Science.gov

Sample records for reaction rate uncertainties

  1. Reaction rate uncertainties and the ν p-process

    NASA Astrophysics Data System (ADS)

    Fröhlich, C.; Rauscher, T.

    2012-11-01

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

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

    SciTech Connect

    Froehlich, C.; Rauscher, T.

    2012-11-12

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

  3. A sensitivity study of s-process: the impact of uncertainties from nuclear reaction rates

    NASA Astrophysics Data System (ADS)

    Vinyoles, N.; Serenelli, A.

    2016-01-01

    The slow neutron capture process (s-process) is responsible for the production of about half the elements beyond the Fe-peak. The production sites and the conditions under which the different components of s-process occur are relatively well established. A detailed quantitative understanding of s-process nucleosynthesis may yield light in physical processes, e.g. convection and mixing, taking place in the production sites. For this, it is important that the impact of uncertainties in the nuclear physics is well understood. In this work we perform a study of the sensitivity of s-process nucleosynthesis, with particular emphasis in the main component, on the nuclear reaction rates. Our aims are: to quantify the current uncertainties in the production factors of s-process elements originating from nuclear physics and, to identify key nuclear reactions that require more precise experimental determinations. In this work we studied two different production sites in which s-process occurs with very different neutron exposures: 1) a low-mass extremely metal-poor star during the He-core flash (nn reaching up to values of ∼ 1014cm-3); 2) the TP-AGB phase of a M⊙, Z=0.01 model, the typical site of the main s-process component (nn up to 108 — 109cm-3). In the first case, the main variation in the production of s-process elements comes from the neutron poisons and with relative variations around 30%-50%. In the second, the neutron poison are not as important because of the higher metallicity of the star that actually acts as a seed and therefore, the final error of the abundances are much lower around 10%-25%.

  4. The Impact of Reaction Rate Uncertainties (and other nuclear physics inputs) on Nucleosynthesis in the Neutrino-p Process

    NASA Astrophysics Data System (ADS)

    Frohlich, Carla; Tang, X.; Truran, J. W.

    2009-10-01

    The neutrino-p (νp) process has been shown to be an important nucleosynthesis process, occurring in core collapse supernovae, that contributes to the synthesis of nuclei in the mass region 64<=A<=120. Such a nucleosynthesis process (in addition to the r- and s-processes) is needed to explain the observed abundance patterns in this mass region - particularly in very low metallicity stars. The νp-process consists of a sequence of (p,γ) and (n,p) or β^+ reactions, where the slowest reactions set the timescale. Nucleosynthesis studies of such events as the νp-process typically involve the use of reaction networks that include several thousand nuclei and associated reaction cross sections and lifetimes, most of which are only known theoretically. A majority of the nuclei involved are unstable and hence pose a challenge for experimental nuclear physicists. With improvements in existing facilities such as NSCL at MSU and ATLAS at ANL and with a future FRIB facility, experimental investigations of reaction rates and other nuclear quantities involving unstable nuclei will become feasible. In this talk, we will demonstrate how uncertainties in the reaction rates influence the resulting nucleosynthesis. In addition, we will identify important reactions and nuclei to be studied experimentally with upcoming techniques at the new facilities.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  6. DEPENDENCE OF s-PROCESS NUCLEOSYNTHESIS IN MASSIVE STARS ON TRIPLE-ALPHA AND {sup 12}C({alpha}, {gamma}){sup 16}O REACTION RATE UNCERTAINTIES

    SciTech Connect

    Tur, Clarisse; Austin, Sam M.; Heger, Alexander E-mail: austin@nscl.msu.edu

    2009-09-10

    We have studied the sensitivity of s-process nucleosynthesis in massive stars to {+-}2{sigma} variations in the rates of the triple-{alpha} and {sup 12}C({alpha}, {gamma}){sup 16}O reactions. We simulated the evolution of massive stars from H burning through Fe-core collapse, followed by a supernova explosion. We found that the production factors of s-process nuclides between {sup 58}Fe and {sup 96}Zr change strongly with changes in the He burning reaction rates; using the Lodders solar abundances rather than those of Anders and Grevesse reduces s-process nucleosynthesis; later burning phases beyond core He burning and shell C burning have a significant effect on post-explosive production factors. We also discuss the implications of the uncertainties in the helium burning rates for evidence of a new primary neutron capture process (LEPP) in massive stars.

  7. Dependence of s-Process Nucleosynthesis in Massive Stars on Triple-Alpha and 12C(α, γ)16O Reaction Rate Uncertainties

    NASA Astrophysics Data System (ADS)

    Tur, Clarisse; Heger, Alexander; Austin, Sam M.

    2009-09-01

    We have studied the sensitivity of s-process nucleosynthesis in massive stars to ±2σ variations in the rates of the triple-α and 12C(α, γ)16O reactions. We simulated the evolution of massive stars from H burning through Fe-core collapse, followed by a supernova explosion. We found that the production factors of s-process nuclides between 58Fe and 96Zr change strongly with changes in the He burning reaction rates; using the Lodders solar abundances rather than those of Anders and Grevesse reduces s-process nucleosynthesis; later burning phases beyond core He burning and shell C burning have a significant effect on post-explosive production factors. We also discuss the implications of the uncertainties in the helium burning rates for evidence of a new primary neutron capture process (LEPP) in massive stars.

  8. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

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

  9. Uncertainty Analysis for Photovoltaic Degradation Rates (Poster)

    SciTech Connect

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

    2014-04-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  11. 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.

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

    SciTech Connect

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

    2014-06-15

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

  13. Cosmological Implications of the Uncertainty in Astrochemical Rate Coefficients

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  14. Renormalized reaction and relaxation rates

    NASA Astrophysics Data System (ADS)

    Gorbachev, Yuriy E.

    2016-06-01

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

  15. Reactions to Uncertainty and the Accuracy of Diagnostic Mammography

    PubMed Central

    Yi, Joyce P.; Abraham, Linn A.; Miglioretti, Diana L.; Aiello, Erin J.; Gerrity, Martha S.; Reisch, Lisa; Berns, Eric A.; Sickles, Edward A.; Elmore, Joann G.

    2007-01-01

    Background Reactions to uncertainty in clinical medicine can affect decision making. Objective To assess the extent to which radiologists’ reactions to uncertainty influence diagnostic mammography interpretation. Design Cross-sectional responses to a mailed survey assessed reactions to uncertainty using a well-validated instrument. Responses were linked to radiologists’ diagnostic mammography interpretive performance obtained from three regional mammography registries. Participants One hundred thirty-two radiologists from New Hampshire, Colorado, and Washington. Measurement Mean scores and either standard errors or confidence intervals were used to assess physicians’ reactions to uncertainty. Multivariable logistic regression models were fit via generalized estimating equations to assess the impact of uncertainty on diagnostic mammography interpretive performance while adjusting for potential confounders. Results When examining radiologists’ interpretation of additional diagnostic mammograms (those after screening mammograms that detected abnormalities), a 5-point increase in the reactions to uncertainty score was associated with a 17% higher odds of having a positive mammogram given cancer was diagnosed during follow-up (sensitivity), a 6% lower odds of a negative mammogram given no cancer (specificity), a 4% lower odds (not significant) of a cancer diagnosis given a positive mammogram (positive predictive value [PPV]), and a 5% higher odds of having a positive mammogram (abnormal interpretation). Conclusion Mammograms interpreted by radiologists who have more discomfort with uncertainty have higher likelihood of being recalled. PMID:17356992

  16. Nova reaction rates and experiments

    NASA Astrophysics Data System (ADS)

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

    2011-04-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2008-01-01

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

  18. 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…

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

    SciTech Connect

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

    2014-01-01

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

  20. The Rate Laws for Reversible Reactions.

    ERIC Educational Resources Information Center

    King, Edward L.

    1986-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  2. 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.

  3. 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.

  4. Impact of THM reaction rates for astrophysics

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  6. 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…

  7. 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…

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

    SciTech Connect

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

    2009-08-06

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

  9. Effective reaction rates for diffusion-limited reaction cycles

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2008-01-01

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

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

    PubMed

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

    2011-01-01

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

  12. Astrophysical Reaction Rates Obtained By Indirect Techniques

    SciTech Connect

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

    2010-08-12

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

  13. 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)

  14. Theoretical uncertainty of (α ,n ) reactions relevant for the nucleosynthesis of light r -process nuclei in neutrino-driven winds

    NASA Astrophysics Data System (ADS)

    Pereira, J.; Montes, F.

    2016-03-01

    Background: Neutrino-driven winds following core-collapse supernova explosions have been proposed as a possible site where light r -process nuclei (between Fe and Ag) might be synthesized. In these events, (α ,n ) reactions are key to moving matter towards the region of higher proton number. Abundance network calculations are very sensitive to the rates for this type of reactions. Purpose: The present work aims at evaluating the theoretical uncertainty of these (α ,n ) reactions calculated with reaction codes based on the Hauser-Feshbach model. Method: We compared several (α ,n ) rates taken from talys and the non-smoker database to determine the uncertainties owing to the existing technical differences between both codes. In addition, we evaluated the sensitivity of talys rates to variations in the α optical potentials, masses, level densities, optical potentials, preequilibrium intranuclear transition rates, level structure, radiative transmission coefficients, and width-fluctuation correction factors. Results: The main source of uncertainty at low temperature is mostly attributable to the use of different α optical potentials. Differences between talys and non-smoker at high temperatures arise from the energy-binning algorithm used by each code. We have also noticed that the (α ,n ) rates from the non-smoker database correspond to the inclusive reaction, instead of the exclusive (α ,1 n ) channel calculated in the present work and used in network calculations. Conclusions: Theoretical uncertainties in calculated reaction rates can be as high as one to two orders of magnitude and strongly dependent on the temperature of the environment. Besides direct measurements of the inclusive and exclusive (α ,1 n ) reaction rates, experimental studies of α optical potentials are crucial to improve the performance of reaction codes.

  15. Critical reaction rates in hypersonic combustion chemistry

    SciTech Connect

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

    1989-01-01

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

  16. Universal reaction rates for ultracold molecular collisions

    NASA Astrophysics Data System (ADS)

    Julienne, Paul; Idziaszek, Zbigniew

    2010-03-01

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

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

    SciTech Connect

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

    2010-10-01

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

  18. Comparison of the inspector and rating protocol uncertainty influence in the condition rating of sewers.

    PubMed

    Sousa, V; Ferreira, F M; Meireles, I; Almeida, N; Saldanha Matos, J

    2014-01-01

    Wastewater drainage systems asset management decisions, in particular regarding rehabilitation interventions, are largely dependent on close-circuit television (CCTV) inspection results. However, the results of CCTV inspections are affected by several sources of uncertainty. Within the present communication, the inspector's uncertainty is quantified by comparing periodic inspection reports from three trunk sewers of a Portuguese sewer system. The inspections were carried out by the same experienced inspector using the same equipment. Therefore, the uncertainties from the lack of experience and the difference of the inspector and equipment were ruled out. The protocol uncertainty is also quantified comparing the results obtained with the Water Research Center (WRc) and the National Research Council of Canada (NRC) protocols condition ratings. Both operational and structural condition rating were analysed, but emphasis was given to the later since it dictates the repair and replacement interventions. PMID:24569288

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  20. Enhanced aqueous photochemical reaction rates after freezing.

