations provide an extremely accurate window into the solar interior; frequencies from the Michaelson Doppler Imager (MDI) on the Solar and Heliospheric Observatory (SOHO) spacecraft, enable the adiabatic sound speed and adiabatic index to be inferred with an accuracy of a few parts in 10(exp 4) and the density with an accuracy of a few parts in 10(exp 3). This has become a Serious challenge to theoretical models of the Sun. Therefore, we have undertaken a self-consistent, systematic study of the sources of uncertainties in the standard solar models. We found that the largest effect on the interior structure arises from the observational uncertainties in the photospheric abundances of the elements, which affect the sound speed profile at the level of 3 parts in 10(exp 3). The estimated 4% uncertainty in the OPAL opacities could lead to effects of 1 part in 10(exp 3); the approximately 5%, uncertainty in the basic pp nuclear reaction rate would have a similar effect, as would uncertainties of approximately 15% in the diffusion constants for the gravitational settling of helium. The approximately 50% uncertainties in diffusion constants for the heavier elements would have nearly as large an effect. Different observational methods for determining the solar radius yield results differing by as much as 7 parts in 10(exp 4); we found that this leads to uncertainties of a few parts in 10(exp 3) in the sound speed int the solar convective envelope, but has negligible effect on the interior. Our reference standard solar model yielded a convective envelope position of 0.7135 solar radius, in excellent agreement with the observed value of 0.713 +/- 0.001 solar radius and was significantly affected only by Z/X, the pp rate, and the uncertainties in helium diffusion constants. Our reference model also yielded envelope helium abundance of 0.2424, in good agreement with the approximate range of 0.24 to 0.25 inferred from helioseismic observations; only

Reaction Rates Of Olivine Carbonation - An Experimental Study Using Synthetic Fluid Inclusions As Micro-Reactors

NASA Astrophysics Data System (ADS)

Sendula, E.; Lamadrid, H. M.; Bodnar, R. J.

2017-12-01

Ultramafic and mafic rocks (e.g. peridotites, serpentinites and basalts) are being considered as possible targets for CO2 sequestration via mineral carbonation. The determination of reaction kinetics and the factors that control mineralization are important in order to understand and predict fluid-rock reactions between the injected CO2 and the host rocks. Here we present results of experiments focused on determining the reaction rates of carbonation of olivine as a function of initial CO2 concentration (20 mol% and 11 mol%) in the aqueous solution and temperature (100°C and 50°C). We used a recently developed experimental method (Lamadrid et al., 2017) that uses synthetic fluid inclusions as micro-reactors. The micro-reactor technique coupled with non-destructive Raman spectroscopy allows us to monitor the reaction progress in situ and in real time, by quantifying the amount of CO2 consumed in the reaction as a function of time. Results show a measurable decrease of CO2 density in the fluid inclusions as a result of the reaction between the CO2-bearing aqueous phase and olivine. Magnesite formation begins within several hours at 100°C and most of the CO2 was consumed within two days. At 50°C, however, magnesite nucleation and precipitation required weeks to months to begin, and the reaction rates were about an order of magnitude slower than in the experiments at 100°C. No significant differences were observed in the reaction rates as a function of initial CO2 concentration. The application of the synthetic fluid inclusion technique as micro-reactors coupled with non-destructive analytical techniques is a promising tool to monitor rates of fluid-rock reactions in situ and in real time, allowing detailed micron-scale investigations. The technique can be applied to a wide variety of chemical systems, host minerals, reaction products, fluid densities, temperatures, and different starting fluid compositions.

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

PubMed

Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

2011-01-20

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF

Astrophysical reaction rates from a symmetry-informed first-principles perspective

NASA Astrophysics Data System (ADS)

Dreyfuss, Alison; Launey, Kristina; Baker, Robert; Draayer, Jerry; Dytrych, Tomas

2017-01-01

With a view toward a new unified formalism for studying bound and continuum states in nuclei, to understand stellar nucleosynthesis from a fully ab initio perspective, we studied the nature of surface α-clustering in 20Ne by considering the overlap of symplectic states with cluster-like states. We compute the spectroscopic amplitudes and factors, α-decay width, and absolute resonance strength - characterizing major contributions to the astrophysical reaction rate through a low-lying 1- resonant state in 20Ne. As a next step, we consider a fully microscopic treatment for the n+4 He system, based on the successful first-principles No-Core Shell Model/Resonating Group Method (NCSM/RGM) for light nuclei, but with the capability to reach intermediate-mass nuclei. The new model takes advantage of the symmetry-based concept central to the Symmetry-Adapted No-Core Shell Model (SA-NCSM) to reduce computational complexity in physically-informed and methodical way, with sights toward first-principles calculations of rates for important astrophysical reactions, such as the 23 Al(p , γ) 24 Si reaction, believed to have a strong influence on X-ray burst light curves. Supported by the U.S. NSF (OCI-0904874, ACI -1516338) and the U.S. DOE (DE-SC0005248), and benefitted from computing resources provided by Blue Waters and the LSU Center for Computation & Technology.

Pharmacological Fingerprints of Contextual Uncertainty

PubMed Central

Ruge, Diane; Stephan, Klaas E.

2016-01-01

Successful interaction with the environment requires flexible updating of our beliefs about the world. By estimating the likelihood of future events, it is possible to prepare appropriate actions in advance and execute fast, accurate motor responses. According to theoretical proposals, agents track the variability arising from changing environments by computing various forms of uncertainty. Several neuromodulators have been linked to uncertainty signalling, but comprehensive empirical characterisation of their relative contributions to perceptual belief updating, and to the selection of motor responses, is lacking. Here we assess the roles of noradrenaline, acetylcholine, and dopamine within a single, unified computational framework of uncertainty. Using pharmacological interventions in a sample of 128 healthy human volunteers and a hierarchical Bayesian learning model, we characterise the influences of noradrenergic, cholinergic, and dopaminergic receptor antagonism on individual computations of uncertainty during a probabilistic serial reaction time task. We propose that noradrenaline influences learning of uncertain events arising from unexpected changes in the environment. In contrast, acetylcholine balances attribution of uncertainty to chance fluctuations within an environmental context, defined by a stable set of probabilistic associations, or to gross environmental violations following a contextual switch. Dopamine supports the use of uncertainty representations to engender fast, adaptive responses. PMID:27846219

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

PubMed

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

2016-01-21

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

Empirical estimation of astrophysical photodisintegration rates of 106Cd

NASA Astrophysics Data System (ADS)

Belyshev, S. S.; Kuznetsov, A. A.; Stopani, K. A.

2017-09-01

It has been noted in previous experiments that the ratio between the photoneutron and photoproton disintegration channels of 106Cd might be considerably different from predictions of statistical models. The thresholds of these reactions differ by several MeV and the total astrophysical rate of photodisintegration of 106Cd, which is mostly produced in photonuclear reactions during the p-process nucleosynthesis, might be noticeably different from the calculated value. In this work the bremsstrahlung beam of a 55.6 MeV microtron and the photon activation technique is used to measure yields of photonuclear reaction products on isotopically-enriched cadmium targets. The obtained results are compared with predictions of statistical models. The experimental yields are used to estimate photodisintegration reaction rates on 106Cd, which are then used in nuclear network calculations to examine the effects of uncertainties on the produced abundences of p-nuclei.

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

NASA Technical Reports Server (NTRS)

Foy, E.; Ronan, G.; Chinitz, W.

1982-01-01

A principal element to be derived from modeling turbulent reacting flows is an expression for the reaction rates of the various species involved in any particular combustion process under consideration. A temperature-derived most-likely probability density function (pdf) was used to describe the effects of temperature fluctuations on the Arrhenius reaction rate constant. A most-likely bivariate pdf described the effects of temperature and species concentrations fluctuations on the reaction rate. A criterion is developed for the use of an "appropriate" temperature pdf. The formulation of models to calculate the mean turbulent Arrhenius reaction rate constant and the mean turbulent reaction rate is considered and the results of calculations using these models are presented.

Combined Uncertainty and A-Posteriori Error Bound Estimates for CFD Calculations: Theory and Implementation

NASA Technical Reports Server (NTRS)

Barth, Timothy J.

2014-01-01

Simulation codes often utilize finite-dimensional approximation resulting in numerical error. Some examples include, numerical methods utilizing grids and finite-dimensional basis functions, particle methods using a finite number of particles. These same simulation codes also often contain sources of uncertainty, for example, uncertain parameters and fields associated with the imposition of initial and boundary data,uncertain physical model parameters such as chemical reaction rates, mixture model parameters, material property parameters, etc.

Gas-phase rate coefficients for the OH + n-, i-, s-, and t-butanol reactions measured between 220 and 380 K: non-Arrhenius behavior and site-specific reactivity.

PubMed

McGillen, Max R; Baasandorj, Munkhbayar; Burkholder, James B

2013-06-06

Butanol (C4H9OH) is a potential biofuel alternative in fossil fuel gasoline and diesel formulations. The usage of butanol would necessarily lead to direct emissions into the atmosphere; thus, an understanding of its atmospheric processing and environmental impact is desired. Reaction with the OH radical is expected to be the predominant atmospheric removal process for the four aliphatic isomers of butanol. In this work, rate coefficients, k, for the gas-phase reaction of the n-, i-, s-, and t-butanol isomers with the OH radical were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to monitor its temporal profile. Rate coefficients were measured over the temperature range 221-381 K at total pressures between 50 and 200 Torr (He). The reactions exhibited non-Arrhenius behavior over this temperature range and no dependence on total pressure with k(296 K) values of (9.68 ± 0.75), (9.72 ± 0.72), (8.88 ± 0.69), and (1.04 ± 0.08) (in units of 10(-12) cm(3) molecule(-1) s(-1)) for n-, i-, s-, and t-butanol, respectively. The quoted uncertainties are at the 2σ level and include estimated systematic errors. The observed non-Arrhenius behavior is interpreted here to result from a competition between the available H-atom abstraction reactive sites, which have different activation energies and pre-exponential factors. The present results are compared with results from previous kinetic studies, structure-activity relationships (SARs), and theoretical calculations and the discrepancies are discussed. Results from this work were combined with available high temperature (1200-1800 K) rate coefficient data and room temperature reaction end-product yields, where available, to derive a self-consistent site-specific set of reaction rate coefficients of the form AT(n) exp(-E/RT) for use in atmospheric and combustion chemistry modeling.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, Catherine A

2013-02-28

Geochemical reactions in deep subsurface environments are complicated by the consolidated nature and mineralogical complexity of sedimentary rocks. Understanding the kinetics of these reactions is critical to our ability to make long-term predictions about subsurface processes such as pH buffering, alteration in rock structure, permeability changes, and formation of secondary precipitates. In this project, we used a combination of experiments and numerical simulation to bridge the gap between our knowledge of these reactions at the lab scale and rates that are meaningful for modeling reactive transport at core scales. The focus is on acid-driven mineral dissolution, which is specifically relevantmore » in the context of CO2-water-rock interactions in geological sequestration of carbon dioxide. The project led to major findings in three areas. First, we modeled reactive transport in pore-network systems to investigate scaling effects in geochemical reaction rates. We found significant scaling effects when CO2 concentrations are high and reaction rates are fast. These findings indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. Second, we used mathematical modeling to investigate the extent to which SO2, if co-injected with CO2, would acidify formation brines. We found that there exist realistic conditions in which the impact on brine acidity will be limited due to diffusion rate-limited SO2 dissolution from the CO2 phase, and the subsequent pH shift may also be limited by the lack of availability of oxidants to produce sulfuric acid. Third, for three Viking sandstones (Alberta sedimentary basin, Canada), we employed backscattered electron microscopy and energy dispersive X-ray spectroscopy to statistically characterize mineral contact with pore space. We determined that for reactive minerals in sedimentary consolidated rocks, abundance alone is not a good

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.

The 12C(α ,γ )16O reaction and its implications for stellar helium burning

NASA Astrophysics Data System (ADS)

deBoer, R. J.; Görres, J.; Wiescher, M.; Azuma, R. E.; Best, A.; Brune, C. R.; Fields, C. E.; Jones, S.; Pignatari, M.; Sayre, D.; Smith, K.; Timmes, F. X.; Uberseder, E.

2017-07-01

The creation of carbon and oxygen in our Universe is one of the forefront questions in nuclear astrophysics. The determination of the abundance of these elements is key to our understanding of both the formation of life on Earth and to the life cycles of stars. While nearly all models of different nucleosynthesis environments are affected by the production of carbon and oxygen, a key ingredient, the precise determination of the reaction rate of 12C(α ,γ )16O, has long remained elusive. This is owed to the reaction's inaccessibility, both experimentally and theoretically. Nuclear theory has struggled to calculate this reaction rate because the cross section is produced through different underlying nuclear mechanisms. Isospin selection rules suppress the E 1 component of the ground state cross section, creating a unique situation where the E 1 and E 2 contributions are of nearly equal amplitudes. Experimentally there have also been great challenges. Measurements have been pushed to the limits of state-of-the-art techniques, often developed for just these measurements. The data have been plagued by uncharacterized uncertainties, often the result of the novel measurement techniques that have made the different results challenging to reconcile. However, the situation has markedly improved in recent years, and the desired level of uncertainty ≈10 % may be in sight. In this review the current understanding of this critical reaction is summarized. The emphasis is placed primarily on the experimental work and interpretation of the reaction data, but discussions of the theory and astrophysics are also pursued. The main goal is to summarize and clarify the current understanding of the reaction and then point the way forward to an improved determination of the reaction rate.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yuanyuan; Liu, Chongxuan; Zhang, Changyong

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 ratesmore » 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

Determining Role of the Chain Mechanism in the Temperature Dependence of the Gas-Phase Rate of Combustion Reactions

NASA Astrophysics Data System (ADS)

Azatyan, V. V.; Bolod'yan, I. A.; Kopylov, N. P.; Kopylov, S. N.; Prokopenko, V. M.; Shebeko, Yu. N.

2018-05-01

It is shown that the strong dependence of the rate of gas-phase combustion reactions on temperature is determined by the high values of the reaction rate constants of free atoms and radicals. It is established that with a branched chain mechanism, a special role in the reaction rate temperature dependence is played by positive feedback between the concentrations of active intermediate species and the rate of their change. The role of the chemical mechanism in the temperature dependence of the process rate with and without inhibitors is considered.

Reaction rates and prediction of thermal instability during aluminum alloy 6061 dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

McFarlane, J.; DePaoli, D. W.; Mattus, C. H.

Here, chemical kinetics of dissolution of aluminum alloy 6061 was investigated for the processing of Pu-238 for deep space missions. The rate of dissolution was measured by the heat release and appeared to be controlled by the rate of release of Al(OH) 4 – from the metal surface. Rates of reaction were measured from 273 to 365 K, giving an activation energy of 72 ± 13 kJ•(mol Al) –1 and a pre-exponential factor of 5 ± 3 × 10 9 dm 3mol –1min –1. Minor alloying elements did not appear to affect the reaction kinetics. The average heat of dissolutionmore » was –360 ± 70 kJ•(mol NaAlO 2) –1. When extrapolated to an infinitely dilute solution of aluminum, kJ•(mol NaAlO 2) –1.« less

Reaction rates and prediction of thermal instability during aluminum alloy 6061 dissolution

DOE PAGES

McFarlane, J.; DePaoli, D. W.; Mattus, C. H.

2017-11-10

Here, chemical kinetics of dissolution of aluminum alloy 6061 was investigated for the processing of Pu-238 for deep space missions. The rate of dissolution was measured by the heat release and appeared to be controlled by the rate of release of Al(OH) 4 – from the metal surface. Rates of reaction were measured from 273 to 365 K, giving an activation energy of 72 ± 13 kJ•(mol Al) –1 and a pre-exponential factor of 5 ± 3 × 10 9 dm 3mol –1min –1. Minor alloying elements did not appear to affect the reaction kinetics. The average heat of dissolutionmore » was –360 ± 70 kJ•(mol NaAlO 2) –1. When extrapolated to an infinitely dilute solution of aluminum, kJ•(mol NaAlO 2) –1.« less

Consistent Modeling of GS 1826-24 X-Ray Bursts for Multiple Accretion Rates Demonstrates the Possibility of Constraining rp-process Reaction Rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meisel, Zach

Type-I X-ray burst light curves encode unique information about the structure of accreting neutron stars and the nuclear reaction rates of the rp-process that powers bursts. Using the first model calculations of hydrogen/helium-burning bursts for a large range of astrophysical conditions performed with the code MESA, this work shows that simultaneous model–observation comparisons for bursts from several accretion ratesmore » $$\\dot{M}$$ are required to remove degeneracies in astrophysical conditions that otherwise reproduce bursts for a single $$\\dot{M}$$ and that such consistent multi-epoch modeling could possibly limit the 15O(α, γ) 19Ne reaction rate. Comparisons to the 1998, 2000, and 2007 bursting epochs of the neutron star GS 1826-24 show that $$\\dot{M}$$ must be larger than previously inferred and that the shallow heating in this source must be below 0.5 MeV/u, providing a new method to constrain the shallow heating mechanism in the outer layers of accreting neutron stars. Lastly, features of the light curve rise are used to demonstrate that a lower limit could likely be placed on the 15O(α, γ) reaction rate, demonstrating the possibility of constraining nuclear reaction rates with X-ray burst light curves.« less

Consistent Modeling of GS 1826-24 X-Ray Bursts for Multiple Accretion Rates Demonstrates the Possibility of Constraining rp-process Reaction Rates

DOE PAGES

Meisel, Zach

2018-06-21

Type-I X-ray burst light curves encode unique information about the structure of accreting neutron stars and the nuclear reaction rates of the rp-process that powers bursts. Using the first model calculations of hydrogen/helium-burning bursts for a large range of astrophysical conditions performed with the code MESA, this work shows that simultaneous model–observation comparisons for bursts from several accretion ratesmore » $$\\dot{M}$$ are required to remove degeneracies in astrophysical conditions that otherwise reproduce bursts for a single $$\\dot{M}$$ and that such consistent multi-epoch modeling could possibly limit the 15O(α, γ) 19Ne reaction rate. Comparisons to the 1998, 2000, and 2007 bursting epochs of the neutron star GS 1826-24 show that $$\\dot{M}$$ must be larger than previously inferred and that the shallow heating in this source must be below 0.5 MeV/u, providing a new method to constrain the shallow heating mechanism in the outer layers of accreting neutron stars. Lastly, features of the light curve rise are used to demonstrate that a lower limit could likely be placed on the 15O(α, γ) reaction rate, demonstrating the possibility of constraining nuclear reaction rates with X-ray burst light curves.« less

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

NASA Astrophysics Data System (ADS)

Schweigert, Igor

2015-06-01

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

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Eight-dimensional quantum reaction rate calculations for the H+CH{sub 4} and H{sub 2}+CH{sub 3} reactions on recent potential energy surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Yong; Zhang, Dong H., E-mail: zhangdh@dicp.ac.cn

2014-11-21

Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH{sub 4} reaction and the H{sub 2}+CH{sub 3} reaction are calculated. Simulations of the H+CH{sub 4} reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable highmore » accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH{sub 4} rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H{sub 2}+CH{sub 3} reaction are found to be in good consistency with experimental observations.« less

Decomposition reaction rate of BCl3-C3H6(propene)-H2 in the gas phase.

PubMed

Xiao, Jun; Su, Kehe; Liu, Yan; Ren, Hongjiang; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

2012-07-05

The decomposition reaction rate in the BCl(3)-C(3)H(6)-H(2) gas phase reaction system in preparing boron carbides was investigated based on the most favorable reaction pathways proposed by Jiang et al. [Theor. Chem. Accs. 2010, 127, 519] and Yang et al. [J. Theor. Comput. Chem. 2012, 11, 53]. The rate constants of all the elementary reactions were evaluated with the variational transition state theory. The vibrational frequencies for the stationary points as well as the selected points along the minimum energy paths (MEPs) were calculated with density functional theory at the B3PW91/6-311G(d,p) level and the energies were refined with the accurate model chemistry method G3(MP2). For the elementary reaction associated with a transition state, the MEP was obtained with the intrinsic reaction coordinates, while for the elementary reaction without transition state, the relaxed potential energy surface scan was employed to obtain the MEP. The rate constants were calculated for temperatures within 200-2000 K and fitted into three-parameter Arrhenius expressions. The reaction rates were investigated by using the COMSOL software to solve numerically the coupled differential rate equations. The results show that the reactions are, consistent with the experiments, appropriate at 1100-1500 K with the reaction time of 30 s for 1100 K, 1.5 s for 1200 K, 0.12 s for 1300 K, 0.011 s for 1400 K, or 0.001 s for 1500 K, for propene being almost completely consumed. The completely dissociated species, boron carbides C(3)B, C(2)B, and CB, have very low concentrations, and C(3)B is the main product at higher temperatures, while C(2)B is the main product at lower temperatures. For the reaction time 1 s, all these concentrations approach into a nearly constant. The maximum value (in mol/m(3)) is for the highest temperature 1500 K with the orders of -13, -17, and -23 for C(3)B, C(2)B, and CB, respectively. It was also found that the logarithm of the overall reaction rate and reciprocal

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.

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

USGS Publications Warehouse

Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven 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, O2 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 O2threshold 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.

Modeling microbial reaction rates in a submarine hydrothermal vent chimney wall

NASA Astrophysics Data System (ADS)

LaRowe, Douglas E.; Dale, Andrew W.; Aguilera, David R.; L'Heureux, Ivan; Amend, Jan P.; Regnier, Pierre

2014-01-01

The fluids emanating from active submarine hydrothermal vent chimneys provide a window into subseafloor processes and, through mixing with seawater, are responsible for steep thermal and compositional gradients that provide the energetic basis for diverse biological communities. Although several models have been developed to better understand the dynamic interplay of seawater, hydrothermal fluid, minerals and microorganisms inside chimney walls, none provide a fully integrated approach to quantifying the biogeochemistry of these hydrothermal systems. In an effort to remedy this, a fully coupled biogeochemical reaction-transport model of a hydrothermal vent chimney has been developed that explicitly quantifies the rates of microbial catalysis while taking into account geochemical processes such as fluid flow, solute transport and oxidation-reduction reactions associated with fluid mixing as a function of temperature. The metabolisms included in the reaction network are methanogenesis, aerobic oxidation of hydrogen, sulfide and methane and sulfate reduction by hydrogen and methane. Model results indicate that microbial catalysis is generally fastest in the hottest habitable portion of the vent chimney (77-102 °C), and methane and sulfide oxidation peak near the seawater-side of the chimney. The fastest metabolisms are aerobic oxidation of H2 and sulfide and reduction of sulfate by H2 with maximum rates of 140, 900 and 800 pmol cm-3 d-1, respectively. The maximum rate of hydrogenotrophic methanogenesis is just under 0.03 pmol cm-3 d-1, the slowest of the metabolisms considered. Due to thermodynamic inhibition, there is no anaerobic oxidation of methane by sulfate (AOM). These simulations are consistent with vent chimney metabolic activity inferred from phylogenetic data reported in the literature. The model developed here provides a quantitative approach to describing the rates of biogeochemical transformations in hydrothermal systems and can be used to constrain the

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.

Some Nuclear Reaction Rates of Importance for Nucleosynthesis around Mass 45

NASA Astrophysics Data System (ADS)

Mitchell, Leon William

1985-06-01

This thesis describes the measurement of absolute cross sections and the determination of thermonuclear reaction rates for a series of reactions which are of importance in stellar nucleosynthesis. The yield of (gamma)-rays from the reaction ('42)Ca(p,(gamma))('43)Sc has been measured as a function of bombarding energy over the range 0.63 - 3.01 MeV, from ('44)Ca(p,(gamma))('45)Sc over the range 0.775 - 4.00 MeV, from ('42)Ca((alpha),(gamma))('46)Ti over the range 3.62 - 5.62 MeV, from ('42)Ca((alpha),p(gamma))('45)Sc over the range 4.06 - 5.92 MeV, from ('44)Ca(p,p'(gamma))('44)Ca over the range 1.90 - 5.03 MeV and from ('42)Ca(p,p'(gamma))('42)Ca over the range 2.24 - 3.01 MeV. High resolution Ge(Li) detectors have been used for all meas- urements. The cross section of the reaction ('44)Ca(p,n)('44)Sc has been measured from threshold up to a bombarding energy of 5.05 MeV by observation of the 1157 keV (gamma)-ray associated with the residual 3.93 h ('44)Sc activity, and the cross section of ('45)Sc(p,n)('45)Ti has been measured from threshold to a bombarding energy of 4.00 MeV both by observation of the annihilation radiation associated with the residual 3.09 h ('45)Ti activity and by measurement of the total neutron yield with a wide angle BF(,3) tube and paraffin detector. The cross section for the ('42)Ca((alpha),p(,0,1))('45)Sc reaction has been measured over the range 4.78 - 5.92 MeV by observing the emitted protons with a surface barrier detector. Experimental procedures for these measurements are detailed in the thesis, and in particular the efficient preparation of calcium targets with very low levels of ('19)F contamination is discussed. Data from all reactions are compared with the predictions of the statistical model code HAUSER*4, which employs global optical model parameters in the calculation of transmission coefficients and includes width fluctuation corrections. Satisfactory agreement is achieved, being better than a factor of 2 for all reactions

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

NASA Astrophysics Data System (ADS)

Schweigert, Igor

2014-03-01

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

Rates and mechanisms of the atomic oxygen reaction with nickel at elevated temperatures

NASA Technical Reports Server (NTRS)

Christian, J. D.; Gilbreath, W. P.