    PubMed

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

    2007-11-01

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

  1. 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

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

    NASA Astrophysics Data System (ADS)

    Hellander, Stefan; Petzold, Linda

    2016-01-01

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

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

    SciTech Connect

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

    2012-03-01

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

  4. Thermodynamic limitations on microbially catalyzed reaction rates

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  5. 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.

  6. 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.

  7. Fusion Reaction Rate in an Inhomogeneous Plasma

    SciTech Connect

    S. Son; N.J. Fisch

    2004-09-03

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  10. Indirect techniques for astrophysical reaction rates determinations

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  11. Representing Rate Equations for Enzyme-Catalyzed Reactions

    ERIC Educational Resources Information Center

    Ault, Addison

    2011-01-01

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

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

    SciTech Connect

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

    2011-01-01

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

  13. Typewriting rate as a function of reaction time.

    PubMed

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

    1977-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

  15. Metallicity-Dependent Isotopic Abundances and the Impact of Helium Rate Uncertainties in Massive Stars

    NASA Astrophysics Data System (ADS)

    West, Christopher

    2013-03-01

    model compared to the linear interpolation method, for the six s--only isotopes along the weak s--process path. As a second project, we study the sensitivity of presupernova evolution and supernova nucleosynthesis yields of massive stars to variations of the helium-burning reaction rates within the range of their uncertainties. The current solar abundances from Lodders (2010) are used for the initial stellar composition. We compute a grid of 12 initial stellar masses and 176 models per stellar mass to explore the effects of independently varying the 12C(alpha,gamma)16O and 3alpha reaction rates, denoted Ralpha,12 and R3alpha, respectively. The production factors of both the intermediate-mass elements (A=16--40) and the s--only isotopes along the weak s--process path ( 70Ge, 76Se, 80Kr, 82Kr, 86Sr, and 87Sr) were found to be in reasonable agreement with predictions for variations of R3alpha and Ralpha,12 of +/-25%; the s--only isotopes, however, tend to favor higher values of R3alpha than the intermediate-mass isotopes. The experimental uncertainty (one standard deviation) in R3alpha(Ralpha,12 ) is approximately +/-10%(+/-25%). The results show that a more accurate measurement of one of these rates would decrease the uncertainty in the other as inferred from the present calculations. We also observe sharp changes in production factors and standard deviations for small changes in the reaction rates, due to differences in the convection structure of the star. The compactness parameter was used to assess which models would likely explode as successful supernovae, and hence contribute explosive nucleosynthesis yields. We also provide the approximate remnant masses for each model and the carbon mass fractions at the end of core-helium burning as a key parameter for later evolution stages.

  16. Multidimensional reaction rate theory with anisotropic diffusion

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  17. DSMC predictions of non-equilibrium reaction rates.

    SciTech Connect

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

    2010-04-01

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

  18. On the rate of relativistic surface chemical reactions.

    PubMed

    Veitsman, E V

    2004-07-15

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

  19. Simulating the formation of massive seed black holes in the early Universe - II. Impact of rate coefficient uncertainties

    NASA Astrophysics Data System (ADS)

    Glover, Simon C. O.

    2015-11-01

    We investigate how uncertainties in the chemical and cooling rate coefficients relevant for a metal-free gas influence our ability to determine the critical ultraviolet field strength required to suppress H2 cooling in high-redshift atomic cooling haloes. The suppression of H2 cooling is a necessary prerequisite for the gas to undergo direct collapse and form an intermediate mass black hole. These black holes can then act as seeds for the growth of the supermassive black holes (SMBHs) observed at redshifts z ˜ 6. The viability of this model for SMBH formation depends on the critical ultraviolet field strength, Jcrit: if this is too large, then too few seeds will form to explain the observed number density of SMBHs. We show in this paper that there are five key chemical reactions whose rate coefficients are uncertain enough to significantly affect Jcrit. The most important of these is the collisional ionization of hydrogen by collisions with other hydrogen atoms, as the rate for this process is very poorly constrained at the low energies relevant for direct collapse. The total uncertainty introduced into Jcrit by this and the other four reactions could in the worst case approach a factor of five. We also show that the use of outdated or inappropriate values for the rates of some chemical reactions in previous studies of the direct collapse mechanism may have significantly affected the values of Jcrit determined by these studies.

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

    PubMed

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Sato, Shin

    2016-05-01

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

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

    PubMed

    Sashi, Pulikallu; Bhuyan, Abani K

    2015-07-28

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

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

    PubMed

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

    2015-03-01

    The minimal dose covering 90 % of the prostate volume--D 90--is arguably the most important dosimetric parameter in low-dose-rate prostate seed brachytherapy. In this study an analysis of the measurement uncertainties in D 90 from low-dose-rate prostate seed brachytherapy was conducted for two common treatment procedures with two different post-implant dosimetry methods. The analysis was undertaken in order to determine the magnitude of D 90 uncertainty, how the magnitude of the uncertainty varied when D 90 was calculated using different dosimetry methods, and which factors were the major contributors to the uncertainty. The analysis considered the prostate as being homogeneous and tissue equivalent and made use of published data, as well as original data collected specifically for this analysis, and was performed according to the Guide to the expression of uncertainty in measurement (GUM). It was found that when prostate imaging and seed implantation were conducted in two separate sessions using only CT images for post-implant analysis, the expanded uncertainty in D 90 values were about 25 % at the 95 % confidence interval. When prostate imaging and seed implantation were conducted during a single session using CT and ultrasound images for post-implant analysis, the expanded uncertainty in D 90 values were about 33 %. Methods for reducing these uncertainty levels are discussed. It was found that variations in contouring the target tissue made the largest contribution to D 90 uncertainty, while the uncertainty in seed source strength made only a small contribution. It is important that clinicians appreciate the overall magnitude of D 90 uncertainty and understand the factors that affect it so that clinical decisions are soundly based, and resources are appropriately allocated. PMID:25555753

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

    NASA Technical Reports Server (NTRS)

    Rizvi, Farheen

    2013-01-01

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

  5. 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

  6. Theory of Crowding Effects on Bimolecular Reaction Rates.

    PubMed

    Berezhkovskii, Alexander M; Szabo, Attila

    2016-07-01

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

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

    SciTech Connect

    Murphy, M J

    2010-03-08

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

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

    NASA Astrophysics Data System (ADS)

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

    1992-06-01

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

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

    SciTech Connect

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

    2014-05-02

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

  10. Rate of reaction between molecular hydrogen and molecular oxygen

    NASA Technical Reports Server (NTRS)

    Brokaw, R. S.

    1973-01-01

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

  11. New estimates of silicate weathering rates and their uncertainties in global rivers

    NASA Astrophysics Data System (ADS)

    Moon, Seulgi; Chamberlain, C. P.; Hilley, G. E.

    2014-06-01

    This study estimated the catchment- and global-scale weathering rates of silicate rocks from global rivers using global compilation datasets from the GEMS/Water and HYBAM. These datasets include both time-series of chemical concentrations of major elements and synchronous discharge. Using these datasets, we first examined the sources of uncertainties in catchment and global silicate weathering rates. Then, we proposed future sampling strategies and geochemical analyses to estimate accurate silicate weathering rates in global rivers and to reduce uncertainties in their estimates. For catchment silicate weathering rates, we considered uncertainties due to sampling frequency and variability in river discharge, concentration, and attribution of weathering to different chemical sources. Our results showed that uncertainties in catchment-scale silicate weathering rates were due mostly to the variations in discharge and cation fractions from silicate substrates. To calculate unbiased silicate weathering rates accounting for the variations from discharge and concentrations, we suggest that at least 10 and preferably ∼40 temporal chemical data points with synchronous discharge from each river are necessary. For the global silicate weathering rate, we examined uncertainties from infrequent sampling within an individual river, the extrapolation from limited rivers to a global flux, and the inverse model selections for source differentiation. For this weathering rate, we found that the main uncertainty came from the extrapolation to the global flux and the model configurations of source differentiation methods. This suggests that to reduce the uncertainties in the global silicate weathering rates, coverage of synchronous datasets of river chemistry and discharge to rivers from tectonically active regions and volcanic provinces must be extended, and catchment-specific silicate end-members for those rivers must be characterized. With current available synchronous datasets, we

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

    PubMed

    Motagamwala, Ali Hussain; Dumesic, James A

    2016-05-24

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

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

    NASA Astrophysics Data System (ADS)

    Hussain Motagamwala, Ali; Dumesic, James A.

    2016-05-01

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

  14. Accurate measurements of OH reaction rate constants over atmospheric temperatures and the atmospheric lifetime of trace gases

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Reactions with hydroxyl radicals and photolysis are the main processes dictating the compound residence time in the atmosphere for a majority of trace gases. In case of very short lived compounds their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the purpose of comprehensive atmospheric modeling of compound's impact on the atmosphere, such as in ozone depletion (ODP) and climate change (GWP). The currently recommended uncertainties of OH reaction rate constants (NASA/JPL Publications and IUPAC Publications) exceed 10% at room temperature for the majority of compounds to be larger at lower temperatures of atmospheric interest. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions may constitute a major source of uncertainty in estimating the compound's environmental impact. We will present the higher accuracy results of OH reaction rate constant determinations between 220 K and 370 K. A statistical analysis of the data will be discussed. The high precision of kinetic measurements performed at low temperatures allows reliable determination of temperature dependences of the rate constants. This is especially important because we found that many OH reactions exhibit the curvature of the Arrhenius plots. A detailed inventory of sources of instrumental uncertainties related to our experiment proves a total uncertainty of the OH reaction rate constant to be as small as ~2-3%. The estimation of the atmospheric lifetime of a compound based on its OH reaction rate constant will be discussed.

  15. Reaction Rates of 64Ge(p,?)65As and 65As(p,?)66Se and the Extent of Nucleosynthesis in Type I X-Ray Bursts

    NASA Astrophysics Data System (ADS)

    Lam, Y. H.; He, J. J.; Parikh, A.; Schatz, H.; Brown, B. A.; Wang, M.; Guo, B.; Zhang, Y. H.; Zhou, X. H.; Xu, H. S.

    2016-02-01

    The extent of nucleosynthesis in models of type I X-ray bursts (XRBs) and the associated impact on the energy released in these explosive events are sensitive to nuclear masses and reaction rates around the 64Ge waiting point. Using the well known mass of 64Ge, the recently measured 65As mass, and large-scale shell model calculations, we have determined new thermonuclear rates of the 64Ge(p,γ)65As and 65As(p,γ)66Se reactions with reliable uncertainties. The new reaction rates differ significantly from previously published rates. Using the new data, we analyze the impact of the new rates and the remaining nuclear physics uncertainties on the 64Ge waiting point in a number of representative one-zone XRB models. We find that in contrast to previous work, when all relevant uncertainties are considered, a strong 64Ge rp-process waiting point cannot be ruled out. The nuclear physics uncertainties strongly affect XRB model predictions of the synthesis of 64Zn, the synthesis of nuclei beyond A = 64, the energy generation, and the burst light curve. We also identify key nuclear uncertainties that need to be addressed to determine the role of the 64Ge waiting point in XRBs. These include the remaining uncertainty in the 65As mass, the uncertainty of the 66Se mass, and the remaining uncertainty in the 65As(p,γ)66Se reaction rate, which mainly originates from uncertain resonance energies.

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

    DOE PAGESBeta

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

    2015-12-01

    Shutdown dose rate (SDDR) analysis requires (a) a neutron transport calculation to estimate neutron flux fields, (b) an activation calculation to compute radionuclide inventories and associated photon sources, and (c) a photon transport calculation to estimate final SDDR. In some applications, accurate full-scale Monte Carlo (MC) SDDR simulations are needed for very large systems with massive amounts of shielding materials. However, these simulations are impractical because calculation of space- and energy-dependent neutron fluxes throughout the structural materials is needed to estimate distribution of radioisotopes causing the SDDR. Biasing the neutron MC calculation using an importance function is not simple 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

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

    SciTech Connect

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  19. 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.

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

    PubMed

    Kawai, Shinnosuke; Komatsuzaki, Tamiki

    2010-07-21

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

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

    SciTech Connect

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

    2010-08-15

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

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

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

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

  3. 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. PMID:22492551

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

    NASA Astrophysics Data System (ADS)

    Rajaram, Harihar; Arshadi, Masoud

    2015-04-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  7. Diagrammatic algorithm for evaluating finite-temperature reaction rates

    NASA Astrophysics Data System (ADS)

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

    1992-05-01

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

  8. THE IMPACT OF HELIUM-BURNING REACTION RATES ON MASSIVE STAR EVOLUTION AND NUCLEOSYNTHESIS

    SciTech Connect

    West, Christopher; Heger, Alexander; Austin, Sam M. E-mail: alexander.heger@monash.edu

    2013-05-20

    We study the sensitivity of presupernova evolution and supernova nucleosynthesis yields of massive stars to variations of the helium-burning reaction rates within the range of their uncertainties. The current solar abundances from Lodders are used for the initial stellar composition. We compute a grid of 12 initial stellar masses and 176 models per stellar mass to explore the effects of independently varying the {sup 12}C({alpha}, {gamma}){sup 16}O and 3{alpha} reaction rates, denoted R{sub {alpha},12} and R{sub 3{alpha}}, respectively. The production factors of both the intermediate-mass elements (A = 16-40) and the s-only isotopes along the weak s-process path ({sup 70}Ge, {sup 76}Se, {sup 80}Kr, {sup 82}Kr, {sup 86}Sr, and {sup 87}Sr) were found to be in reasonable agreement with predictions for variations of R{sub 3{alpha}} and R{sub {alpha},12} of {+-}25%; the s-only isotopes, however, tend to favor higher values of R{sub 3{alpha}} than the intermediate-mass isotopes. The experimental uncertainty (one standard deviation) in R{sub 3{alpha}}(R{sub {alpha},12}) is approximately {+-}10%({+-}25%). The results show that a more accurate measurement of one of these rates would decrease the uncertainty in the other as inferred from the present calculations. We also observe sharp changes in production factors and standard deviations for small changes in the reaction rates, due to differences in the convection structure of the star. The compactness parameter was used to assess which models would likely explode as successful supernovae, and hence contribute explosive nucleosynthesis yields. We also provide the approximate remnant masses for each model and the carbon mass fractions at the end of core-helium burning as a key parameter for later evolution stages.

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

    NASA Astrophysics Data System (ADS)

    Arshadi, Masoud; Rajaram, Harihar

    2015-09-01

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

  10. 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

  11. 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. PMID:25830910

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  13. 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

  14. 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.

  15. A transport equation for reaction rate in turbulent flows

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  16. Quantum and semiclassical theories of chemical reaction rates

    SciTech Connect

    Miller, W.H. |

    1995-09-01

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

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

    PubMed

    Catlow, C Richard A

    2016-08-01

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

  18. Modeling compressive reaction and estimating model uncertainty in shock loaded porous samples of Hexanitrostilbene (HNS)

    NASA Astrophysics Data System (ADS)

    Brundage, Aaron; Gump, Jared

    2011-06-01

    Neat pressings of HNS powders have been used in many explosive applications for over 50 years. However, characterization of its crystalline properties has lagged that of other explosives, and the solid stress has been inferred from impact experiments or estimated from mercury porosimetry. This lack of knowledge of the precise crystalline isotherm can contribute to large model uncertainty in the reacted response of pellets to shock impact. At high impact stresses, deflagration-to-detonation transition (DDT) processes initiated by compressive reaction have been interpreted from velocity interferometry at the surface of distended HNS-FP pellets. In particular, the Baer-Nunziato multiphase model in CTH, Sandia's Eulerian, finite volume shock propagation code, was used to predict compressive waves in pellets having approximately a 60% theoretical maximum density (TMD). These calculations were repeated with newly acquired isothermal compression measurements of fine-particle HNS using diamond anvil cells to compress the sample and powder x-ray diffraction to obtain the sample volume at each pressure point. Hence, estimating the model uncertainty provides a simple method for conveying the impact of future model improvements based upon new experimental data.

  19. Modeling compressive reaction and estimating model uncertainty in shock loaded porous samples of hexanitrostilbene (HNS)

    NASA Astrophysics Data System (ADS)

    Brundage, Aaron L.; Gump, Jared C.

    2012-03-01

    Neat pressings of HNS powders have been used in many explosive applications for over 50 years. However, characterization of its crystalline properties has lagged that of other explosives, and the solid stress has been inferred from impact experiments or estimated from mercury porosimetry. This lack of knowledge of the precise crystalline isotherm can contribute to large model uncertainty in the reacted response of pellets to shock impact. At high impact stresses, deflagration-to-detonation transition (DDT) processes initiated by compressive reaction have been interpreted from velocity interferometry at the surface of distended HNS-FP pellets. In particular, the Baer-Nunziato multiphase model in CTH, Sandia's Eulerian, finite volume shock propagation code, was used to predict compressive waves in pellets having approximately a 60% theoretical maximum density (TMD). These calculations were repeated with newly acquired isothermal compression measurements of fineparticle HNS using diamond anvil cells to compress the sample and powder x-ray diffraction to obtain the sample volume at each pressure point. Hence, estimating the model uncertainty provides a simple method for conveying the impact of future model improvements based upon new experimental data.

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

    SciTech Connect

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

    2010-06-01

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

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

    Energy Science and Technology Software Center (ESTSC)

    1994-10-25

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

  2. Rate of reaction of OH with HNO3

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

  3. Relative rate constants for the reactions of OH with methane and methyl chloroform

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1992-01-01

    Atmospheric lifetimes of methane and methyl chloroform are largely determined by the rates of their reactions with hydroxyl radical. The relative lifetimes for this loss path are inversely proportional to the ratio of the corresponding rate coefficients. The relative rate constants were measured in a slow-flow, temperature-controlled photochemical reactor, and were based on rates of disappearance of the parent compounds as measured by FTIR spectroscopy. The temperature range was 277-356 K. Hydroxyl radicals were generated by 254 nm photolysis of O3 in the presence of water vapor. The preferred Arrhenius expression for the results is k(CH3CCl3)/k(CH4) = 0.62 exp (291/T), corresponding to a value of 1.65 at 298 K and 1.77 at 277 K. The respective uncertainties are 5 and 7 percent.

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

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

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

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

    PubMed

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

    2015-07-01

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

  6. Scaling of geochemical reaction rates via advective solute transport

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

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

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

    SciTech Connect

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

    2011-11-01

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

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

    SciTech Connect

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

    1996-03-01

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

  10. 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. PMID:21318005

  11. Relative contributions of the uncertainty in climate sensitivity and rate of the heat uptake by the ocean in the uncertainty of the projected climate change

    NASA Astrophysics Data System (ADS)

    Sokolov, A. P.; Monier, E.; Forest, C. E.

    2013-12-01

    Climate sensitivity and rate of the heat uptake by the deep ocean are two main characteristics of the Climate System defining its response to a prescribed external forcing. We study relative contributions of the uncertainty in these two characteristics by means of numerical simulations with the MIT Earth System Model (MESM) of intermediate complexity. The MESM consists of a 2D (zonally averaged) atmospheric model coupled to an anomaly diffusing ocean model. Probability distributions for climate sensitivity and rate of oceanic heat uptake are obtained using available data on radiative forcing and temperature changes over 20th century. The results from three 400-member ensembles of long-term (years 1860 to 3000) climate simulations for the IPCC RCP6.0 forcing scenario will be presented. The values of climate sensitivity and rate of oceanic heat uptake, used in the first ensemble, were chosen by sampling their joint probability distribution. In the other two ensembles uncertainty in only one characteristic was taken into account, while the median value was used for the other. Results show that contribution of the uncertainty in climate sensitivity and rate of heat uptake by the deep ocean into the overall uncertainty in projected surface warming and sea level rise is time dependent. Contribution of the uncertainty in rate of heat uptake into uncertainty in the projected surface air temperature increase is rather similar to that of the uncertainty in climate sensitivity while forcing is increasing, but it becomes significantly smaller after forcing is stabilized. The magnitude of surface warming at the end of 30th century is defined almost exclusively by the climate sensitivity distribution. In contrast, uncertainty in the heat uptake has a noticeable effect on projected sea level rise for the whole period of simulations.

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

    SciTech Connect

    Not Available

    1993-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  14. The effect of 12C +12C rate uncertainties on the evolution and nucleosynthesis of massive stars

    NASA Astrophysics Data System (ADS)

    Bennett, M. E.; Hirschi, R.; Pignatari, M.; Diehl, S.; Fryer, C.; Herwig, F.; Hungerford, A.; Nomoto, K.; Rockefeller, G.; Timmes, F. X.; Wiescher, M.

    2012-03-01

    Over the last 40 years, the 12C +12C fusion reaction has been the subject of considerable experimental efforts to constrain uncertainties at temperatures relevant for stellar nucleosynthesis. Recent studies have indicated that the reaction rate may be higher than that currently used in stellar models. In order to investigate the effect of an enhanced carbon-burning rate on massive star structure and nucleosynthesis, new stellar evolution models and their yields are presented exploring the impact of three different 12C +12C reaction rates. Non-rotating stellar models considering five different initial masses, 15, 20, 25, 32 and 60 M⊙, at solar metallicity, were generated using the Geneva Stellar Evolution Code (GENEC) and were later post-processed with the NuGrid Multi-zone Post-Processing Network tool (MPPNP). A dynamic nuclear reaction network of ˜1100 isotopes was used to track the s-process nucleosynthesis. An enhanced 12C +12C reaction rate causes core carbon burning to be ignited more promptly and at lower temperature. This reduces the neutrino losses, which increases the core carbon-burning lifetime. An increased carbon-burning rate also increases the upper initial mass limit for which a star exhibits a convective carbon core (rather than a radiative one). Carbon-shell burning is also affected, with fewer convective-shell episodes and convection zones that tend to be larger in mass. Consequently, the chance of an overlap between the ashes of carbon-core burning and the following carbon shell convection zones is increased, which can cause a portion of the ashes of carbon-core burning to be included in the carbon shell. Therefore, during the supernova explosion, the ejecta will be enriched by s-process nuclides synthesized from the carbon-core s-process. The yields were used to estimate the weak s-process component in order to compare with the Solar system abundance distribution. The enhanced rate models were found to produce a significant proportion of Kr

  15. An uncertainty model for snowfall rate retrievals from the GPM DPR

    NASA Astrophysics Data System (ADS)

    Nesbitt, S. W.; Reed, K. A.