1973-01-01

The oxidation of nickel by atomic oxygen at pressure from 1 to 45 N/sq m between 1050 and 1250 K was investigated. In these ranges, the oxidation was found to follow the parobolic rate law, viz., K sub p = 0.0000114 exp(-13410/T) g squared/cm4/sec for films of greater than 1 micron thickness and was pressure independent. The activation enthalpy for the oxidation reaction was 112 + or - 11 kj/mole (27 + or - 3 kcal/mole). Of a number of possible mechanisms and defect structures considered, it was shown that the most likely was a saturated surface defect model for atomic oxidation, based on reaction activation enthalpies, impurity effects, pressure independence, and magnitudes of rates. A model judged somewhat less likely was one having doubly ionized cationic defects rate controlling in both atomic and molecular oxygen. From comparisons of the appropriate processes, the following enthalpy values were derived: enthalpy of activation (Ni diffusion in Ni0) = 110 + or - 30 kj/mole and standard enthalpy change for reaction formation (doubly ionized cation vacancies in Ni0 from atomic oxygen)= -9 + or - 25 kj/mole.

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

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

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.

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

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.

An effective rate equation approach to reaction kinetics in small volumes: theory and application to biochemical reactions in nonequilibrium steady-state conditions.

PubMed

Grima, R

2010-07-21

Chemical master equations provide a mathematical description of stochastic reaction kinetics in well-mixed conditions. They are a valid description over length scales that are larger than the reactive mean free path and thus describe kinetics in compartments of mesoscopic and macroscopic dimensions. The trajectories of the stochastic chemical processes described by the master equation can be ensemble-averaged to obtain the average number density of chemical species, i.e., the true concentration, at any spatial scale of interest. For macroscopic volumes, the true concentration is very well approximated by the solution of the corresponding deterministic and macroscopic rate equations, i.e., the macroscopic concentration. However, this equivalence breaks down for mesoscopic volumes. These deviations are particularly significant for open systems and cannot be calculated via the Fokker-Planck or linear-noise approximations of the master equation. We utilize the system-size expansion including terms of the order of Omega(-1/2) to derive a set of differential equations whose solution approximates the true concentration as given by the master equation. These equations are valid in any open or closed chemical reaction network and at both the mesoscopic and macroscopic scales. In the limit of large volumes, the effective mesoscopic rate equations become precisely equal to the conventional macroscopic rate equations. We compare the three formalisms of effective mesoscopic rate equations, conventional rate equations, and chemical master equations by applying them to several biochemical reaction systems (homodimeric and heterodimeric protein-protein interactions, series of sequential enzyme reactions, and positive feedback loops) in nonequilibrium steady-state conditions. In all cases, we find that the effective mesoscopic rate equations can predict very well the true concentration of a chemical species. This provides a useful method by which one can quickly determine the

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).

The C 12 ( α , γ ) O 16 reaction and its implications for stellar helium burning

DOE Office of Scientific and Technical Information (OSTI.GOV)

deBoer, R. J.; Gorres, J.; Wiescher, M.

The creation of carbon and oxygen in our Universe is one of the forefront questions in nuclear astrophysics. The determination of the abundance of these elements is key to our understanding of both the formation of life on Earth and to the life cycles of stars. While nearly all models of different nucleosynthesis environments are affected by the production of carbon and oxygen, a key ingredient, the precise determination of the reaction rate of 12C (α, γ) 16O , has long remained elusive. This is owed to the reaction’s inaccessibility, both experimentally and theoretically. Nuclear theory has struggled to calculatemore » this reaction rate because the cross section is produced through different underlying nuclear mechanisms. Isospin selection rules suppress the E 1 component of the ground state cross section, creating a unique situation where the E 1 and E 2 contributions are of nearly equal amplitudes. Experimentally there have also been great challenges. Measurements have been pushed to the limits of state-of-the-art techniques, often developed for just these measurements. The data have been plagued by uncharacterized uncertainties, often the result of the novel measurement techniques that have made the different results challenging to reconcile. However, the situation has markedly improved in recent years, and the desired level of uncertainty ≈ 10 % may be in sight. In this review the current understanding of this critical reaction is summarized. The emphasis is placed primarily on the experimental work and interpretation of the reaction data, but discussions of the theory and astrophysics are also pursued. In conclusion, the main goal is to summarize and clarify the current understanding of the reaction and then point the way forward to an improved determination of the reaction rate.« less

The C 12 ( α , γ ) O 16 reaction and its implications for stellar helium burning

DOE PAGES

deBoer, R. J.; Gorres, J.; Wiescher, M.; ...

2017-09-07

The creation of carbon and oxygen in our Universe is one of the forefront questions in nuclear astrophysics. The determination of the abundance of these elements is key to our understanding of both the formation of life on Earth and to the life cycles of stars. While nearly all models of different nucleosynthesis environments are affected by the production of carbon and oxygen, a key ingredient, the precise determination of the reaction rate of 12C (α, γ) 16O , has long remained elusive. This is owed to the reaction’s inaccessibility, both experimentally and theoretically. Nuclear theory has struggled to calculatemore » this reaction rate because the cross section is produced through different underlying nuclear mechanisms. Isospin selection rules suppress the E 1 component of the ground state cross section, creating a unique situation where the E 1 and E 2 contributions are of nearly equal amplitudes. Experimentally there have also been great challenges. Measurements have been pushed to the limits of state-of-the-art techniques, often developed for just these measurements. The data have been plagued by uncharacterized uncertainties, often the result of the novel measurement techniques that have made the different results challenging to reconcile. However, the situation has markedly improved in recent years, and the desired level of uncertainty ≈ 10 % may be in sight. In this review the current understanding of this critical reaction is summarized. The emphasis is placed primarily on the experimental work and interpretation of the reaction data, but discussions of the theory and astrophysics are also pursued. In conclusion, the main goal is to summarize and clarify the current understanding of the reaction and then point the way forward to an improved determination of the reaction rate.« less

Electron capture rates in stars studied with heavy ion charge exchange reactions

NASA Astrophysics Data System (ADS)

Bertulani, C. A.

2018-01-01

Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean ~ 50 MeV/nucleon and higher) are now routinely used to extract information of interest for nuclear astrophysics. This is of extreme relevance as many of the nuclei involved in stellar evolution are short-lived. Therefore, indirect methods became the focus of recent studies carried out in major nuclear physics facilities. Among such methods, heavy ion charge exchange is thought to be a useful tool to infer Gamow-Teller matrix elements needed to describe electron capture rates in stars and also double beta-decay experiments. In this short review, I provide a theoretical guidance based on a simple reaction model for charge exchange reactions.

Combined effect of whole-body vibration and ambient lighting on human discomfort, heart rate, and reaction time.

PubMed

Monazzam, Mohammad Reza; Shoja, Esmaeil; Zakerian, Seyed Abolfazl; Foroushani, Abbas Rahimi; Shoja, Mohsen; Gharaee, Masoumeh; Asgari, Amin

2018-07-01

This study aimed to investigate the effect of whole-body vibration and ambient lighting, as well as their combined effect on human discomfort, heart rate, and reaction time in laboratory conditions. 44 men were recruited with an average age of 25.4 ± 1.9 years. Each participant was subjected to 12 experimental steps, each step lasting five minutes for four different vibration accelerations in X, Y, and Z axes at a fixed frequency; three different lighting intensities of 50, 500, and 1000 lx were also considered. At each step, a visual computerized reaction test was taken from subjects and their heart rate recorded by pulse oximeter. In addition, the discomfort rate of subjects was measured using Borg scale. Increasing vibration acceleration significantly increased the discomfort rate and heart beat but not the reaction time. Lack of lighting caused more discomfort in the subjects, but there was no significant correlation between lighting intensity with heart rate and reaction time. The results also showed that the combined effect of vibration and lighting had no significant effect on any of the discomfort, heart rate, and reaction time variables. Whole-body vibration is an important factor in the development of human subjective and physiological reactions compared to lighting. Therefore, consideration of the level of vibration to which an individual is exposed in workplaces subject to vibration plays an important role in reducing the level of human discomfort, but its interaction with ambient lighting does not have a significant effect on human subjective and physiological responses.

Shock Layer Radiation Modeling and Uncertainty for Mars Entry

NASA Technical Reports Server (NTRS)

Johnston, Christopher O.; Brandis, Aaron M.; Sutton, Kenneth

2012-01-01

A model for simulating nonequilibrium radiation from Mars entry shock layers is presented. A new chemical kinetic rate model is developed that provides good agreement with recent EAST and X2 shock tube radiation measurements. This model includes a CO dissociation rate that is a factor of 13 larger than the rate used widely in previous models. Uncertainties in the proposed rates are assessed along with uncertainties in translational-vibrational relaxation modeling parameters. The stagnation point radiative flux uncertainty due to these flowfield modeling parameter uncertainties is computed to vary from 50 to 200% for a range of free-stream conditions, with densities ranging from 5e-5 to 5e-4 kg/m3 and velocities ranging from of 6.3 to 7.7 km/s. These conditions cover the range of anticipated peak radiative heating conditions for proposed hypersonic inflatable aerodynamic decelerators (HIADs). Modeling parameters for the radiative spectrum are compiled along with a non-Boltzmann rate model for the dominant radiating molecules, CO, CN, and C2. A method for treating non-local absorption in the non-Boltzmann model is developed, which is shown to result in up to a 50% increase in the radiative flux through absorption by the CO 4th Positive band. The sensitivity of the radiative flux to the radiation modeling parameters is presented and the uncertainty for each parameter is assessed. The stagnation point radiative flux uncertainty due to these radiation modeling parameter uncertainties is computed to vary from 18 to 167% for the considered range of free-stream conditions. The total radiative flux uncertainty is computed as the root sum square of the flowfield and radiation parametric uncertainties, which results in total uncertainties ranging from 50 to 260%. The main contributors to these significant uncertainties are the CO dissociation rate and the CO heavy-particle excitation rates. Applying the baseline flowfield and radiation models developed in this work, the

Uncertainty in BRCA1 cancer susceptibility testing.

PubMed

Baty, Bonnie J; Dudley, William N; Musters, Adrian; Kinney, Anita Y

2006-11-15

This study investigated uncertainty in individuals undergoing genetic counseling/testing for breast/ovarian cancer susceptibility. Sixty-three individuals from a single kindred with a known BRCA1 mutation rated uncertainty about 12 items on a five-point Likert scale before and 1 month after genetic counseling/testing. Factor analysis identified a five-item total uncertainty scale that was sensitive to changes before and after testing. The items in the scale were related to uncertainty about obtaining health care, positive changes after testing, and coping well with results. The majority of participants (76%) rated reducing uncertainty as an important reason for genetic testing. The importance of reducing uncertainty was stable across time and unrelated to anxiety or demographics. Yet, at baseline, total uncertainty was low and decreased after genetic counseling/testing (P = 0.004). Analysis of individual items showed that after genetic counseling/testing, there was less uncertainty about the participant detecting cancer early (P = 0.005) and coping well with their result (P < 0.001). Our findings support the importance to clients of genetic counseling/testing as a means of reducing uncertainty. Testing may help clients to reduce the uncertainty about items they can control, and it may be important to differentiate the sources of uncertainty that are more or less controllable. Genetic counselors can help clients by providing anticipatory guidance about the role of uncertainty in genetic testing. (c) 2006 Wiley-Liss, Inc.

Re-evaluating reaction rates relevant to nova nucleosynthesis from a nuclear structure perspective

NASA Astrophysics Data System (ADS)

Jenkins, D. G.; Lister, C. J.; Janssens, R. V. F.; Khoo, T. L.; Moore, E. F.; Rehm, K. E.; Seweryniak, D.; Wuosmaa, A. H.; Davinson, T.; Woods, P. J.; Jokinen, A.; Penttila, H.; Martınez-Pinedo, G.; Jose, J.

2006-03-01

Conventionally, reaction rates relevant to nova nucleosynthesis are determined by performing the relevant proton capture reactions directly for stable species, or as has become possible more recently in inverse kinematics using short-lived accelerated radioactive beams with recoil separators. A secondary approach is to compile information on the properties of levels in the Gamow window using transfer reactions. We present a complementary technique where the states of interest are populated in a heavy-ion fusion reaction and their gamma decay studied with a state-of-the-art array of high-purity germanium detectors. The advantages of this approach, including the ability to determine resonance energies with high precision and the possibility of determining spins and parities from gamma-ray angular distributions are discussed. Two specific examples related to the 22Na(p,γ) and 30P(p,γ) reactions are presented.

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.

Reaction Rate Theory in Coordination Number Space: An Application to Ion Solvation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.

2016-04-14

Understanding reaction mechanisms in many chemical and biological processes require application of rare event theories. In these theories, an effective choice of a reaction coordinate to describe a reaction pathway is essential. To this end, we study ion solvation in water using molecular dynamics simulations and explore the utility of coordination number (n = number of water molecules in the first solvation shell) as the reaction coordinate. Here we compute the potential of mean force (W(n)) using umbrella sampling, predicting multiple metastable n-states for both cations and anions. We find with increasing ionic size, these states become more stable andmore » structured for cations when compared to anions. We have extended transition state theory (TST) to calculate transition rates between n-states. TST overestimates the rate constant due to solvent-induced barrier recrossings that are not accounted for. We correct the TST rates by calculating transmission coefficients using the reactive flux method. This approach enables a new way of understanding rare events involving coordination complexes. We gratefully acknowledge Liem Dang and Panos Stinis for useful discussion. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.« less

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.