    2015-12-01

    In this presentation, a simple version of the operational GPM DPR retrieval algorithm will be used to explore uncertainties in snowfall rate retrievals using single-frequency and dual-frequency retrieval methods. This model will be used to quantify uncertainties in retrieval of the profile of snowfall rate within the column as well as at the surface below clutter ranges. The DPR uncertainty model will use data from GPM-GV field campaigns including C3VP (Canadian CloudSat/CALIPSO Validation Programme, conducted in 2007 near Barrie, Ontario, Canada) and GCPEx (Global Precipitation Measurement mission Cold Season Precipitation Experiment, conducted in 2012 near Barrie, Ontario, Canada) to gather a priori microphysical assumptions from surface disdrometer and aircraft data. These assumptions will be used to explore the impact of varying a priori assumptions on measured dual frequency radar profiles observed in snowfall from the ground, aircraft, and spaceborne radars to ascertain sensitivities and key parameters which cause the snowfall rate retrievals to vary in the profile and at the surface. The variability in snowfall parameters the near surface bins within spaceborne radar measurements will also be examined, and suggestions for the treatment of these bins in algorithms will be addressed.

  16. Uncertainty in silicate mineral weathering rate estimates: source partitioning and policy implications

    NASA Astrophysics Data System (ADS)

    Futter, M. N.; Klaminder, J.; Lucas, R. W.; Laudon, H.; Köhler, S. J.

    2012-06-01

    Precise and accurate estimates of silicate mineral weathering rates are crucial when setting policy targets for long-term forest sustainability, critical load calculations and assessing consequences of proposed geo-engineering solutions to climate change. In this paper, we scrutinize 394 individual silicate mineral weathering estimates from 82 sites on three continents. We show that within-site differences of several hundred per cent arise when different methods are used to estimate weathering rates, mainly as a result of uncertainties related to input data rather than conceptually different views of the weathering process. While different methods tend to rank sites congruently from high to low weathering rates, large within-site differences in estimated weathering rate suggest that policies relying on quantitative estimates based upon a single method may have undesirable outcomes. We recommend the use of at least three independent estimates when making management decisions related to silicate mineral weathering rates.

  17. A model for reaction rates in turbulent reacting flows

    NASA Technical Reports Server (NTRS)

    Chinitz, W.; Evans, J. S.

    1984-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Rauscher, T.

    2013-09-01

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

  19. 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.

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

    SciTech Connect

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

    2012-11-12

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

  1. Explicit Solution of Worst-Case Secrecy Rate for MISO Wiretap Channels With Spherical Uncertainty

    NASA Astrophysics Data System (ADS)

    Li, Jiangyuan; Petropulu, Athina P.

    2012-07-01

    A multiple-input single-output (MISO) wiretap channel model is considered, that includes a multi-antenna transmitter, a single-antenna legitimate receiver and a single-antenna eavesdropper. For the scenario in which spherical uncertainty for both the legitimate and the eavesdropper channels is included, the problem of finding the optimal input covariance that maximizes the worst-case secrecy rate subject to a power constraint, is considered, and an explicit expression for the maximum worst-case secrecy rate is provided.

  2. Application of semiclassical methods to reaction rate theory

    SciTech Connect

    Hernandez, R.

    1993-11-01

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

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

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

    SciTech Connect

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

    2010-12-01

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

  6. Omphacite breakdown reactions and relation to eclogite exhumation rates

    NASA Astrophysics Data System (ADS)

    Anderson, Eric D.; Moecher, David P.

    2007-09-01

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

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

    SciTech Connect

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

    2010-02-16

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

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

  10. The effect of 12C + 12C rate uncertainties on the weak s-process component

    SciTech Connect

    Fryer, Christopher Lee; Hungerford, Aimee L; Hirschi, Raphael; Pignatari, Marco; Bennett, Michael E; Diehl, Steven; Herwig, Falk; Hillary, William; Richman, Debra; Rockefeller, Gabriel; Timmes, Frank X; Wiescher, Michael

    2010-09-10

    The contribution by massive stars (M > 15M{sub {circle_dot}}) to the weak s-process component of the solar system abundances is primarily due to the {sup 22}Ne neutron source, which is activated near the end of helium-core burning. The residual {sup 22}Ne left over from helium-core burning is then reignited during carbon burning, initiating further s-processing that modifies the isotopic distribution. This modification is sensitive to the stellar structure and the carbon burning reaction rate. Recent work on the {sup 12}C + {sup 12}C reaction suggests that resonances located within the Gamow peak may exist, causing a strong increase in the astrophysical S-factor and consequently the reaction rate. To investigate the effect of such a rate, 25M{sub {circle_dot}} stellar models with different carbon burning rates, at solar metallicity, were generated using the Geneva Stellar Evolution Code (GENEC) with nucleosynthesis post-processing calculated using the NuGrid Multi-zone Post-Processing Network code (MPPNP). A strongly enhanced rate can cause carbon burning to occur in a convective core rather than a radiative one and the convective core mixes the matter synthesized there up into the carbon shell, significantly altering the initial composition of the carbon-shell. In addition, an enhanced rate causes carbon-shell burning episodes to ignite earlier in the evolution of the star, igniting the {sup 22}Ne source at lower temperatures and reducing the neutron density.

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

    SciTech Connect

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

    1986-12-01

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

  12. Uncertainty in degradation rates for organic micro-pollutants during full-scale sewage sludge composting.

    PubMed

    Sadef, Yumna; Poulsen, Tjalfe G; Habib, Kashif; Iqbal, Tariq; Nizami, Abdul Sattar

    2016-10-01

    Composting can potentially remove organic pollutants in sewage sludge. When estimating pollutant removal efficiency, knowledge of estimate uncertainty is important for understanding estimate reliability. In this study the uncertainty (coefficient of variation, CV) in pollutant degradation rate (K1) and relative concentration at 35days of composting (C35/C0) was evaluated. This was done based on recently presented pollutant concentration data, measured under full-scale composting conditions using two different sampling methods for a range of organic pollutants commonly found in sewage sludge. Non-parametric statistical procedures were used to estimate CV values for K1 and C35/C0 for individual pollutants. These were then used to compare the two sampling methods with respect to CV and to determine confidence intervals for average CV. Results showed that sampling method is crucial for reducing uncertainty. The results further indicated that it is possible to achieve CV values for both K1 and C35/C0 of about 15%. PMID:27342191

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Keck, James C.

    2008-08-01

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

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

    ERIC Educational Resources Information Center

    Lombardo, Anthony

    1982-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Kawano, Lawrence; Schramm, David; Steigman, Gary

    1988-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  19. Measuring OH Reaction Rate Constants and Estimating the Atmospheric Lifetimes of Trace Gases.

    NASA Astrophysics Data System (ADS)

    Orkin, Vladimir; Kurylo, Michael

    2015-04-01

    Reactions with hydroxyl radicals and photolysis are the main processes dictating a compound's residence time in the atmosphere for a majority of trace gases. In case of very short-lived halocarbons their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the comprehensive modeling of a compound's impact on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP), each of which are dependent on the atmospheric lifetime of the compound. We have demonstrated the ability to conduct very high accuracy determinations of OH reaction rate constants over the temperature range of atmospheric interest, thereby decreasing the uncertainty of kinetic data to 2-3%. The atmospheric lifetime of a well-mixed compound due to its reaction with tropospheric hydroxyl radicals can be estimated by using a simple scaling procedure that is based on the results of field observations of methyl chloroform concentrations and detailed modeling of the OH distribution in the atmosphere. The currently available modeling results of the atmospheric fate of various trace gases allow for an improved understanding of the ability and accuracy of simplified semi-empirical estimations of atmospheric lifetimes. These aspects will be illustrated in this presentation for a variety of atmospheric trace gases.

  20. Measuring OH Reaction Rate Constants and Estimating the Atmospheric Lifetimes of Trace Gases.

    NASA Astrophysics Data System (ADS)

    Orkin, V. L.; Kurylo, M. J., III

    2014-12-01

    Reactions with hydroxyl radicals and photolysis are the main processes dictating a compound's residence time in the atmosphere for a majority of trace gases. In case of very short-lived halocarbons their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the comprehensive modeling of a compound's impact on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP), each of which are dependent on the atmospheric lifetime of the compound. We have demonstrated the ability to conduct very high accuracy determinations of OH reaction rate constants over the temperature range of atmospheric interest, thereby decreasing the uncertainty of kinetic data to 2-3%. The atmospheric lifetime of a tropospherically well-mixed compound due to its reaction with tropospheric hydroxyl radicals can be estimated by using a simple scaling procedure that is based on the results of field observations of methyl chloroform concentrations and detailed modeling of the OH distribution in the atmosphere. The currently available modeling results of the atmospheric fate of various trace gases allow for an improved understanding of the ability and accuracy of simplified semi-empirical estimations of atmospheric lifetimes. These aspects will be illustrated in this presentation for a variety of atmospheric trace gases.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

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

    PubMed

    Liu, Yingdi; Sander, Stanley P

    2015-10-01

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

  3. 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.

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

    NASA Astrophysics Data System (ADS)

    Morlot, Thomas; Perret, Christian; Favre, Anne-Catherine; Despax, Aurélien; Hauet, Alexandre; Sevrez, Damien; Belleville, Arnaud

    2015-04-01

    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 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. Moreover, the current 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. 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

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

    NASA Astrophysics Data System (ADS)

    Ladeinde, Foluso; Lou, Zhipeng; Li, Wenhai

    2015-11-01

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

  6. The effects of vacuum polarization on thermonuclear reaction rates

    NASA Technical Reports Server (NTRS)

    Gould, Robert J.

    1990-01-01

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

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

    SciTech Connect

    Snider, J.R.

    1989-01-01

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

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

    ERIC Educational Resources Information Center

    Copper, Christine L.; Koubeck, Edward

    1999-01-01

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

  9. 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

  10. 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.

  11. Charge-exchange reactions and electron-capture rates for presupernova stellar evolution

    NASA Astrophysics Data System (ADS)

    Zegers, Remco

    2015-04-01

    Weak reaction rates such as electron captures and beta decays play major roles in a variety of astrophysical phenomena, such as core-collapse and thermonuclear supernovae and accreting neutron stars. Consequently, the use of accurate weak reaction rates in astrophysical simulations to understand these phenomena is important. Unfortunately, the number of relevant nuclei is typically very large, and, except for a few special cases, it is impossible to rely on experimental results only: theoretical models must be used to estimate the weak reaction rates. These models can then be benchmarked and improved on the basis of a limited number of experimental data. The most important nuclear structure input that is required for calculating weak reaction rates are Gamow-Teller transition strengths. Although these can be extracted from beta and electron-capture decay data, the energy window accessible by such experiments is limited, if accessible at all. However, at the high temperatures and densities that occur in massive stars prior to the cataclysmic demise, transitions to final states at high excitation energies are important. In addition, to properly test theory, full Gamow-Teller transition strength distributions are very valuable. Fortunately, nature is kind: charge-exchange experiments at intermediate energies can provide the relevant strength distributions over a wide energy window and a variety of charge-exchange probes, such as (p,n), (n,p), (d,2 He) and (t,3 He) have been used to extract strengths of relevance for astrophysics (and for other purposes). This presentation will focus on efforts to validate electron capture rates calculated based on nuclear structure models for nuclei with masses ranging from A ~ 40-65, and on studies aimed at testing astrophysical sensitivities to uncertainties/deviations in the theoretical rates. These efforts include experiments with unstable isotopes, and special gamma-ray coincidence techniques to localize very weak, but

  12. Photonuclear and radiative capture reaction rates for Nuclear Astrophysics

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

  13. Enhanced reaction rates in NDP analysis with neutron scattering

    SciTech Connect

    Downing, R. Gregory

    2014-04-15

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

  14. Assessment of Uncertainty in the Determination of Kinetic Reaction Parameters for Polymeric Materials

    NASA Technical Reports Server (NTRS)

    Darby, Stephanie P.; Landrum, D. Brian

    1996-01-01

    The use of thermogravimetric analysis to obtain data describing the thermal response of a polymeric resin with temperature. This data can then be used to obtain activation energy and pre-exponential factor used in an Arrhenius representation of material ablation. The methods which allow to assess the uncertainties associated with the experimental determination of activation energy and pre-exponential factor are employed.

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

    NASA Astrophysics Data System (ADS)

    Ribeiro, Joao Marcelo; Mebel, Alexander M.

    2015-07-01

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

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

    SciTech Connect

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

    2009-08-01

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

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

    PubMed

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

    2016-07-13

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

  18. 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

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

    PubMed

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

    2016-01-01

    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

  20. Optimal reconstruction of reaction rates from particle distributions

    NASA Astrophysics Data System (ADS)

    Fernandez-Garcia, Daniel; Sanchez-Vila, Xavier

    2010-05-01

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

  1. 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

  2. Cross sections and reaction rates of relevance to aeronomy

    SciTech Connect

    Fox, J.L. )

    1991-01-01

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

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

    SciTech Connect

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

    1994-10-27

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    ERIC Educational Resources Information Center

    Chesick, John P.

    1988-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  7. Quick and Easy Rate Equations for Multistep Reactions

    ERIC Educational Resources Information Center

    Savage, Phillip E.

    2008-01-01

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

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

    ERIC Educational Resources Information Center

    Simoni, Jane M.; And Others

    1995-01-01

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

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

    SciTech Connect

    Veshchunov, M. S.

    2012-04-15

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

  10. The Effects of Thermonuclear Reaction Rate Variations on 26Al Production in Massive Stars: A Sensitivity Study

    NASA Astrophysics Data System (ADS)

    Iliadis, Christian; Champagne, Art; Chieffi, Alessandro; Limongi, Marco

    2011-03-01

    We investigate the effects of thermonuclear reaction rate variations on 26Al production in massive stars. The dominant production sites in such events were recently investigated by using stellar model calculations: explosive neon-carbon burning, convective shell carbon burning, and convective core hydrogen burning. Post-processing nucleosynthesis calculations are performed for each of these sites by adopting temperature-density-time profiles from recent stellar evolution models. For each profile, we individually multiplied the rates of all relevant reactions by factors of 10, 2, 0.5, and 0.1, and analyzed the resulting abundance changes of 26Al. In total, we performed ≈900 nuclear reaction network calculations. Our simulations are based on a next-generation nuclear physics library, called STARLIB, which contains a recent evaluation of Monte Carlo reaction rates. Particular attention is paid to quantifying the rate uncertainties of those reactions that most sensitively influence 26Al production. For stellar modelers our results indicate to what degree predictions of 26Al nucleosynthesis depend on currently uncertain nuclear physics input, while for nuclear experimentalists our results represent a guide for future measurements. We also investigate equilibration effects of 26Al. In all previous massive star investigations, either a single species or two species of 26Al were taken into account, depending on whether thermal equilibrium was achieved or not. These are two extreme assumptions, and in a hot stellar plasma the ground and isomeric states may communicate via γ-ray transitions involving higher-lying 26Al levels. We tabulate the results of our reaction rate sensitivity study for each of the three distinct massive star sites referred to above. It is found that several current reaction rate uncertainties influence the production of 26Al. Particularly important reactions are 26Al(n,p)26Mg, 25Mg(α,n)28Si, 24Mg(n,γ)25Mg, and 23Na(α,p)26Mg. These reactions

  11. Effects of uncertainty in position on the dissipation rates and the entanglement of two atoms collectively interacting with a reservoir

    NASA Astrophysics Data System (ADS)

    Castaños, L. O.; Jáuregui, R.

    2011-06-01

    We consider two two-level atoms interacting collectively with all the modes of the quantum electromagnetic field. The center-of-mass motion of each atom is quantized in three dimensions and each atom is placed in a harmonic oscillator potential. We describe a method that factorizes an approximate density operator of the two atoms in parts which evolve under different portions of the Hamiltonian. We apply this method to the system under consideration to study the effect of the uncertainty in the position of the atoms on the dissipation rates and on the entanglement between the internal degrees of freedom of the two atoms. We find that the uncertainty in position can give rise to smaller dissipation rates. This in turn affects the entanglement which may decay exponentially with smaller decay rates or may even decay asymptotically by a power law.

  12. Effects of uncertainty in position on the dissipation rates and the entanglement of two atoms collectively interacting with a reservoir

    SciTech Connect

    Castanos, L. O.; Jauregui, R.

    2011-06-15

    We consider two two-level atoms interacting collectively with all the modes of the quantum electromagnetic field. The center-of-mass motion of each atom is quantized in three dimensions and each atom is placed in a harmonic oscillator potential. We describe a method that factorizes an approximate density operator of the two atoms in parts which evolve under different portions of the Hamiltonian. We apply this method to the system under consideration to study the effect of the uncertainty in the position of the atoms on the dissipation rates and on the entanglement between the internal degrees of freedom of the two atoms. We find that the uncertainty in position can give rise to smaller dissipation rates. This in turn affects the entanglement which may decay exponentially with smaller decay rates or may even decay asymptotically by a power law.

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

    NASA Astrophysics Data System (ADS)

    Plag, H.; Bye, B.

    2011-12-01

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

  14. Fluctuation enhanced electrochemical reaction rates at the nanoscale.

    PubMed

    García-Morales, Vladimir; Krischer, Katharina

    2010-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Heyne, Joshua S.

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

  16. 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.

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

    PubMed

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

    2014-01-01

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

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

    DOE PAGESBeta

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

    2014-01-01

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

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

    PubMed Central

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

    2014-01-01

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

  20. 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.

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

    NASA Technical Reports Server (NTRS)

    Eberstein, I. J.

    1974-01-01

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

  2. Upper atmosphere research: Reaction rate and optical measurements

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

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

    SciTech Connect

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

    1980-09-01

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

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

    SciTech Connect

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

    2013-11-07

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

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

    PubMed

    Peira, Nathalie; Fredrikson, Mats; Pourtois, Gilles

    2014-03-01

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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

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

    SciTech Connect

    Thanh, Vo Hong; Priami, Corrado

    2015-08-07

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

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

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

  10. 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).

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

    PubMed

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

    2012-08-01

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

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

    PubMed

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

    2010-06-01

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

  13. Key Rate Available from Mismatched Measurements in the BB84 Protocol and the Uncertainty Principle

    NASA Astrophysics Data System (ADS)

    Matsumoto, Ryutaroh; Watanabe, Shun

    We consider the mismatched measurements in the BB84 quantum key distribution protocol, in which measuring bases are different from transmitting bases. We give a lower bound on the amount of a secret key that can be extracted from the mismatched measurements. Our lower bound shows that we can extract a secret key from the mismatched measurements with certain quantum channels, such as the channel over which the Hadamard matrix is applied to each qubit with high probability. Moreover, the entropic uncertainty principle implies that one cannot extract the secret key from both matched measurements and mismatched ones simultaneously, when we use the standard information reconciliation and privacy amplification procedure.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  15. Revision of the 15N(p, γ)16O reaction rate and oxygen abundance in H-burning zones

    NASA Astrophysics Data System (ADS)

    Caciolli, A.; Mazzocchi, C.; Capogrosso, V.; Bemmerer, D.; Broggini, C.; Corvisiero, P.; Costantini, H.; Elekes, Z.; Formicola, A.; Fülöp, Zs.; Gervino, G.; Guglielmetti, A.; Gustavino, C.; Gyürky, Gy.; Imbriani, G.; Junker, M.; Lemut, A.; Marta, M.; Menegazzo, R.; Palmerini, S.; Prati, P.; Roca, V.; Rolfs, C.; Rossi Alvarez, C.; Somorjai, E.; Straniero, O.; Strieder, F.; Terrasi, F.; Trautvetter, H. P.; Vomiero, A.

    2011-09-01

    Context. The NO cycle takes place in the deepest layer of a H-burning core or shell, when the temperature exceeds T ≃ 30 × 106 K. The O depletion observed in some globular cluster giant stars, always associated with a Na enhancement, may be due to either a deep mixing during the red giant branch (RGB) phase of the star or to the pollution of the primordial gas by an early population of massive asymptotic giant branch (AGB) stars, whose chemical composition was modified by the hot bottom burning. In both cases, the NO cycle is responsible for the O depletion. Aims: The activation of this cycle depends on the rate of the 15N(p, γ)16O reaction. A precise evaluation of this reaction rate at temperatures as low as experienced in H-burning zones in stellar interiors is mandatory to understand the observed O abundances. Methods: We present a new measurement of the 15N(p, γ)16O reaction performed at LUNA covering for the first time the center of mass energy range 70-370 keV, which corresponds to stellar temperatures between 65 × 106 K and 780 × 106 K. This range includes the 15N(p, γ)16O Gamow-peak energy of explosive H-burning taking place in the external layer of a nova and the one of the hot bottom burning (HBB) nucleosynthesis occurring in massive AGB stars. Results: With the present data, we are also able to confirm the result of the previous R-matrix extrapolation. In particular, in the temperature range of astrophysical interest, the new rate is about a factor of 2 smaller than reported in the widely adopted compilation of reaction rates (NACRE or CF88) and the uncertainty is now reduced down to the 10% level.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2016-11-01

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

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

    SciTech Connect

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

    2000-01-20

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    SciTech Connect

    Judd, J.L.

    1981-12-01

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

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  4. 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.

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

    SciTech Connect

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

    1984-01-01

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

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

    SciTech Connect

    Skakun, Ye.; Rauscher, T.

    2010-08-12

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

  7. The branchings of the main s-process: their sensitivity to α-induced reactions on 13C and 22Ne and to the uncertainties of the nuclear network

    NASA Astrophysics Data System (ADS)

    Bisterzo, S.; Gallino, R.; Käppeler, F.; Wiescher, M.; Imbriani, G.; Straniero, O.; Cristallo, S.; Görres, J.; deBoer, R. J.

    2015-05-01

    This paper provides a detailed analysis of the main component of the slow neutron capture process (the s-process), which accounts for the solar abundances of half of the nuclei with 90 ≲ A ≲ 208. We examine the impact of the uncertainties of the two neutron sources operating in low-mass asymptotic giant branch (AGB) stars: the 13C(α, n)16O reaction, which releases neutrons radiatively during interpulse periods (kT ˜ 8 keV), and the 22Ne(α, n)25Mg reaction, partially activated during the convective thermal pulses (TPs). We focus our attention on the branching points that mainly influence the abundance of s-only isotopes. In our AGB models, the 13C is fully consumed radiatively during interpulse. In this case, we find that the present uncertainty associated with the 13C(α, n)16O reaction has marginal effects on s-only nuclei. On the other hand, a reduction of this rate may increase the amount of residual (or unburned) 13C at the end of the interpulse: in this condition, the residual 13C is burned at higher temperature in the convective zone powered by the following TP. The neutron burst produced by the 22Ne(α, n)25Mg reaction has major effects on the branches along the s-path. The contributions of s-only isotopes with 90 ≲ A ≤ 204 are reproduced within solar and nuclear uncertainties, even if the 22Ne(α, n)25Mg rate is varied by a factor of 2. Improved β-decay and neutron capture rates of a few key radioactive nuclides would help to attain a comprehensive understanding of the solar main component.