Effect of Abrupt Substitution of Gadobenate Dimeglumine for Gadopentetate Dimeglumine on Rate of Allergic-like Reactions

PubMed Central

Dillman, Jonathan R.; Cohan, Richard H.; Hussain, Hero K.; Khalatbari, Shokoufeh; McHugh, Jonathan B.; Ellis, James H.

2013-01-01

Purpose: To evaluate the effect of abruptly substituting gadobenate dimeglumine for gadopentetate dimeglumine on allergic-like reactions. Materials and Methods: The institutional review board approved and waived patient consent for this HIPAA-compliant retrospective study. Allergic-like reactions related to gadolinium-based contrast media were assessed 2 years before and 3.5 years after gadobenate dimeglumine was substituted for gadopentetate dimeglumine. Reaction rates and severity were compared by using χ2 tests, Fisher exact tests, odds ratios (ORs), and confidence intervals (CIs). Results: Allergic-like reactions (137 mild, 19 moderate, and six severe) occurred in 162 (0.15%) of 105 607 injections of gadolinium-based contrast media (gadopentetate dimeglumine, 31 540; gadobenate dimeglumine, 66 152; other, 7915). Gadobenate dimeglumine was associated with significantly more overall (0.19% [123 of 66 152] vs 0.08% [24 of 31 540]; OR, 2.4; 95% CI: 1.6, 3.8; P < .0001) and mild (0.16% [107 of 66 152] vs 0.06% [18 of 31 540]; OR, 2.8; 95% CI: 1.7, 4.7; P < .0001) allergic-like reactions than was gadopentetate dimeglumine. The reaction rate for gadobenate dimeglumine peaked (maximum per quarter, 0.38% [16 of 4262]; minimum per quarter, 0.07% [three of 4237]) in the 2nd year after it replaced gadopentetate dimeglumine (maximum per quarter, 0.10% [four of 4122]; minimum per quarter, 0.05% [two of 4222]) and then declined in the 3rd year. The final gadobenate dimeglumine reaction rate (last 3 quarters, 0.12% [17 of 14 387]) did not significantly differ from the original baseline reaction rate with gadopentetate dimeglumine. Conclusion: After gadobenate dimeglumine was substituted for gadopentetate dimeglumine, a significant transient increase occurred in the frequency of reported allergic-like reactions that demonstrated a temporal pattern suggestive of the Weber effect (a transient increase in adverse event reporting that tends to peak in the 2nd year after a new

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

DTIC Science & Technology

2003-06-12

Raghunath Behera, Belinda Bashore, Richard Jendrejak and Susan C. Tucker*, “How local density enhancements influence solute reaction rates in supercritical...water,” National Meeting of the American Chemical Society, San Diego, CA, April 2001. Raghunath Behera, Belinda Bashore, Richard Jendrejak and... Raghunath Behera, Belinda Bashore, Richard Jendrejak and Susan C. Tucker*, “How local density enhancements influence solute reaction rates in supercritical

Rate coefficients of exchange reactions accounting for vibrational excitation of reagents and products

NASA Astrophysics Data System (ADS)

Kustova, E. V.; Savelev, A. S.; Kunova, O. V.

2018-05-01

Theoretical models for the vibrational state-resolved Zeldovich reaction are assessed by comparison with the results of quasi-classical trajectory (QCT) calculations. An error in the model of Aliat is corrected; the model is generalized taking into account NO vibrational states. The proposed model is fairly simple and can be easily implemented to the software for non-equilibrium flow modeling. It provides a good agreement with the QCT rate coefficients in the whole range of temperatures and reagent/product vibrational states. The developed models are tested in simulations of vibrational and chemical relaxation of air mixture behind a shock wave. The importance of accounting for excitated NO vibrational states and accurate prediction of Zeldovich reactions rates is shown.

Propagation of stage measurement uncertainties to streamflow time series

NASA Astrophysics Data System (ADS)

Horner, Ivan; Le Coz, Jérôme; Renard, Benjamin; Branger, Flora; McMillan, Hilary

2016-04-01

Streamflow uncertainties due to stage measurements errors are generally overlooked in the promising probabilistic approaches that have emerged in the last decade. We introduce an original error model for propagating stage uncertainties through a stage-discharge rating curve within a Bayesian probabilistic framework. The method takes into account both rating curve (parametric errors and structural errors) and stage uncertainty (systematic and non-systematic errors). Practical ways to estimate the different types of stage errors are also presented: (1) non-systematic errors due to instrument resolution and precision and non-stationary waves and (2) systematic errors due to gauge calibration against the staff gauge. The method is illustrated at a site where the rating-curve-derived streamflow can be compared with an accurate streamflow reference. The agreement between the two time series is overall satisfying. Moreover, the quantification of uncertainty is also satisfying since the streamflow reference is compatible with the streamflow uncertainty intervals derived from the rating curve and the stage uncertainties. Illustrations from other sites are also presented. Results are much contrasted depending on the site features. In some cases, streamflow uncertainty is mainly due to stage measurement errors. The results also show the importance of discriminating systematic and non-systematic stage errors, especially for long term flow averages. Perspectives for improving and validating the streamflow uncertainty estimates are eventually discussed.

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.

Calculation of astrophysical S-factor and reaction rate in 12C(p, γ)13N reaction

NASA Astrophysics Data System (ADS)

Moghadasi, A.; Sadeghi, H.; Pourimani, R.

2018-02-01

The 12C(p, γ)13N reaction is the first process in the CNO cycle. Also it is a source of low-energy solar neutrinos in various neutrino experiments. Therefore, it is of high interest to gain data of the astrophysical S-factor in low energies. By applying Faddeev's method, we calculated wave functions for the bound state of 13N. Then the cross sections for resonance and non-resonance were calculated through using Breit-Wigner and direct capture cross section formulae, respectively. After that, we calculated the total S-factor and compared it with previous experimental data, revealing a good agreement altogether. Then, we extrapolated the S-factor in zero energy and the result was 1.32 ± 0.19 (keV.b). In the end, we calculated reaction rate and compared it with NACRE data.

Variational RRKM theory calculation of thermal rate constant for carbon—hydrogen bond fission reaction of nitro benzene

NASA Astrophysics Data System (ADS)

Manesh, Afshin Taghva; Heidarnezhad, Zabi alah; Masnabadi, Nasrin

2013-07-01

The present work provides quantitative results for the rate of unimolecular carbon-hydrogen bond fission reaction of benzene and nitro benzene at elevated temperatures up to 2000 K. The potential energy surface for each C-H (in the ortho, meta, and para sites) bond fission reaction of nitro benzene was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C-H bond fission channel is barrier less reaction, we have used variational RRKM theory to predict rate constants. By means of calculated rate constant at the different temperatures, the activation energy and exponential factor were determined. The Arrhenius expression for C-H bond fission reaction of nitro benzene on the ortho, meta and para sites are k( T) = 2.1 × 1017exp(-56575.98/ T), k( T) = 2.1 × 1017exp(-57587.45/ T), and k( T) = 3.3 × 1016exp(-57594.79/ T) respectively. The Arrhenius expression for C-H bond fission reaction of benzene is k( T) = 2 × 1018exp(-59343.48.18/ T). The effect of NO2 group, location of hydrogen atoms on the substituted benzene ring, reaction degeneracy, benzene ring resonance and tunneling effect on the rate expression have been discussed.

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.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.

PubMed

Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger

2013-11-21

The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.

Correlation between discrete probability and reaction front propagation rate in heterogeneous mixtures

NASA Astrophysics Data System (ADS)

Naine, Tarun Bharath; Gundawar, Manoj Kumar

2017-09-01

We demonstrate a very powerful correlation between the discrete probability of distances of neighboring cells and thermal wave propagation rate, for a system of cells spread on a one-dimensional chain. A gamma distribution is employed to model the distances of neighboring cells. In the absence of an analytical solution and the differences in ignition times of adjacent reaction cells following non-Markovian statistics, invariably the solution for thermal wave propagation rate for a one-dimensional system with randomly distributed cells is obtained by numerical simulations. However, such simulations which are based on Monte-Carlo methods require several iterations of calculations for different realizations of distribution of adjacent cells. For several one-dimensional systems, differing in the value of shaping parameter of the gamma distribution, we show that the average reaction front propagation rates obtained by a discrete probability between two limits, shows excellent agreement with those obtained numerically. With the upper limit at 1.3, the lower limit depends on the non-dimensional ignition temperature. Additionally, this approach also facilitates the prediction of burning limits of heterogeneous thermal mixtures. The proposed method completely eliminates the need for laborious, time intensive numerical calculations where the thermal wave propagation rates can now be calculated based only on macroscopic entity of discrete probability.

Reacting gas mixtures in the state-to-state approach: The chemical reaction rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kustova, Elena V.; Kremer, Gilberto M.

2014-12-09

In this work chemically reacting mixtures of viscous flows are analyzed within the framework of Boltzmann equation. By applying a modified Chapman-Enskog method to the system of Boltzmann equations general expressions for the rates of chemical reactions and vibrational energy transitions are determined as functions of two thermodynamic forces: the velocity divergence and the affinity. As an application chemically reacting mixtures of N{sub 2} across a shock wave are studied, where the first lowest vibrational states are taken into account. Here we consider only the contributions from the first four single quantum vibrational-translational energy transitions. It is shown that themore » contribution to the chemical reaction rate related to the affinity is much larger than that of the velocity divergence.« less

Absolute rate constants of alkoxyl radical reactions in aqueous solution. [Tert-butyl hydroperoxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erben-Russ, M.; Michel, C.; Bors, W.

1987-04-23

The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA)more » was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.« less

Uncertainty of exploitation estimates made from tag returns

USGS Publications Warehouse

Miranda, L.E.; Brock, R.E.; Dorr, B.S.

2002-01-01

Over 6,000 crappies Pomoxis spp. were tagged in five water bodies to estimate exploitation rates by anglers. Exploitation rates were computed as the percentage of tags returned after adjustment for three sources of uncertainty: postrelease mortality due to the tagging process, tag loss, and the reporting rate of tagged fish. Confidence intervals around exploitation rates were estimated by resampling from the probability distributions of tagging mortality, tag loss, and reporting rate. Estimates of exploitation rates ranged from 17% to 54% among the five study systems. Uncertainty around estimates of tagging mortality, tag loss, and reporting resulted in 90% confidence intervals around the median exploitation rate as narrow as 15 percentage points and as broad as 46 percentage points. The greatest source of estimation error was uncertainty about tag reporting. Because the large investments required by tagging and reward operations produce imprecise estimates of the exploitation rate, it may be worth considering other approaches to estimating it or simply circumventing the exploitation question altogether.

Effect of Substrate Character on Heterogeneous Ozone Reaction Rate with Individual PAHs and Their Reaction Mixtures

NASA Astrophysics Data System (ADS)

Holmen, B. A.; Stevens, T.

2009-12-01

Vehicle exhaust contains many unregulated chemical compounds that are harmful to human health and the natural environment, including polycyclic aromatic hydrocarbons (PAH), a class of organic compounds derived from fuel combustion that can be carcinogenic and mutagenic. PAHs have been quantified in vehicle-derived ultrafine particles (Dp<100nm), which are more toxic than larger particles and are linked to adverse health problems, including respiratory and cardiac disease. Once emitted into the atmosphere, particle-bound PAHs can undergo “aging” reactions with oxidants, such as ozone, to form more polar species. These polar reaction products include species such as quinones that can be more toxic than the parent PAH compounds. Here, 0.4ppm ozone was reacted over a 24-hour period with the 16 EPA priority PAHs plus coronene adsorbed to (i) a quartz fiber filter and (ii) NIST diesel PM. The difference in the PAH/O3 heterogeneous reaction rate resulting from the two substrates will be discussed. The experiments were completed by spiking a known PAH mixture to the solid, reacting the samples with gas-phase ozone, and determining both PAH loss over time and products formed, using thermal-desorption gas chromatography / mass spectrometry (TD-GC/MS). The individual PAHs anthracene, phenanthrene, and fluorene, adsorbed to a QFF were also separately reacted with 0.4 ppm ozone. A volatilization control and the collection of volatilized PAHs using a Tenax-packed thermal desorption vial completed the mass balance and aided determination parent-product relationships. Heterogeneous reaction products analyzed directly without derivatization indicate the formation of 9,10-anthracenedione, 9H-fluoren-9-one, and (1,1’-biphenyl)-2,2’-dicarboxaldehyde from the reaction of ozone with the PAH mix on a QFF, but only 9,10-anthracenedione was detected for the diesel PM reaction. The implications of these results for aging of diesel particulate in urban environments will be discussed.

Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

NASA Astrophysics Data System (ADS)

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

2017-12-01

In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than

Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.

PubMed

Beniwal, Vijay; Manna, Arpan; Kumar, Anil

2016-07-04

The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-steady state mass action dynamics without rate constants: dynamics of coupled reactions using chemical potentials

NASA Astrophysics Data System (ADS)

Cannon, William R.; Baker, Scott E.

2017-10-01

Comprehensive and predictive simulation of coupled reaction networks has long been a goal of biology and other fields. Currently, metabolic network models that utilize enzyme mass action kinetics have predictive power but are limited in scope and application by the fact that the determination of enzyme rate constants is laborious and low throughput. We present a statistical thermodynamic formulation of the law of mass action for coupled reactions at both steady states and non-stationary states. The formulation uses chemical potentials instead of rate constants. When used to model deterministic systems, the method corresponds to a rescaling of the time dependent reactions in such a way that steady states can be reached on the same time scale but with significantly fewer computational steps. The relationships between reaction affinities, free energy changes and generalized detailed balance are central to the discussion. The significance for applications in systems biology are discussed as is the concept and assumption of maximum entropy production rate as a biological principle that links thermodynamics to natural selection.

Rate constant for the reaction of atomic chlorine with methane

NASA Technical Reports Server (NTRS)

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

1978-01-01

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

Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.

PubMed

Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua

2016-03-03

The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error.

Effect of chemical kinetics uncertainties on calculated constituents in a tropospheric photochemical model

NASA Technical Reports Server (NTRS)

Thompson, Anne M.; Stewart, Richard W.

1991-01-01

Random photochemical reaction rates are employed in a 1D photochemical model to examine uncertainties in tropospheric concentrations and thereby determine critical kinetic processes and significant correlations. Monte Carlo computations are used to simulate different chemical environments and their related imprecisions. The most critical processes are the primary photodissociation of O3 (which initiates ozone destruction) and NO2 (which initiates ozone formation), and the OH/methane reaction is significant. Several correlations and anticorrelations between species are discussed, and the ozone/transient OH correlation is examined in detail. One important result of the modeling is that estimates of global OH are generally about 25 percent uncertain, limiting the precision of photochemical models. Techniques for reducing the imprecision are discussed which emphasize the use of species and radical species measurements.

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

Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Walch, Stephen P.

2002-01-01

As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

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.

Photonuclear reactions in astrophysical p-process: Theoretical calculations and experiment simulation based on ELI-NP

NASA Astrophysics Data System (ADS)

Xu, Yi; Luo, Wen; Balabanski, Dimiter; Goriely, Stephane; Matei, Catalin; Tesileanu, Ovidiu

2017-09-01

The astrophysical p-process is an important way of nucleosynthesis to produce the stable and proton-rich nuclei beyond Fe which can not be reached by the s- and r-processes. In the present study, the astrophysical reaction rates of (γ,n), (γ,p), and (γ,α) reactions are computed within the modern reaction code TALYS for about 3000 stable and proton-rich nuclei with 12 < Z < 110. The nuclear structure ingredients involved in the calculation are determined from experimental data whenever available and, if not, from global microscopic nuclear models. In particular, both of the Wood-Saxon potential and the double folding potential with density dependent M3Y (DDM3Y) effective interaction are used for the calculations. It is found that the photonuclear reaction rates are very sensitive to the nuclear potential, and the better determination of nuclear potential would be important to reduce the uncertainties of reaction rates. Meanwhile, the Extreme Light Infrastructure-Nuclear Physics (ELI-NP) facility is being developed, which will provide the great opportunity to experimentally study the photonuclear reactions in p-process. Simulations of the experimental setup for the measurements of the photonuclear reactions 96Ru(γ,p) and 96Ru(γ,α) are performed. It is shown that the experiments of photonuclear reactions in p-process based on ELI-NP are quite promising.

Kinetic Modeling of the Reaction Rate for Quartz and Carbon Pellet

NASA Astrophysics Data System (ADS)

Li, Fei; Tangstad, Merete

2018-04-01

Kinetic modeling of quartz and carbon pellet at temperatures of 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) was investigated in this study. The carbon materials used were charcoal, coke, coal, and preheated coal. The overall SiC producing reaction can be described by the reaction SiO2 + 3C = SiC + 2CO. In the SiC-producing step, the reaction rate of quartz and carbon pellet can be expressed as {d{ pct}}/dt = ( {1 - 0.40 × X_{fix - C}^{ - 0.86} × FC × {pct}} ) × A × \\exp ( { - E/{{RT}}} ) The carbon factor F C was used to describe the influence of different carbon materials that effect the gas-solid interface reaction. For charcoal, coke, coal, and preheated coal, the F C values were 0.83, 0.80, 0.94, and 0.83, respectively. The pre-exponential factor A values for the preceding four carbon materials were 1.06 × 1016 min-1, 4.21 × 1015 min-1, 3.85 × 109 min-1, and 1.00 × 1025 min-1, respectively. The activation energies E for the SiC-producing step were 570, 563, 336, and 913 kJ/mole for charcoal, coke, coal, and preheated coal pellets, respectively.

Kinetic Modeling of the Reaction Rate for Quartz and Carbon Black Pellet

NASA Astrophysics Data System (ADS)

Li, Fei; Tangstad, Merete

2018-06-01

The kinetic modeling for the carbothermal reduction reaction rate in quartz and carbon black pellets is studied at different temperatures, under varying CO partial pressures in ambient atmosphere, varying carbon contents, different quartz particle sizes, and different crucible opening areas. Carbon black is produced by the cracking of natural gas. The activation energy of the SiC-producing step was determined to be 594 kJ/mol. The averaged pre-exponential factor A obtained from 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) is 2.62E+16 min-1. The reaction rate of the gas-solid interface factor, fix-C content ( X fix-C), temperature ( T), and CO partial pressure ( X CO) can be expressed as follows: {{d/pct}}{{{d}t}} = (1 - 0.40 × X_{{{fix} - C}}^{ - 0.86} × {pct}) × 2.62 × 10^{16} × \\exp ( { - 594000/RT} ) × (2.6 - 0.015 × X_{co} ).

Cluster states and container picture in light nuclei, and triple-alpha reaction rate

NASA Astrophysics Data System (ADS)

Funaki, Yasuro

2015-04-01

The excited states in 12C are investigated by using an extended version of the so- called Tohsaki-Horiuchi-Schuck-Röpke (THSR) wave function, where both the 3α condensate and 8Be + α cluster asymptotic configurations are included. We focus on the structures of the “Hoyle band” states, 2+2, and 4+2 states, which are recently observed above the Hoyle state, and of the 0+3 and 0+4 states, which are also quite recently identified in experiment. We show that the Hoyle band is not simply considered to be the 8Be(0+) + α rotation as suggested by previous cluster model calculations, nor to be a rotation of a rigid-body triangle-shaped object composed of the 3α particles. We also discuss the rate of the triple-alpha radiative capture reaction, applyng the imaginary-time method. Results of the triple-alpha reaction rate are consistent with NACRE rate for both high (≈ 109K) and low (≈ 107 K) temperatures. We show that the rate of the imaginary-time calculation in coupled-channels approach has a large enhancement for low temperatures if we truncate the number of channels.

E2C mechanism of elimination reactions. IX. Secondary deuterium isotope effects on rates of bimolecular reactions in alicyclic systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, D.

1976-06-11

Secondary ..cap alpha..-deuterium isotope effects on the rates of NBu/sub 4/OAc and NBu/sub 4/Cl promoted bimolecular reactions (E2 and SN2) of cyclohexyl tosylate and cyclohexyl bromide have been studied. The E2 reactions, previously categorized as E2C-like, show ..cap alpha..-deuterium isotope effects in the range 1.14--1.22, while the related SN2 reactions give values in the range 1.05--1.08. The discrepancy in the magnitude of the ..cap alpha..-deuterium isotope effect for the E2 and SN2 processes is consistent with the view that E2C-like reactions use ''looser'' transition states than those used in the concurrent SN2 reactions. While the reported ..cap alpha..-d isotope effectsmore » do not provide positive evidence to support the idea that the base interacts with C/sub ..cap alpha../ in the E2 transition states of the reactions studied, neither do they substantiate claims for dismissal of the concept. A comparison of the secondary ..gamma..-deuterium and ..beta..'-deuterium isotope effects arising in the reaction of cyclohexyl tosylate with NBu/sub 4/OAc in acetone indicates the two isotope effects to be of equivalent magnitude (k/sub ..beta..'-d/k/sub ..gamma..-d/ = 0.98). This observation can only be rationalized for this reaction in terms of a transition state structure in which there is extensive double bond development. It provides compelling evidence against the involvement of any transition state structure which accommodates extensive positive charge development at C/sub ..cap alpha../.« less

Negativization rates of IgE radioimmunoassay and basophil activation test in immediate reactions to penicillins.

PubMed

Fernández, T D; Torres, M J; Blanca-López, N; Rodríguez-Bada, J L; Gomez, E; Canto, G; Mayorga, C; Blanca, M

2009-02-01

Skin test sensitivity in patients with immediate allergy to penicillins tends to decrease over time, but no information is available concerning in vitro tests. We analysed the negativization rates of two in vitro methods that determine specific immunoglobulin E (IgE) antibodies, the basophil activation test using flow cytometry (BAT) and the radioallergosorbent test (RAST), in immediate allergic reactions to penicillins. Forty-one patients with immediate allergic reactions to amoxicillin were followed up over a 4-year period. BAT and RAST were performed at 6-month intervals. Patients were randomized into groups: Group I, skin tests carried out at regular intervals; Group II, skin tests made only at the beginning of the study. Differences were observed between RAST and BAT (P < 0.01), the latter showing earlier negativization. Considering different haptens, significant differences for the rate of negativization were only found for amoxicillin (P < 0.05). Comparisons between Groups I (n = 10) and II (n = 31) showed a tendency to become negative later in Group I with RAST. Levels of specific IgE antibodies tended to decrease over time in patients with immediate allergic reactions to amoxicillin. Conversion to negative took longer for the RAST assay, although the differences were only detected with the amoxicillin hapten. Skin testing influenced the rate of negativization of the RAST assay, contributing to maintenance of in vitro sensitivity. Because of the loss of sensitivity over time, the determination of specific IgE antibodies to penicillins in patients with immediate allergic reactions must be done as soon as possible after the reaction.

Anisotropic transverse mixing and its effect on reaction rates in multi-scale, 3D heterogeneous porous media

NASA Astrophysics Data System (ADS)

Engdahl, N. B.

2016-12-01

Mixing rates in porous media have been a heavily research topic in recent years covering analytic, random, and structured fields. However, there are some persistent assumptions and common features to these models that raise some questions about the generality of the results. One of these commonalities is the orientation of the flow field with respect to the heterogeneity structure, which are almost always defined to be parallel each other if there is an elongated axis of permeability correlation. Given the vastly different tortuosities for flow parallel to bedding and flow transverse to bedding, this assumption of parallel orientation may have significant effects on reaction rates when natural flows deviate from this assumed setting. This study investigates the role of orientation on mixing and reaction rates in multi-scale, 3D heterogeneous porous media with varying degrees of anisotropy in the correlation structure. Ten realizations of a small flow field, with three anisotropy levels, were simulated for flow parallel and transverse to bedding. Transport was simulated in each model with an advective-diffusive random walk and reactions were simulated using the chemical Langevin equation. The reaction system is a vertically segregated, transverse mixing problem between two mobile reactants. The results show that different transport behaviors and reaction rates are obtained by simply rotating the direction of flow relative to bedding, even when the net flux in both directions is the same. This kind of behavior was observed for three different weightings of the initial condition: 1) uniform, 2) flux-based, and 3) travel time based. The different schemes resulted in 20-50% more mass formation in the transverse direction than the longitudinal. The greatest variability in mass was observed for the flux weights and these were proportionate to the level of anisotropy. The implications of this study are that flux or travel time weights do not provide any guarantee of a fair

Efficient kinetic Monte Carlo method for reaction-diffusion problems with spatially varying annihilation rates

NASA Astrophysics Data System (ADS)

Schwarz, Karsten; Rieger, Heiko

2013-03-01

We present an efficient Monte Carlo method to simulate reaction-diffusion processes with spatially varying particle annihilation or transformation rates as it occurs for instance in the context of motor-driven intracellular transport. Like Green's function reaction dynamics and first-passage time methods, our algorithm avoids small diffusive hops by propagating sufficiently distant particles in large hops to the boundaries of protective domains. Since for spatially varying annihilation or transformation rates the single particle diffusion propagator is not known analytically, we present an algorithm that generates efficiently either particle displacements or annihilations with the correct statistics, as we prove rigorously. The numerical efficiency of the algorithm is demonstrated with an illustrative example.

How to Make Data a Blessing to Parametric Uncertainty Quantification and Reduction?

NASA Astrophysics Data System (ADS)

Ye, M.; Shi, X.; Curtis, G. P.; Kohler, M.; Wu, J.