  8. 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.

  9. 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

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    ERIC Educational Resources Information Center

    Sroufe, L. Alan; And Others

    1973-01-01

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

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

    PubMed

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

    2014-06-01

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

  14. 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.

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

    PubMed

    Lizana, L; Bauer, B; Orwar, O

    2008-03-18

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

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

    SciTech Connect

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

    2007-10-26

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    SciTech Connect

    Lindquist, W Brent

    2009-03-03

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    SciTech Connect

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

    2009-02-06

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

  1. 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).

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

    SciTech Connect

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

    2011-09-10

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

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

    PubMed

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

    2003-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Thomsen, Kyle; Smith, Michael

    2011-10-01

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

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

    SciTech Connect

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

    1987-12-17

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

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

    SciTech Connect

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

    2015-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Anderson, Philip Neal

    1995-01-01

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

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

    SciTech Connect

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

    2014-06-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    SciTech Connect

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

    2014-08-01

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

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

    PubMed

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Vissapragada, Shreyas; Buzard, Cam; Miller, Kenneth A.; O'Connor, Aodh; De Ruette, Nathalie; Urbain, Xavier; Savin, Daniel Wolf

    2016-06-01

    We have incorporated our experimentally derived thermal rate coefficients for C + H3+ forming CH+ and CH2+ into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and use instead a more versatile fitting formula. At a temperature of 10 K and a density of 104 cm-3, we find no significant differences in the predicted abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. Additionally, we find that the relatively small error on our measurements (~15%) significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.

  14. Evaluating effective reaction rates of kinetically driven solutes in large-scale, anisotropic media: human health risk implications in CO2 leakage

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    The role of high and low hydraulic conductivity (K) regions in heterogeneous, stratified and non-stratified flow fields and the subsequent effect of rate dependent geochemical reactions are investigated with regards to mobilized arsenic from CO2 leakage at a Carbon Capture and Storage (CCS) site. Following the methodology of previous work, human health risk is used as an endpoint for comparison via a two-stage or nested Monte Carlo scheme, explicitly considering joint uncertainty and variability for a hypothetical population of individuals. This study identifies geo-hydrologic conditions where solute reactions are either rate limited (non-reactive), in equilibrium (linear equilibrium assumption, LEA, is appropriate), or are sensitive to time-dependent kinetic reaction rates. Potential interplay between multiple parameters (i.e. positive or negative feedbacks) is shown utilizing stochastic ensembles. In particular, the effect of preferential flow pathways and solute mixing on the field-scale (macrodispersion) and sub-grid (local dispersion) is examined for varying degrees of stratification and regional groundwater velocities. Results show effective reaction rates of kinetic ensembles are dissimilar from LEA ensembles with the inclusion of local dispersion, resulting in an additive tailing effect of the solute plume, a retarded peak time, and an increased cancer risk. This discrepancy between kinetic and LEA ensembles is augmented in highly anisotropic media, especially at intermediate regional groundwater velocities. The distribution, magnitude, and associated uncertainty of cancer risk are controlled by these factors, but are also strongly dependent on the regional groundwater velocity. We demonstrate a higher associated uncertainty of cancer risk in stratified domains is linked to higher aquifer connectivity and less macrodispersion in the flow field. This study has implications in CCS site selection and groundwater driven risk assessment modeling.

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

    NASA Astrophysics Data System (ADS)

    Meisel, Zachary

    2008-10-01

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

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

    EPA Science Inventory

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

  17. 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.

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

    DOEpatents

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

    2006-05-16

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

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

    PubMed

    Baxter; DePaolo

    2000-05-26

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

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  1. 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.

  2. 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.

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

    SciTech Connect

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

    2007-03-15

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

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

    PubMed

    Tsujiuchi, Yutaka; Masumoto, Hiroshi; Goto, Takashi

    2016-04-01

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

  5. Laboratory Measurement of the Gas-Phase Rate Constant for Formation of Nitric Acid from the Reaction of OH and NO2

    NASA Astrophysics Data System (ADS)

    Mollner, A. K.; Feng, L.; Sprague, M. K.; Okumura, M.; Vallavudasan, S.; Sander, S. P.; Martien, P. T.; Harley, R. A.; McCoy, A. B.

    2007-12-01

    The rate constant for the reaction OH + NO2 + M → HONO2 + M is among the most influential parameters affecting air pollution levels. There remains significant uncertainty about this rate, due to lack of laboratory data at 1 atm and to the unknown yield of a secondary channel forming peroxynitrous acid (HOONO). New experimental measurements of both the kinetics and HOONO/HONO2 branching ratios at 760 Torr are presented. The results are compared with current recommendations; when incorporated in models, the new parameters lead to significantly higher modeled ozone levels and reduced formation of nitric acid.

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

    NASA Astrophysics Data System (ADS)

    Reilinger, R. E.; McClusky, S.

    2008-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    PubMed

    Piccini, GiovanniMaria; Alessio, Maristella; Sauer, Joachim

    2016-04-18

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

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

    PubMed Central

    Piccini, GiovanniMaria; Alessio, Maristella

    2016-01-01

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

  11. Satellite Rainfall Uncertainty Estimation by Mathematical Models Using Geophysical Features and Rainfall Rate

    NASA Astrophysics Data System (ADS)

    Gebregiorgis, A. S.; Hossain, F.

    2012-12-01

    This study addresses the estimation of error variance of three satellite rainfall products: i) Tropical Rainfall Measuring Mission (TRMM) Multi-satellite Precipitation Analysis (TMPA) product of 3B42RT; ii) Climate Prediction Center (CPC) Morph (CMORPH); and iii) Precipitation Estimation from Remotely Sensed Information using Artificial Neural Networks - Cloud Classification System (PERSIANN-CCS). Nonlinear regression model is used to fit the response variable (satellite rainfall error variance) with explanatory variable (satellite rainfall rate) by grouping them as function of three key geophysical features: topography, climate, and season. The results of the study suggest that the error variance of a rainfall product is strongly correlated with rainfall rate and can be expressed as a power-law function. The geophysical feature based error classification analysis helps in achieving superior functional accuracy for prognostic error variance quantification in the absence of ground truth data. The multiple correlation coefficients between the estimated and observed error variance over an independent validation region (Upper Mississippi River basin) and time period (2007 - 2010) are found to be 0.75, 0.86, and 0.87 for 3B42RT, CMORPH, and PERSIANN-CCS products, respectively. In another validation region (Arkansas-Red River basin), the correlation coefficients are 0.59, 0.89, and 0.92 for the same products, respectively. Results of the assessment of error variance models reveal that the type of error component present in a satellite rainfall product directly impacts on the accuracy of estimated error variance. The model estimates the error variance more accurately when the precipitation error components are mostly hit bias or false precipitation, while for a product with extensive missed precipitation, the accuracy of estimated error variance is significantly compromised. The study clearly demonstrates the feasibility of quantifying the error variance of satellite

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  16. 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.

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

    SciTech Connect

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

    1985-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Newton, Joseph; Longland, Richard; Iliadis, Christian

    2009-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

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

    SciTech Connect

    Ishikawa, Souichi

    2012-11-12

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

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

    NASA Astrophysics Data System (ADS)

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

    1998-03-01

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

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

    SciTech Connect

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

    2009-07-15

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

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

    SciTech Connect

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

    1991-01-05

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

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

    NASA Astrophysics Data System (ADS)

    Hullar, T.; Anastasio, C.

    2015-12-01

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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2004-08-01

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

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

    PubMed

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

    2015-11-01

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

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

    SciTech Connect

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

    1996-07-01

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

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

    SciTech Connect

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

    2013-03-15

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

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

    PubMed

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

    2014-02-27

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Markelj, Jernej; Pompe, Matevž

    2016-04-01

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

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed

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

    2014-06-28

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

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

    SciTech Connect

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

    2015-08-01

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

  17. Element synthesis calculations for stellar explosions: robust uncertainties, sensitivities, and radioactive ion beam measurements

    NASA Astrophysics Data System (ADS)

    Smith, Michael S.; Hix, W. Raphael; Parete-Koon, Suzanne; Dessieux, Luc; Ma, Zhanwen; Starrfield, Sumner; Bardayan, Daniel W.; Guidry, Michael W.; Smith, Donald L.; Blackmon, Jeffery C.; Mezzacappa, Anthony

    2004-12-01

    We utilize multiple-zone, post-processing element synthesis calculations to determine the impact of recent ORNL radioactive ion beam measurements on predictions of novae and X-ray burst simulations. We also assess the correlations between all relevant reaction rates and all synthesized isotopes, and translate nuclear reaction rate uncertainties into abundance prediction uncertainties, via a unique Monte Carlo technique.

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

    PubMed

    Wróbel, Rafał; Arabczyk, Walerian

    2006-07-27

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

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

    SciTech Connect

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

    2015-07-15

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

  20. 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.

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

    PubMed

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

    2016-01-21

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

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

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Leu, M. T.

    1985-01-01

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

  3. 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.

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

    PubMed

    Meisner, Jan; Kästner, Johannes

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Meisner, Jan; Kästner, Johannes

    2016-05-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Lopez, Evelyn; Simon, Sindee L.

    2015-03-01

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

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

    SciTech Connect

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

    1992-06-25

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

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

    ERIC Educational Resources Information Center

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

    2007-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Handley, Caroline

    2015-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Brooke, George M., IV

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

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

    DOE R&D Accomplishments Database

    Marcus, R. A.

    1964-01-01

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

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

    SciTech Connect

    Karraker, D.G.

    2001-03-28

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

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

    ERIC Educational Resources Information Center

    Kingir, Sevgi; Geban, Omer

    2012-01-01

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

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

    SciTech Connect

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

    1980-01-01

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

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

    SciTech Connect

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

    2015-08-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

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

    USGS Publications Warehouse

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-06-01

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

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

    PubMed

    Habershon, Scott

    2016-04-12

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

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

    NASA Technical Reports Server (NTRS)

    Torr, D. G.

    1979-01-01

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

  3. 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.

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

    SciTech Connect

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

    2015-01-15

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

  5. 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

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

    SciTech Connect

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

    2011-03-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

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

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

    USGS Publications Warehouse

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

    1984-01-01

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

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

    PubMed

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

    2015-08-14

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

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

    PubMed

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

    2007-04-01

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

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

    SciTech Connect

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

    1998-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

    Ren, Hongjiang; Li, Xiaojun

    2015-12-01

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

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

    SciTech Connect

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

    2006-06-01

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

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

    SciTech Connect

    Funaki, Yasuro; Yabana, Kazuhiro; Akahori, Takahiko

    2012-11-12

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

  17. 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.

  18. 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.