2013-12-01

In a Bayesian point of view, probability of model parameters and predictions are conditioned on data used for parameter inference and prediction analysis. It is critical to use appropriate data for quantifying parametric uncertainty and its propagation to model predictions. However, data are always limited and imperfect. When a dataset cannot properly constrain model parameters, it may lead to inaccurate uncertainty quantification. While in this case data appears to be a curse to uncertainty quantification, a comprehensive modeling analysis may help understand the cause and characteristics of parametric uncertainty and thus turns data into a blessing. In this study, we illustrate impacts of data on uncertainty quantification and reduction using an example of surface complexation model (SCM) developed to simulate uranyl (U(VI)) adsorption. The model includes two adsorption sites, referred to as strong and weak sites. The amount of uranium adsorption on these sites determines both the mean arrival time and the long tail of the breakthrough curves. There is one reaction on the weak site but two reactions on the strong site. The unknown parameters include fractions of the total surface site density of the two sites and surface complex formation constants of the three reactions. A total of seven experiments were conducted with different geochemical conditions to estimate these parameters. The experiments with low initial concentration of U(VI) result in a large amount of parametric uncertainty. A modeling analysis shows that it is because the experiments cannot distinguish the relative adsorption affinity of the strong and weak sites on uranium adsorption. Therefore, the experiments with high initial concentration of U(VI) are needed, because in the experiments the strong site is nearly saturated and the weak site can be determined. The experiments with high initial concentration of U(VI) are a blessing to uncertainty quantification, and the experiments with low initial

The uncertainty of biodegradation rate constants of emerging organic compounds in soil and groundwater - A compilation of literature values for 82 substances.

PubMed

Greskowiak, Janek; Hamann, Enrico; Burke, Victoria; Massmann, Gudrun

2017-12-01

The present study reports on biodegradation rate constants of emerging organic compounds (EOCs) in soil and groundwater available in the literature. The major aim of this compilation was to provide an assessment of the uncertainty of hydrological models with respect to the fate of EOCs. The literature search identified a total number of 82 EOCs for which 1st-order rate constants could be derived. It was found that for the majority of compounds degradation rate constants vary over more than three orders of magnitude. Correlation to factors that are well known to affect the degradation rate, such as temperature or redox condition was weak. No correlation at all was found with results from available quantitative structure-activity relationship models. This suggests that many unknown site specific or experimentally specific factors influence the degradation behavior of EOCs in the environment. Thus, local and catchment scale predictive models to estimate EOC concentration at receptors, e.g., receiving waters or drinking water wells, need to consider the large uncertainty in 1st-order rate constants. As a consequence, applying rate constants that were derived from one experiment or field site investigation to other experiments or field sites should be done with extreme caution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of the uncertainties of several European low-dose calibration facilities

NASA Astrophysics Data System (ADS)

Dombrowski, H.; Cornejo Díaz, N. A.; Toni, M. P.; Mihelic, M.; Röttger, A.

2018-04-01

The typical uncertainty of a low-dose rate calibration of a detector, which is calibrated in a dedicated secondary national calibration laboratory, is investigated, including measurements in the photon field of metrology institutes. Calibrations at low ambient dose equivalent rates (at the level of the natural ambient radiation) are needed when environmental radiation monitors are to be characterised. The uncertainties of calibration measurements in conventional irradiation facilities above ground are compared with those obtained in a low-dose rate irradiation facility located deep underground. Four laboratories quantitatively evaluated the uncertainties of their calibration facilities, in particular for calibrations at low dose rates (250 nSv/h and 1 μSv/h). For the first time, typical uncertainties of European calibration facilities are documented in a comparison and the main sources of uncertainty are revealed. All sources of uncertainties are analysed, including the irradiation geometry, scattering, deviations of real spectra from standardised spectra, etc. As a fundamental metrological consequence, no instrument calibrated in such a facility can have a lower total uncertainty in subsequent measurements. For the first time, the need to perform calibrations at very low dose rates (< 100 nSv/h) deep underground is underpinned on the basis of quantitative data.

Uncertainty in hydrological signatures for gauged and ungauged catchments

NASA Astrophysics Data System (ADS)

Westerberg, Ida K.; Wagener, Thorsten; Coxon, Gemma; McMillan, Hilary K.; Castellarin, Attilio; Montanari, Alberto; Freer, Jim

2016-03-01

Reliable information about hydrological behavior is needed for water-resource management and scientific investigations. Hydrological signatures quantify catchment behavior as index values, and can be predicted for ungauged catchments using a regionalization procedure. The prediction reliability is affected by data uncertainties for the gauged catchments used in prediction and by uncertainties in the regionalization procedure. We quantified signature uncertainty stemming from discharge data uncertainty for 43 UK catchments and propagated these uncertainties in signature regionalization, while accounting for regionalization uncertainty with a weighted-pooling-group approach. Discharge uncertainty was estimated using Monte Carlo sampling of multiple feasible rating curves. For each sampled rating curve, a discharge time series was calculated and used in deriving the gauged signature uncertainty distribution. We found that the gauged uncertainty varied with signature type, local measurement conditions and catchment behavior, with the highest uncertainties (median relative uncertainty ±30-40% across all catchments) for signatures measuring high- and low-flow magnitude and dynamics. Our regionalization method allowed assessing the role and relative magnitudes of the gauged and regionalized uncertainty sources in shaping the signature uncertainty distributions predicted for catchments treated as ungauged. We found that (1) if the gauged uncertainties were neglected there was a clear risk of overconditioning the regionalization inference, e.g., by attributing catchment differences resulting from gauged uncertainty to differences in catchment behavior, and (2) uncertainty in the regionalization results was lower for signatures measuring flow distribution (e.g., mean flow) than flow dynamics (e.g., autocorrelation), and for average flows (and then high flows) compared to low flows.

A Framework for Quantifying Measurement Uncertainties and Uncertainty Propagation in HCCI/LTGC Engine Experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petitpas, Guillaume; McNenly, Matthew J.; Whitesides, Russell A.

In this study, a framework for estimating experimental measurement uncertainties for a Homogenous Charge Compression Ignition (HCCI)/Low-Temperature Gasoline Combustion (LTGC) engine testing facility is presented. Detailed uncertainty quantification is first carried out for the measurement of the in-cylinder pressure, whose variations during the cycle provide most of the information for performance evaluation. Standard uncertainties of other measured quantities, such as the engine geometry and speed, the air and fuel flow rate and the intake/exhaust dry molar fractions are also estimated. Propagating those uncertainties using a Monte Carlo simulation and Bayesian inference methods then allows for estimation of uncertainties of themore » mass-average temperature and composition at IVC and throughout the cycle; and also of the engine performances such as gross Integrated Mean Effective Pressure, Heat Release and Ringing Intensity. Throughout the analysis, nominal values for uncertainty inputs were taken from a well-characterized engine test facility. However, the analysis did not take into account the calibration practice of experiments run in that facility and the resulting uncertainty values are therefore not indicative of the expected accuracy of those experimental results. A future study will employ the methodology developed here to explore the effects of different calibration methods on the different uncertainty values in order to evaluate best practices for accurate engine measurements.« less

A Framework for Quantifying Measurement Uncertainties and Uncertainty Propagation in HCCI/LTGC Engine Experiments

DOE PAGES

Petitpas, Guillaume; McNenly, Matthew J.; Whitesides, Russell A.

2017-03-28

In this study, a framework for estimating experimental measurement uncertainties for a Homogenous Charge Compression Ignition (HCCI)/Low-Temperature Gasoline Combustion (LTGC) engine testing facility is presented. Detailed uncertainty quantification is first carried out for the measurement of the in-cylinder pressure, whose variations during the cycle provide most of the information for performance evaluation. Standard uncertainties of other measured quantities, such as the engine geometry and speed, the air and fuel flow rate and the intake/exhaust dry molar fractions are also estimated. Propagating those uncertainties using a Monte Carlo simulation and Bayesian inference methods then allows for estimation of uncertainties of themore » mass-average temperature and composition at IVC and throughout the cycle; and also of the engine performances such as gross Integrated Mean Effective Pressure, Heat Release and Ringing Intensity. Throughout the analysis, nominal values for uncertainty inputs were taken from a well-characterized engine test facility. However, the analysis did not take into account the calibration practice of experiments run in that facility and the resulting uncertainty values are therefore not indicative of the expected accuracy of those experimental results. A future study will employ the methodology developed here to explore the effects of different calibration methods on the different uncertainty values in order to evaluate best practices for accurate engine measurements.« less

Responses to clinical uncertainty in Australian general practice trainees: a cross-sectional analysis.

PubMed

Cooke, Georga; Tapley, Amanda; Holliday, Elizabeth; Morgan, Simon; Henderson, Kim; Ball, Jean; van Driel, Mieke; Spike, Neil; Kerr, Rohan; Magin, Parker

2017-12-01

Tolerance for ambiguity is essential for optimal learning and professional competence. General practice trainees must be, or must learn to be, adept at managing clinical uncertainty. However, few studies have examined associations of intolerance of uncertainty in this group. The aim of this study was to establish levels of tolerance of uncertainty in Australian general practice trainees and associations of uncertainty with demographic, educational and training practice factors. A cross-sectional analysis was performed on the Registrar Clinical Encounters in Training (ReCEnT) project, an ongoing multi-site cohort study. Scores on three of the four independent subscales of the Physicians' Reaction to Uncertainty (PRU) instrument were analysed as outcome variables in linear regression models with trainee and practice factors as independent variables. A total of 594 trainees contributed data on a total of 1209 occasions. Trainees in earlier training terms had higher scores for 'Anxiety due to uncertainty', 'Concern about bad outcomes' and 'Reluctance to disclose diagnosis/treatment uncertainty to patients'. Beyond this, findings suggest two distinct sets of associations regarding reaction to uncertainty. Firstly, affective aspects of uncertainty (the 'Anxiety' and 'Concern' subscales) were associated with female gender, less experience in hospital prior to commencing general practice training, and graduation overseas. Secondly, a maladaptive response to uncertainty (the 'Reluctance to disclose' subscale) was associated with urban practice, health qualifications prior to studying medicine, practice in an area of higher socio-economic status, and being Australian-trained. This study has established levels of three measures of trainees' responses to uncertainty and associations with these responses. The current findings suggest differing 'phenotypes' of trainees with high 'affective' responses to uncertainty and those reluctant to disclose uncertainty to patients. More

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

NASA Technical Reports Server (NTRS)

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

1998-01-01

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

Uncertainties in modeling low-energy neutrino-induced reactions on iron-group nuclei

NASA Astrophysics Data System (ADS)

Paar, N.; Suzuki, T.; Honma, M.; Marketin, T.; Vretenar, D.

2011-10-01

Charged-current neutrino-nucleus cross sections for 54,56Fe and 58,60Ni are calculated and compared using frameworks based on relativistic and Skyrme energy-density functionals and on the shell model. The current theoretical uncertainties in modeling neutrino-nucleus cross sections are assessed in relation to the predicted Gamow-Teller transition strength and available data, to multipole decomposition of the cross sections, and to cross sections averaged over the Michel flux and Fermi-Dirac distribution. By employing different microscopic approaches and models, the decay-at-rest (DAR) neutrino-56Fe cross section and its theoretical uncertainty are estimated to be <σ>th=(258±57)×10-42cm2, in very good agreement with the experimental value <σ>exp=(256±108±43)×10-42cm2.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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{supmore » 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

Theoretical derivation for reaction rate constants of H abstraction from thiophenol by the H/O radical pool

PubMed Central

Batiha, Marwan; Altarawneh, Mohammednoor; Al-Harahsheh, Mohammad; Altarawneh, Ibrahem; Rawadieh, Saleh

2011-01-01

Reaction and activation energy barriers are calculated for the H abstraction reactions (C6H5SH + X• → C6H5S + XH, X = H, OH and HO2) at the BB1K/GTLarge level of theory. The corresponding reactions with H2S and CH3SH are also investigated using the G3B3 and CBS-QB3 methods in order to demonstrate the accuracy of BB1K functional in finding activation barriers for hydrogen atom transfer reactions. Arrhenius parameters for the title reactions are fitted in the temperature range of 300 K–2000 K. The calculated reaction enthalpies are in good agreement with their corresponding experimental reaction enthalpies. It is found that H abstraction by OH radicals from the thiophenol molecule proceed in a much slower rate in reference to the analogous phenol molecule. ΔfH298o of thiophenoxy radical is calculated to be 63.3 kcal/mol. Kinetic parameters presented herein should be useful in describing the decomposition rate of thiophenol; i.e., one of the major aromatic sulfur carriers, at high temperatures. PMID:22485200

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

NASA Technical Reports Server (NTRS)

Chinitz, W.; Foy, E.; Rowan, G.; Goldstein, D.

1982-01-01

The use of probability theory to determine the effects of turbulent fluctuations on reaction rates in turbulent combustion systems is briefly reviewed. Results are presented for the effect of species fluctuations in particular. It is found that turbulent fluctuations of species act to reduce the reaction rates, in contrast with the temperature fluctuations previously determined to increase Arrhenius reaction rate constants. For the temperature fluctuations, a criterion is set forth for determining if, in a given region of a turbulent flow field, the temperature can be expected to exhibit ramp like fluctuations. Using the above results, along with results previously obtained, a model is described for testing the effects of turbulent fluctuations of temperature and species on reaction rates in computer programs dealing with turbulent reacting flows. An alternative model which employs three variable probability density functions (temperature and two species) and is currently being formulated is discussed as well.

Rate constant for reaction of vitamin C with protein radicals in γ-irradiated aqueous albumin solution at 295 K

NASA Astrophysics Data System (ADS)

Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami

1995-02-01

When an aqueous solution of albumin (0.1 kg dm -3) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 s -1, which is much smaller than the reported rate constants (10 6-10 10 dm 3 mol -1 s -1) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils.

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

Rate Constants and Activation Energies for Gas-Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical.

PubMed

Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew

2015-07-01

Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.

Assessment of Uncertainty in Cloud Radiative Effects and Heating Rates through Retrieval Algorithm Differences: Analysis using 3-years of ARM data at Darwin, Australia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Comstock, Jennifer M.; Protat, Alain; McFarlane, Sally A.

2013-05-22

Ground-based radar and lidar observations obtained at the Department of Energy’s Atmospheric Radiation Measurement Program’s Tropical Western Pacific site located in Darwin, Australia are used to retrieve ice cloud properties in anvil and cirrus clouds. Cloud microphysical properties derived from four different retrieval algorithms (two radar-lidar and two radar only algorithms) are compared by examining mean profiles and probability density functions of effective radius (Re), ice water content (IWC), extinction, ice number concentration, ice crystal fall speed, and vertical air velocity. Retrieval algorithm uncertainty is quantified using radiative flux closure exercises. The effect of uncertainty in retrieved quantities on themore » cloud radiative effect and radiative heating rates are presented. Our analysis shows that IWC compares well among algorithms, but Re shows significant discrepancies, which is attributed primarily to assumptions of particle shape. Uncertainty in Re and IWC translates into sometimes-large differences in cloud radiative effect (CRE) though the majority of cases have a CRE difference of roughly 10 W m-2 on average. These differences, which we believe are primarily driven by the uncertainty in Re, can cause up to 2 K/day difference in the radiative heating rates between algorithms.« less

Quantifying the Uncertainty in Discharge Data Using Hydraulic Knowledge and Uncertain Gaugings

NASA Astrophysics Data System (ADS)

Renard, B.; Le Coz, J.; Bonnifait, L.; Branger, F.; Le Boursicaud, R.; Horner, I.; Mansanarez, V.; Lang, M.

2014-12-01

River discharge is a crucial variable for Hydrology: as the output variable of most hydrologic models, it is used for sensitivity analyses, model structure identification, parameter estimation, data assimilation, prediction, etc. A major difficulty stems from the fact that river discharge is not measured continuously. Instead, discharge time series used by hydrologists are usually based on simple stage-discharge relations (rating curves) calibrated using a set of direct stage-discharge measurements (gaugings). In this presentation, we present a Bayesian approach to build such hydrometric rating curves, to estimate the associated uncertainty and to propagate this uncertainty to discharge time series. The three main steps of this approach are described: (1) Hydraulic analysis: identification of the hydraulic controls that govern the stage-discharge relation, identification of the rating curve equation and specification of prior distributions for the rating curve parameters; (2) Rating curve estimation: Bayesian inference of the rating curve parameters, accounting for the individual uncertainties of available gaugings, which often differ according to the discharge measurement procedure and the flow conditions; (3) Uncertainty propagation: quantification of the uncertainty in discharge time series, accounting for both the rating curve uncertainties and the uncertainty of recorded stage values. In addition, we also discuss current research activities, including the treatment of non-univocal stage-discharge relationships (e.g. due to hydraulic hysteresis, vegetation growth, sudden change of the geometry of the section, etc.).

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.

The Role of Type and Source of Uncertainty on the Processing of Climate Models Projections.

PubMed

Benjamin, Daniel M; Budescu, David V

2018-01-01

Scientists agree that the climate is changing due to human activities, but there is less agreement about the specific consequences and their timeline. Disagreement among climate projections is attributable to the complexity of climate models that differ in their structure, parameters, initial conditions, etc. We examine how different sources of uncertainty affect people's interpretation of, and reaction to, information about climate change by presenting participants forecasts from multiple experts. Participants viewed three types of sets of sea-level rise projections: (1) precise, but conflicting ; (2) imprecise , but agreeing, and (3) hybrid that were both conflicting and imprecise. They estimated the most likely sea-level rise, provided a range of possible values and rated the sets on several features - ambiguity, credibility, completeness, etc. In Study 1, everyone saw the same hybrid set. We found that participants were sensitive to uncertainty between sources, but not to uncertainty about which model was used. The impacts of conflict and imprecision were combined for estimation tasks and compromised for feature ratings . Estimates were closer to the experts' original projections, and sets were rated more favorably under imprecision. Estimates were least consistent with (narrower than) the experts in the hybrid condition, but participants rated the conflicting set least favorably. In Study 2, we investigated the hybrid case in more detail by creating several distinct interval sets that combine conflict and imprecision. Two factors drive perceptual differences: overlap - the structure of the forecast set (whether intersecting, nested, tangent, or disjoint) - and a symmetry - the balance of the set. Estimates were primarily driven by asymmetry, and preferences were primarily driven by overlap. Asymmetric sets were least consistent with the experts: estimated ranges were narrower, and estimates of the most likely value were shifted further below the set mean

The Role of Type and Source of Uncertainty on the Processing of Climate Models Projections

PubMed Central

Benjamin, Daniel M.; Budescu, David V.

2018-01-01

Scientists agree that the climate is changing due to human activities, but there is less agreement about the specific consequences and their timeline. Disagreement among climate projections is attributable to the complexity of climate models that differ in their structure, parameters, initial conditions, etc. We examine how different sources of uncertainty affect people’s interpretation of, and reaction to, information about climate change by presenting participants forecasts from multiple experts. Participants viewed three types of sets of sea-level rise projections: (1) precise, but conflicting; (2) imprecise, but agreeing, and (3) hybrid that were both conflicting and imprecise. They estimated the most likely sea-level rise, provided a range of possible values and rated the sets on several features – ambiguity, credibility, completeness, etc. In Study 1, everyone saw the same hybrid set. We found that participants were sensitive to uncertainty between sources, but not to uncertainty about which model was used. The impacts of conflict and imprecision were combined for estimation tasks and compromised for feature ratings. Estimates were closer to the experts’ original projections, and sets were rated more favorably under imprecision. Estimates were least consistent with (narrower than) the experts in the hybrid condition, but participants rated the conflicting set least favorably. In Study 2, we investigated the hybrid case in more detail by creating several distinct interval sets that combine conflict and imprecision. Two factors drive perceptual differences: overlap – the structure of the forecast set (whether intersecting, nested, tangent, or disjoint) – and asymmetry – the balance of the set. Estimates were primarily driven by asymmetry, and preferences were primarily driven by overlap. Asymmetric sets were least consistent with the experts: estimated ranges were narrower, and estimates of the most likely value were shifted further below the set

Stochastic theory of large-scale enzyme-reaction networks: Finite copy number corrections to rate equation models

NASA Astrophysics Data System (ADS)

Thomas, Philipp; Straube, Arthur V.; Grima, Ramon

2010-11-01

Chemical reactions inside cells occur in compartment volumes in the range of atto- to femtoliters. Physiological concentrations realized in such small volumes imply low copy numbers of interacting molecules with the consequence of considerable fluctuations in the concentrations. In contrast, rate equation models are based on the implicit assumption of infinitely large numbers of interacting molecules, or equivalently, that reactions occur in infinite volumes at constant macroscopic concentrations. In this article we compute the finite-volume corrections (or equivalently the finite copy number corrections) to the solutions of the rate equations for chemical reaction networks composed of arbitrarily large numbers of enzyme-catalyzed reactions which are confined inside a small subcellular compartment. This is achieved by applying a mesoscopic version of the quasisteady-state assumption to the exact Fokker-Planck equation associated with the Poisson representation of the chemical master equation. The procedure yields impressively simple and compact expressions for the finite-volume corrections. We prove that the predictions of the rate equations will always underestimate the actual steady-state substrate concentrations for an enzyme-reaction network confined in a small volume. In particular we show that the finite-volume corrections increase with decreasing subcellular volume, decreasing Michaelis-Menten constants, and increasing enzyme saturation. The magnitude of the corrections depends sensitively on the topology of the network. The predictions of the theory are shown to be in excellent agreement with stochastic simulations for two types of networks typically associated with protein methylation and metabolism.

The reaction H + C4H2 - Absolute rate constant measurement and implication for atmospheric modeling of Titan

NASA Technical Reports Server (NTRS)

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

1986-01-01

The absolute rate constant for the reaction H + C4H2 has been measured over the temperature (T) interval 210-423 K, using the technique of flash photolysis-resonance fluorescence. At each of the five temperatures employed, the results were independent of variations in C4H2 concentration, total pressure of Ar or N2, and flash intensity (i.e., the initial H concentration). The rate constant, k, was found to be equal to 1.39 x 10 to the -10th exp (-1184/T) cu cm/s, with an error of one standard deviation. The Arrhenius parameters at the high pressure limit determined here for the H + C4H2 reaction are consistent with those for the corresponding reactions of H with C2H2 and C3H4. Implications of the kinetic carbon chemistry results, particularly those at low temperature, are considered for models of the atmospheric carbon chemistry of Titan. The rate of this reaction, relative to that of the analogous, but slower, reaction of H + C2H2, appears to make H + C4H2 a very feasible reaction pathway for effective conversion of H atoms to molecular hydrogen in the stratosphere of Titan.

The effect of addition of primary positive salts, complex salt, on the ionic strength and rate constant at various temperatures by reaction kinetics

NASA Astrophysics Data System (ADS)

Kurade, S. S.; Ramteke, A. A.

2018-05-01

In this work, we have investigated the rate of reaction by using ionic strength at different temperatures. The main goal of this experiment is to determine the relation between ionic strength with reaction rate, reaction time and rate constant with temperature. It is observed that the addition of positive salt indicate the increasing ionic strength with increase in run time at various temperatures. Thus the temperature affects the speed of reaction and mechanism by which chemical reaction occurs and time variable plays vital role in the progress of reaction at different temperatures.

Actinometric measurement of solar ultraviolet and development of a weighted solar UV integral. [photochemical reaction rate determination

NASA Technical Reports Server (NTRS)

Gupta, A.; Coulbert, C.

1978-01-01

An actinometer has been developed to measure outdoor irradiance in the range 295-400 nm. Actinometric measurements of radiation are based on determination of photochemical reaction rates for reactions of known quantum efficiency. Actinometers have the advantage of providing irradiance data over surfaces of difficult accessibility; in addition, actinometrically determined irradiance data are wavelength weighted and therefore provide a useful means of assessing the degradation rates of polymers employed in solar energy systems.

First measurement of 30S+α resonant elastic scattering for the 30S(α ,p ) reaction rate

NASA Astrophysics Data System (ADS)

Kahl, D.; Yamaguchi, H.; Kubono, S.; Chen, A. A.; Parikh, A.; Binh, D. N.; Chen, J.; Cherubini, S.; Duy, N. N.; Hashimoto, T.; Hayakawa, S.; Iwasa, N.; Jung, H. S.; Kato, S.; Kwon, Y. K.; Nishimura, S.; Ota, S.; Setoodehnia, K.; Teranishi, T.; Tokieda, H.; Yamada, T.; Yun, C. C.; Zhang, L. Y.

2018-01-01

Background: Type I x-ray bursts are the most frequently observed thermonuclear explosions in the galaxy, resulting from thermonuclear runaway on the surface of an accreting neutron star. The 30S(α ,p ) reaction plays a critical role in burst models, yet insufficient experimental information is available to calculate a reliable, precise rate for this reaction. Purpose: Our measurement was conducted to search for states in 34Ar and determine their quantum properties. In particular, natural-parity states with large α -decay partial widths should dominate the stellar reaction rate. Method: We performed the first measurement of 30S+α resonant elastic scattering up to a center-of-mass energy of 5.5 MeV using a radioactive ion beam. The experiment utilized a thick gaseous active target system and silicon detector array in inverse kinematics. Results: We obtained an excitation function for 30S(α ,α ) near 150∘ in the center-of-mass frame. The experimental data were analyzed with R -matrix calculations, and we observed three new resonant patterns between 11.1 and 12.1 MeV, extracting their properties of resonance energy, widths, spin, and parity. Conclusions: We calculated the resonant thermonuclear reaction rate of 30S(α ,p ) based on all available experimental data of 34Ar and found an upper limit about one order of magnitude larger than a rate determined using a statistical model. The astrophysical impact of these two rates has been investigated through one-zone postprocessing type I x-ray burst calculations. We find that our new upper limit for the 30S(α ,p )33Cl rate significantly affects the predicted nuclear energy generation rate during the burst.