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

    PubMed Central

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

    2015-01-01

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

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

    SciTech Connect

    Beste, Ariana; Buchanan III, A C

    2010-01-01

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

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

    SciTech Connect

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

    2015-02-24

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Wojnárovits, László; Takács, Erzsébet

    2014-03-01

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

  5. Rate constants for reactions between atmospheric reservoir species. 2. H sub 2 O

    SciTech Connect

    Hatakeyama, Shiro; Leu, Mingtaun )

    1989-07-27

    The kinetics of the reactions of H{sub 2}O with ClONO{sub 2}, N{sub 2}O{sub 5}, O{sub 3}, and COCl{sub 2} have been investigated by using a large-volume static cell and a Fourier transform infrared spectrometer at 296 K. Upper limits for the homogeneous gas-phase reaction rate constants of the ClONO{sub 2} + H{sub 2}O, N{sub 2}O{sub 5} + H{sub 2}O, O{sub 3} + H{sub 2}O, and COCl{sub 2} + H{sub 2}O reactions were found to be 3.4 {times} 10{sup {minus}21}, 2.8 {times} 10{sup {minus}21}, 1.1 {times} 10{sup {minus}22}, and 1.2 {times} 10{sup {minus}23}, respectively (all in units of cm{sup 3} s{sup {minus}1}), based on the observed decay rates of ClONO{sub 2}, N{sub 2}O{sub 5}, O{sub 3}, and COCl{sub 2}. Product analyses gave 0.82 {plus minus} 0.07 for the yield of HNO{sub 3} in the ClONO{sub 2} + H{sub 2}O {yields} HOCl + HNO{sub 3} reaction and 1.1 {plus minus} 0.3 for the yield of HNO{sub 3} from the N{sub 2}O{sub 5} + H{sub 2}O {yields} 2HNO{sub 3} reaction. The quoted error represents one standard deviation of the measurement. An attempt was also made to monitor possible reaction products such as H{sub 2}O{sub 2} for the O{sub 3} + H{sub 2}O reaction, and CO{sub 2} or HCl for the COCl{sub 2} + H{sub 2}O reaction. These results may be important in the elucidation of the springtime Antarctic ozone depletion over the past decade. The implication for NO{sub x} chemistry in the nighttime troposphere based on their results of the N{sub 2}O{sub 5} + H{sub 2}O reaction will be discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

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

    PubMed

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

    2014-09-01

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

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

    SciTech Connect

    Parikh, A.; Faestermann, Th.; Kruecken, R.; Bildstein, V.; Bishop, S.; Eppinger, K.; Herlitzius, C.; Lepyoshkina, O.; Maierbeck, P.; Seiler, D.; Wimmer, K.; Hertenberger, R.; Wirth, H.-F.; Fallis, J.; Hager, U.; Hutcheon, D.; Ruiz, Ch.; Buchmann, L.; Ottewell, D.; Freeman, B.

    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 the 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.

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

    PubMed Central

    2015-01-01

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

  10. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension

    NASA Astrophysics Data System (ADS)

    Greene, Samuel M.; Shan, Xiao; Clary, David C.

    2016-06-01

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.

  11. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension.

    PubMed

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2016-06-28

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods. PMID:27369506

  12. Investigation of Mixing and Chemical Reaction Interactions Using Rate-Controlled Constrained-Equilibrium

    NASA Astrophysics Data System (ADS)

    Hadi, Fatemeh; Janbozorgi, Mohammad; Sheikhi, Reza H.; Metghalchi, Hameed

    2014-11-01

    The Rate-Controlled Constrained-Equilibrium (RCCE) method is applied to study the interaction between mixing and chemical reaction in a constant pressure Partially-Stirred Reactor (PaSR). The objective is to understand the influence of mixing on RCCE predictions. The RCCE is a computationally efficient method based on thermodynamics to implement the combustion chemistry. In the RCCE the dynamics of reacting systems is described by a small number of rate-controlling reactions and slowly-varying constraints. The method is applied to study methane combustion via 12 constraints and 133 reaction steps. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The RCCE predictions are assessed by comparing with those of detailed kinetics model, in which the same kinetics, involving 29 species and 133 reaction steps, is integrated directly. Chemical kinetics and mixing interactions are studied for different residence and mixing time scales. Results show that the RCCE accurately represents the effect of mixing with different mixing strengths. An assessment of numerical performance of the RCCE is also performed. It is shown that the method is effective to reduce the stiffness of the kinetics and thus allows simulations with much lower computation costs.

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

    SciTech Connect

    Peters, Catherine A

    2013-02-28

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

  14. Rate of reactions between D 2O and Ca xAl yO z

    NASA Astrophysics Data System (ADS)

    Christensen, A. Nørlund; Lehmann, M. S.

    1984-02-01

    The rate of the reaction between D 2O and the calcium aluminum oxides Ca 3Al 2O 6, Ca 5Al 6O 14, CaAl 2O 4, and CaAl 4O 7 was investigated by on-line neutron diffraction powder methods at temperatures from room temperature to 100°C. The rate of the reaction increases with increasing calcium content of the compounds and with increasing temperature for each of the compounds. The crystallographic stable hydrate Ca 3Al 2(OD) 12 is obtained from CaAl 4O 7 and CaAl 2O 4 at temperatures above 63°C, from Ca 5Al 6O 14 at temperatures above 49°C, and from Ca 3Al 2O 6 at temperatures as low as 7°C.

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

    SciTech Connect

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-12-09

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

  16. Absolute rate of the reaction of bromine atoms with ozone from 200-360 K

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

    The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at lambda 165nm.O3 was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3, total pressure and limited variations in flash intensity. The measured rate constants obeyed the Arrhenius expression, where the error quoted is two standard deviations. Results are compared with previous determinations which employed the discharge flow-mass spectrometric technique.

  17. Absolute rate of the reaction of bromine atoms with ozone from 200 to 360 K

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

    The rate constant for the reaction Br + O3 yields BrO + O2 has been measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at a wavelength of 165 nm. O3 concentration was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3 concentration, total pressure (Ar), and limited variations in flash intensity (i.e., initial Br concentration). The measured rate constants obey the Arrhenius expression, k = (7.74 plus or minus 0.50) x 10 to the -12th exp(-603 plus or minus 16/T) cu cm/molecule/sec, where the error quoted is two standard deviations.

  18. Absolute rate parameters for the reaction of atomic hydrogen with hydrazine

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Payne, W. A.

    1976-01-01

    Absolute rate parameters for the reaction of atomic hydrogen with hydrazine H + N2H4 yields H2 + N2H3 have been determined in a direct manner using flash photolysis of dilute mixtures of hydrazine in helium and time dependent observation of H via resonance fluorescence. By measuring the H-atom decay under pseudo-first-order conditions, the bimolecular rate constant K sub 1 was obtained over the temperature range 228-400 K. The data were fitted with good linearity to the Arrhenius expression K sub 1 = (9.87 plus or minus 1.17) x 10 to the -12th exp(-2380 plus or minus 100/RT) cu cm/molecule/s. The data were shown to be free of any contributions from secondary reactions involving H as a reactant or product.

  19. 23Na (α,p )26Mg Reaction Rate at Astrophysically Relevant Energies

    NASA Astrophysics Data System (ADS)

    Howard, A. M.; Munch, M.; Fynbo, H. O. U.; Kirsebom, O. S.; Laursen, K. L.; Diget, C. Aa.; Hubbard, N. J.

    2015-07-01

    The production of 26Al in massive stars is sensitive to the 23Na (α,p )26Mg cross section. Recent experimental data suggest the currently recommended cross sections are underestimated by a factor of ˜40 . We present here differential cross sections for the 23Na (α,p )26Mg reaction measured in the energy range Ec .m .=1.7 - 2.5 MeV . Concurrent measurements of Rutherford scattering provide absolute normalizations that are independent of variations in target properties. Angular distributions are measured for both p0 and p1 permitting the determination of total cross sections. The results show no significant deviation from the statistical model calculations upon which the recommended rates are based. We therefore retain the previous recommendation without the increase in cross section and resulting stellar reaction rates by a factor of 40, impacting the 26Al yield from massive stars by more than a factor of 3.

  20. Computational Approach for Ranking Mutant Enzymes According to Catalytic Reaction Rates

    PubMed Central

    Kumarasiri, Malika; Baker, Gregory A.; Soudackov, Alexander V.

    2009-01-01

    A computationally efficient approach for ranking mutant enzymes according to the catalytic reaction rates is presented. This procedure requires the generation and equilibration of the mutant structures, followed by the calculation of partial free energy curves using an empirical valence bond potential in conjunction with biased molecular dynamics simulations and umbrella integration. The individual steps are automated and optimized for computational efficiency. This approach is used to rank a series of 15 dihydrofolate reductase mutants according to the hydride transfer reaction rate. The agreement between the calculated and experimental changes in the free energy barrier upon mutation is encouraging. The computational approach predicts the correct direction of the change in free energy barrier for all mutants, and the correlation coefficient between the calculated and experimental data is 0.82. This general approach for ranking protein designs has implications for protein engineering and drug design. PMID:19235997

  1. Hydrolysis of lanthanide dicarbides: Rates of reaction of cubic and tetragonal solid solutions with water

    SciTech Connect

    McColm, I.J. )

    1993-05-01

    Two series of solid solutions, Ho[sub 1[minus]x]La[sub x]C[sub 2] and Nd[sub 1[minus]x]LaC[sub 2], have been made and their X-ray unit cell parameters measured. The Ho[sub 1[minus]x]La[sub x]C[sub 2] series contains two tetragonal phases and a cubic solid solution series which has enabled the reaction rate constants for the water hydrolysis reaction of a cubic dicarbide phase to be determined for the first time. By comparing the linear rate constants and the activation energies across the two series the nature of bonding in general and the structure of the cubic phase are elucidated. A comparison with microhardness data is made and the change in M-C[sub 2] bonding as a function of composition is considered. 10 refs., 9 figs., 3 tabs.

  2. Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

    The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

  3. Quantitative determination of the steady-state kinetics of multienzyme reactions using the algebraic rate equations for the component single-enzyme reactions.

    PubMed Central

    Stoner, C D

    1993-01-01

    Methods are given whereby the steady-state kinetic characteristics of multienzyme reactions consisting of individual single-enzyme reactions linked by freely diffusible intermediates can be determined quantitatively from the experimentally determined complete algebraic rate equations for the individual reactions. The approach is based on the fact that a valid steady-state rate equation for such a multienzyme reaction, in terms of the rate equations for the individual reactions, can be obtained simply from knowledge of the relative rates of the individual reactions when the multienzyme reaction is in the steady state. A number of model multienzyme reactions, which differ as to structural arrangement of the individual reactions, are examined by this approach. Simple mathematical methods which are applicable to most of these models are given for direct calculation of dependent variables. It is either pointed out or demonstrated with Mathematica that the rate equations for all of these models can be handled very easily with the aid of a personal computer equipped with appropriate equation-solving software. Since the approach permits evaluation of all dependent variables for any specific combination of values for the kinetic parameters and independent variables, numerical values for the flux control coefficients of the individual enzymes can be obtained by direct calculation for a wide variety of conditions and can be compared with those obtained according to the methods of Metabolic Control Analysis. Several such comparisons have been made and in all cases identical results were obtained. The intuitive notion that the individual enzymes of a multienzyme reaction would be equally rate limiting if the total amount of enzyme were being used with maximum efficiency is tested and shown to be incorrect. In the course of this test the flux control coefficient for the individual enzymes were found to be appropriate indicators of relative rate limitation or control by the

  4. Turnover rate, reaction order, and elementary steps for the hydrodechlorination of chlorofluorocarbon compounds on palladium catalysts

    SciTech Connect

    Thompson, C.D.; Rioux, R.M.; Chen, N.; Ribeiro, F.H.