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. © 2014 Blackwell Verlag GmbH.

Breakdown of the reaction-diffusion master equation with nonelementary rates

NASA Astrophysics Data System (ADS)

Smith, Stephen; Grima, Ramon

2016-05-01

The chemical master equation (CME) is the exact mathematical formulation of chemical reactions occurring in a dilute and well-mixed volume. The reaction-diffusion master equation (RDME) is a stochastic description of reaction-diffusion processes on a spatial lattice, assuming well mixing only on the length scale of the lattice. It is clear that, for the sake of consistency, the solution of the RDME of a chemical system should converge to the solution of the CME of the same system in the limit of fast diffusion: Indeed, this has been tacitly assumed in most literature concerning the RDME. We show that, in the limit of fast diffusion, the RDME indeed converges to a master equation but not necessarily the CME. We introduce a class of propensity functions, such that if the RDME has propensities exclusively of this class, then the RDME converges to the CME of the same system, whereas if the RDME has propensities not in this class, then convergence is not guaranteed. These are revealed to be elementary and nonelementary propensities, respectively. We also show that independent of the type of propensity, the RDME converges to the CME in the simultaneous limit of fast diffusion and large volumes. We illustrate our results with some simple example systems and argue that the RDME cannot generally be an accurate description of systems with nonelementary rates.

Rate Constants and Activation Energies for Gas‐Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical

PubMed Central

Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

2015-01-01

ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500

Characterization of the energy-dependent uncertainty and correlation in silicon neutron displacement damage metrics

NASA Astrophysics Data System (ADS)

Griffin, Patrick; Rochman, Dimitri; Koning, Arjan

2017-09-01

A rigorous treatment of the uncertainty in the underlying nuclear data on silicon displacement damage metrics is presented. The uncertainty in the cross sections and recoil atom spectra are propagated into the energy-dependent uncertainty contribution in the silicon displacement kerma and damage energy using a Total Monte Carlo treatment. An energy-dependent covariance matrix is used to characterize the resulting uncertainty. A strong correlation between different reaction channels is observed in the high energy neutron contributions to the displacement damage metrics which supports the necessity of using a Monte Carlo based method to address the nonlinear nature of the uncertainty propagation.

A reaction-diffusion-based coding rate control mechanism for camera sensor networks.

PubMed

Yamamoto, Hiroshi; Hyodo, Katsuya; Wakamiya, Naoki; Murata, Masayuki

2010-01-01

A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal.

The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

NASA Technical Reports Server (NTRS)

Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

2004-01-01

The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

Helium Mass Spectrometer Leak Detection: A Method to Quantify Total Measurement Uncertainty

NASA Technical Reports Server (NTRS)

Mather, Janice L.; Taylor, Shawn C.

2015-01-01

In applications where leak rates of components or systems are evaluated against a leak rate requirement, the uncertainty of the measured leak rate must be included in the reported result. However, in the helium mass spectrometer leak detection method, the sensitivity, or resolution, of the instrument is often the only component of the total measurement uncertainty noted when reporting results. To address this shortfall, a measurement uncertainty analysis method was developed that includes the leak detector unit's resolution, repeatability, hysteresis, and drift, along with the uncertainty associated with the calibration standard. In a step-wise process, the method identifies the bias and precision components of the calibration standard, the measurement correction factor (K-factor), and the leak detector unit. Together these individual contributions to error are combined and the total measurement uncertainty is determined using the root-sum-square method. It was found that the precision component contributes more to the total uncertainty than the bias component, but the bias component is not insignificant. For helium mass spectrometer leak rate tests where unit sensitivity alone is not enough, a thorough evaluation of the measurement uncertainty such as the one presented herein should be performed and reported along with the leak rate value.

Survival behavior in the cyclic Lotka-Volterra model with a randomly switching reaction rate

NASA Astrophysics Data System (ADS)

West, Robert; Mobilia, Mauro; Rucklidge, Alastair M.

2018-02-01

We study the influence of a randomly switching reproduction-predation rate on the survival behavior of the nonspatial cyclic Lotka-Volterra model, also known as the zero-sum rock-paper-scissors game, used to metaphorically describe the cyclic competition between three species. In large and finite populations, demographic fluctuations (internal noise) drive two species to extinction in a finite time, while the species with the smallest reproduction-predation rate is the most likely to be the surviving one (law of the weakest). Here we model environmental (external) noise by assuming that the reproduction-predation rate of the strongest species (the fastest to reproduce and predate) in a given static environment randomly switches between two values corresponding to more and less favorable external conditions. We study the joint effect of environmental and demographic noise on the species survival probabilities and on the mean extinction time. In particular, we investigate whether the survival probabilities follow the law of the weakest and analyze their dependence on the external noise intensity and switching rate. Remarkably, when, on average, there is a finite number of switches prior to extinction, the survival probability of the predator of the species whose reaction rate switches typically varies nonmonotonically with the external noise intensity (with optimal survival about a critical noise strength). We also outline the relationship with the case where all reaction rates switch on markedly different time scales.

Rate constants for reactions of ClO/x/ of atmospheric interest

NASA Technical Reports Server (NTRS)

Watson, R. T.

1977-01-01

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

The loss rates of O+ in the inner magnetosphere caused by both magnetic field line curvature scattering and charge exchange reactions

NASA Astrophysics Data System (ADS)

Ji, Y.; Shen, C.

2014-03-01

With consideration of magnetic field line curvature (FLC) pitch angle scattering and charge exchange reactions, the O+ (>300 keV) in the inner magnetosphere loss rates are investigated by using an eigenfunction analysis. The FLC scattering provides a mechanism for the ring current O+ to enter the loss cone and influence the loss rates caused by charge exchange reactions. Assuming that the pitch angle change is small for each scattering event, the diffusion equation including a charge exchange term is constructed and solved; the eigenvalues of the equation are identified. The resultant loss rates of O+ are approximately equal to the linear superposition of the loss rate without considering the charge exchange reactions and the loss rate associated with charge exchange reactions alone. The loss time is consistent with the observations from the early recovery phases of magnetic storms.

Absolute rate constants for the reaction of OH with cyclopentane and cycloheptane from 233 to 351 K.

PubMed

Gennaco, Michael A; Huang, Yi-wen; Hannun, Reem A; Dransfield, Timothy J

2012-12-27

Absolute rate constant measurements for the reactions of OH with cyclopentane and cycloheptane in the gas phase in 6-8 Torr of nitrogen from 233 to 351 K in the Harvard University High-Pressure Flow System (HPFS) are reported. Hydroxyl concentrations were measured using laser-induced fluorescence, and alkane concentrations were measured using Fourier transform infrared spectroscopy. Results were fit to a modified Arrhenius equation based on transition state theory (ignoring tunneling): k(T) = B e(-E(a)/T)/T(1 - e(-1.44ν(1)/T))(2)(1 - e(-1.44ν(2)/T)), with ν(1) and ν(2) bending frequencies set to 280 and 500 cm(-1) . Results were as follows for E(a) (K) and k (298) (10(-12) cm(3) s(-1)): cyclopentane, 460 ± 32, 4.85; cycloheptane, 319 ± 36, 9.84. This work represents the second absolute temperature-dependent rate constant measurement reported for cycloheptane, and the third absolute temperature-dependent rate constant measurement reported near room temperature for the reaction of OH and cyclopentane. For the title reactions, the reaction barriers reported here are in agreement with the reaction barrier previously reported for cyclohexane and considerably higher than the barrier previously reported for cyclo-octane, a result that is not predicted by our current understanding of hydrocarbon reactivity.

Kinetic Analysis for the Multistep Profiles of Organic Reactions: Significance of the Conformational Entropy on the Rate Constants of the Claisen Rearrangement.

PubMed

Sumiya, Yosuke; Nagahata, Yutaka; Komatsuzaki, Tamiki; Taketsugu, Tetsuya; Maeda, Satoshi

2015-12-03

The significance of kinetic analysis as a tool for understanding the reactivity and selectivity of organic reactions has recently been recognized. However, conventional simulation approaches that solve rate equations numerically are not amenable to multistep reaction profiles consisting of fast and slow elementary steps. Herein, we present an efficient and robust approach for evaluating the overall rate constants of multistep reactions via the recursive contraction of the rate equations to give the overall rate constants for the products and byproducts. This new method was applied to the Claisen rearrangement of allyl vinyl ether, as well as a substituted allyl vinyl ether. Notably, the profiles of these reactions contained 23 and 84 local minima, and 66 and 278 transition states, respectively. The overall rate constant for the Claisen rearrangement of allyl vinyl ether was consistent with the experimental value. The selectivity of the Claisen rearrangement reaction has also been assessed using a substituted allyl vinyl ether. The results of this study showed that the conformational entropy in these flexible chain molecules had a substantial impact on the overall rate constants. This new method could therefore be used to estimate the overall rate constants of various other organic reactions involving flexible molecules.

Chemical reaction rates of ozone in water infusions of wheat, beech, oak and pine leaves of different ages

NASA Astrophysics Data System (ADS)

Potier, Elise; Loubet, Benjamin; Durand, Brigitte; Flura, Dominique; Bourdat-Deschamps, Marjolaine; Ciuraru, Raluca; Ogée, Jérôme

2017-02-01

In this study we present results from a laboratory experiment designed to evaluate the first-order chemical reaction rate (k) of ozone in water films on plant leaves occurring during dew or rain events. Ozone deposition to wet cuticles is indeed known to be a significant pathway of ozone deposition, but the underlying processes are not yet well understood. Leaf infusions obtained by infusing plant leaves with water at room temperature were introduced into a wet effluent denuder fed with a flux of ozone-rich air. Ozone, water vapour concentrations and temperature were measured in both inlet and outlet airflows in order to compute ozone reaction rates kr using an ozone reaction-diffusion model in the water film. Ascorbate solutions were used to validate the set up and led to kr = 3.6 107 M-1 s-1 consistent with the literature. Ozone reaction rates were determined for wheat, beech, oak and pine leaves infusions at several developmental stages, as well as for rain samples. Leaf infusions reaction rates were between 240 s-1 and 3.4 105 s-1 depending on species and developmental stage, while k for rain water ranged from 130 to 830 s-1. Wheat leaves solutions showed significantly (P < 0.001) higher kr (median 73800 s-1) compared to the other tree species (median 4560 s-1). Senescing or dead leaves also showed significantly (P < 0.001) larger k (median 21100 s-1) compared to non-senescent leaves (median 3200 s-1). In wheat, k also increased with increasing yellow leaf fraction. Our results are in the range of previously reported ozone deposition on wet leaves in field or chamber studies. Composition of leaves infusions and previous studies on throughfall and dew composition shows that reaction of ozone with inorganic compounds may only explain the smallest measured k. The largest k observed during senescent are most likely due to reaction with organic material. This is confirmed by LC-MS measurements which showed detection of ascorbate and VOCs as well as the reaction

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…

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.

Evaluating free vs bound oxygen on ignition of nano-aluminum based energetics leads to a critical reaction rate criterion

NASA Astrophysics Data System (ADS)

Zhou, Wenbo; DeLisio, Jeffery B.; Wang, Xizheng; Egan, Garth C.; Zachariah, Michael R.

2015-09-01

This study investigates the ignition of nano-aluminum (n-Al) and n-Al based energetic materials (nanothermites) at varying O2 pressures (1-18 atm), aiming to differentiate the effects of free and bound oxygen on ignition and to assess if it is possible to identify a critical reaction condition for ignition independent of oxygen source. Ignition experiments were conducted by rapidly heating the samples on a fine Pt wire at a heating rate of ˜105 °C s-1 to determine the ignition time and temperature. The ignition temperature of n-Al was found to reduce as the O2 pressure increased, whereas the ignition temperatures of nanothermites (n-Al/Fe2O3, n-Al/Bi2O3, n-Al/K2SO4, and n-Al/K2S2O8) had different sensitivities to O2 pressure depending on the formulations. A phenomenological kinetic/transport model was evaluated to correlate the concentrations of oxygen both in condensed and gaseous phases, with the initiation rate of Al-O at ignition temperature. We found that a constant critical reaction rate (5 × 10-2 mol m-2 s-1) for ignition exists which is independent to ignition temperature, heating rate, and free vs bound oxygen. Since for both the thermite and the free O2 reaction the critical reaction rate for ignition is the same, the various ignition temperatures are simply reflecting the conditions when the critical reaction rate for thermal runaway is achieved.

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

Rate kernel theory for pseudo-first-order kinetics of diffusion-influenced reactions and application to fluorescence quenching kinetics.

PubMed

Yang, Mino

2007-06-07

Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.

Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

PubMed

Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

2017-07-06

The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

On the use temperature parameterized rate coefficients in the estimation of non-equilibrium reaction rates