    2000-04-13

    The rates of hydrodechlorination catalyzed by Pd supported on carbon for four chlorofluorocarbons spanned a range of 7 orders of magnitude. The rates scaled up to the bond strength of the carbon-chlorine bond for the gas-phase reactant. This finding demonstrates that the rate-determining step involves the scission of the C-Cl bond and suggests, through Polanyi and linear free-energy relationships, that rates for other compounds can be estimated if the C-Cl bond strength is known. The reaction orders for the most abundant products are approximately first-order for the chlorine-containing compound, half-order in H{sub 2}, and inverse first-order in HCl. The reaction steps consistent with these orders include a rate-determining step involving the adsorption of the chlorofluorocarbon to a single site (which could be a single surface palladium atom) and equilibrated steps between gas-phase H{sub 2}, gas-phase HCl, and adsorbed hydrogen and chlorine atoms. The rates on the supported catalysts are comparable to the ones reported before on a Pd foil, indicating that the support does not play a role in the reaction. The product distribution is independent of conversion, implying that the various products are formed from a single visit of the reactant on the surface and not from readsorption of gas-phase products. The four compounds studied were chloropentafluoroethane (CF{sub 3}-CF{sub 2}Cl), 2-chloro-1,1,1,2-tetrafluoroethane (CF{sub 3}-CFClH), 1,1-dichlorotetrafluoroethane (CF{sub 3}-CFCl{sub 2}), and 1,1,1-trichloro-2,2,2-trifluoroethane (CF{sub 3}-CCl{sub 3}).

  5. A Review of the Thermodynamic, Transport, and Chemical Reaction Rate Properties of High-temperature Air

    NASA Technical Reports Server (NTRS)

    Hansen, C Frederick; Heims, Steve P

    1958-01-01

    Thermodynamic and transport properties of high temperature air, and the reaction rates for the important chemical processes which occur in air, are reviewed. Semiempirical, analytic expressions are presented for thermodynamic and transport properties of air. Examples are given illustrating the use of these properties to evaluate (1) equilibrium conditions following shock waves, (2) stagnation region heat flux to a blunt high-speed body, and (3) some chemical relaxation lengths in stagnation region flow.

  6. Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

    Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically.

  7. 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.

  8. 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.

  9. Rate of the reaction of atomic hydrogen with propyne over an extended pressure and temperature range

    NASA Technical Reports Server (NTRS)

    Whytock, D. A.; Payne, W. A.; Stief, L. J.

    1976-01-01

    The technique of flash photolysis coupled with time resolved detection of H via resonance fluorescence has been used to obtain rate constants for the reaction of atomic hydrogen with propyne at temperatures from 215 to 460 K and at pressures in the range 5-600 torr. The rate constants are strongly pressure dependent and the high pressure limiting values give rise to the Arrhenius expression K = approximately 6 x 10 to the minus 11th exp(-2450T) cu cm per molecule per sec. The results are discussed and compared with those of previous studies

  10. Foaming and the Rate of the Carbon-Iron Oxide Reaction in Slag

    NASA Astrophysics Data System (ADS)

    Corbari, Rodrigo; Matsuura, Hiroyuki; Halder, Sabuj; Walker, Matthew; Fruehan, Richard J.

    2009-12-01

    Foaming in the electric arc furnace is achieved by injecting carbon into slag, where the resulting reaction of the carbon with FeO dissolved in the slag generates gas (CO) that causes the slag to foam. In this research, the rate of the reaction of FeO in slag with carbon and the resulting foam height were measured. In these experiments, the FeO content of the slag ranged from 15 to 45 mass pct, and several different types of carbon were used including graphite, coals, and chars. The rate of the slag-carbon reaction and the consequent CO generation increased with FeO content of the slag from 15 to 45 mass pct. However, the slag foam height reached a maximum at about 25 mass pct FeO and decreased at higher FeO contents. The decrease in foaming is apparently due to a decrease in the foam index or foamability caused by a decrease in viscosity and an increase in density of the slag with FeO content. The results of this work indicate that the foam height is influenced more significantly by the decrease in the foam index compared to the increase in the CO gas generation rate at higher FeO contents. The decrease in the foam index with FeO agrees with that predicted from the slag properties.

  11. 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.

  12. Rate and product measurements for the reactions of OH with I/sub 2/ and ICl at 298 K: separation of gas-phase and surface reaction components

    SciTech Connect

    Loewenstein, L.M.; Anderson, J.G.

    1985-12-05

    The kinetic behavior of OH with I/sub 2/ and ICl is reported within the context of a series of radical-halogen reactions to investigate the mechanism of such reactions through studies of reactivity trends. Atomic I and Cl products of the title reactions are measured by resolved resonance fluorescence vapor lamps. IO and ClO are detected by chemically converting them, using NO, to I and Cl, respectively. The rate constant of the reaction H + ICl has been measured at 298 K; its only product channel is I + HCl. Magnitudes of the rate constants of these OH reactions substantiate the reactivity trends in the OH-halogen system based on an electron-transfer mechanism from the highest occupied molecular orbital of the halogen to the lowest unoccupied orbital of the hydroxyl. The rapidity of the OH + I/sub 2/ reaction makes it a possible source of HOI for photochemical studies. 31 references, 11 figures, 2 tables.

  13. A reinvestigation of the rate of the C/+/ + H2 radiative association reaction. [interstellar chemistry

    NASA Technical Reports Server (NTRS)

    Herbst, E.

    1982-01-01

    It is noted that new experimental results and statistical theories have prompted a reinvestigation of the rate coefficient of the interstellar reaction in which C(+) + H2 yields CH2(+) + h(nu) in the 10-100 K temperature range. The results presented here indicate a rate coefficient between 10 to the -16 and 10 to the -15 cu cm/s at all temperatures studied. In applying the modified thermal and phase space theories, it is expected that they will be as accurate as for radiative association as for three-body association, provided the ab initio value for the radiative decay rate is correct. It is expected that the calculated values of the rate coefficient will be accurate to within an order of magnitude and will have the correct temperature dependence.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  16. Assessing the Effects of New Reaction Rates and Convection Theory on Studies of Supernova Progenitors

    NASA Astrophysics Data System (ADS)

    Starrfield, Sumner

    We request funding to carry out a systematic evaluation of nuclear reaction rates and convection on the pre-explosion evolution of core-collapse (SN II) and thermonuclear (SN Ia) supernovae. We will use MESA (Modules for Experiments in Stellar Astrophysics) a new stellar evolution computer code that is co-authored by Co-PI Timmes. One goal of this proposal is to determine the effects of new thermonuclear reaction rates, taken from the next-generation library STARLIB developed by Co-PI Iliadis, on the resulting evolution. Another goal is to test the effects of the latest convection theory, microphysics changes, and numerical techniques on the results. STARLIB is a first-of-its-kind nuclear reaction rate library and, unlike all other libraries, it contains the full reaction rate probability densities at all stellar temperatures. It is publicly available as of June 2013. Consequently, we are now in a unique position to model stellar evolution and nucleosynthesis in a quantitative manner that makes predictions for key observations by NASA ground-based and satellite observatories. We will use two complementary strategies. First, we will take the modern and multiple prescriptions of convection that are implemented in MESA, together with the recommended thermonuclear reaction rates provided by STARLIB, to generate new hydrodynamic simulations of SN Ia and SN II progenitor evolution. Second, we will take the temperature-density-time trajectories from the evolutionary results and do Monte Carlo post-processing nucleosynthesis calculations by sampling over the reaction rate probability densities. This procedure could not be applied previously and has only become feasible with the availability of STARLIB. Calculations of pre-supernova evolution with the STARLIB reaction rates and new convection prescriptions will provide, for the first time, statistically rigorous estimates for both their evolutionary structures and resulting nucleosynthesis. Significant insight into pre

  17. Impact of a Revised 25Mg(p, γ)26Al Reaction Rate on the Operation of the Mg-Al Cycle

    NASA Astrophysics Data System (ADS)

    Straniero, O.; Imbriani, G.; Strieder, F.; Bemmerer, D.; Broggini, C.; Caciolli, A.; Corvisiero, P.; Costantini, H.; Cristallo, S.; DiLeva, A.; Formicola, A.; Elekes, Z.; Fülöp, Zs.; Gervino, G.; Guglielmetti, A.; Gustavino, C.; Gyürky, Gy.; Junker, M.; Lemut, A.; Limata, B.; Marta, M.; Mazzocchi, C.; Menegazzo, R.; Piersanti, L.; Prati, P.; Roca, V.; Rolfs, C.; Rossi Alvarez, C.; Somorjai, E.; Terrasi, F.; Trautvetter, H.-P.

    2013-02-01

    Proton captures on Mg isotopes play an important role in the Mg-Al cycle active in stellar H-burning regions. In particular, low-energy nuclear resonances in the 25Mg(p, γ)26Al reaction affect the production of radioactive 26Algs as well as the resulting Mg/Al abundance ratio. Reliable estimations of these quantities require precise measurements of the strengths of low-energy resonances. Based on a new experimental study performed at the Laboratory for Underground Nuclear Astrophysics, we provide revised rates of the 25Mg(p, γ)26Algs and the 25Mg(p, γ)26Al m reactions with corresponding uncertainties. In the temperature range 50-150 MK, the new recommended rate of 26Al m production is up to five times higher than previously assumed. In addition, at T = 100 MK, the revised total reaction rate is a factor of two higher. Note that this is the range of temperature at which the Mg-Al cycle operates in a H-burning zone. The effects of this revision are discussed. Due to the significantly larger 25Mg(p, γ)26Al m rate, the estimated production of 26Algs in H-burning regions is less efficient than previously obtained. As a result, the new rates should imply a smaller contribution from Wolf-Rayet stars to the galactic 26Al budget. Similarly, we show that the asymptotic giant branch (AGB) extra-mixing scenario does not appear able to explain the most extreme values of 26Al/27Al, i.e., >10-2, found in some O-rich presolar grains. Finally, the substantial increase of the total reaction rate makes the hypothesis of self-pollution by massive AGBs a more robust explanation for the Mg-Al anticorrelation observed in globular-cluster stars.

  18. Reaction rate of a composite core-shell nanoreactor with multiple nanocatalysts.

    PubMed

    Galanti, Marta; Fanelli, Duccio; Angioletti-Uberti, Stefano; Ballauff, Matthias; Dzubiella, Joachim; Piazza, Francesco

    2016-07-27

    We present a detailed theory for the total reaction rate constant of a composite core-shell nanoreactor, consisting of a central solid core surrounded by a hydrogel layer of variable thickness, where a given number of small catalytic nanoparticles are embedded at prescribed positions and are endowed with a prescribed surface reaction rate constant. Besides the precise geometry of the assembly, our theory accounts explicitly for the diffusion coefficients of the reactants in the hydrogel and in the bulk as well as for their transfer free energy jump upon entering the hydrogel shell. Moreover, we work out an approximate analytical formula for the overall rate constant, which is valid in the physically relevant range of geometrical and chemical parameters. We discuss in depth how the diffusion-controlled part of the rate depends on the essential variables, including the size of the central core. In particular, we derive some simple rules for estimating the number of nanocatalysts per nanoreactor for an efficient catalytic performance in the case of small to intermediate core sizes. Our theoretical treatment promises to provide a very useful and flexible tool for the design of superior performing nanoreactor geometries with optimized nanoparticle load. PMID:27411947

  19. Characterization of the reaction rate coefficient of DNA with the hydroxyl radical

    SciTech Connect

    Milligan, J.R.; Ward, J.F.; Aguilera, J.A.

    1996-11-01

    Using agarose gel electrophoresis, we have measured the yield of single-strand breaks (SSBs) induced by {sup 137}Cs {gamma} irradiation in a variety of plasmid DNA substrates ranging in size from 2.7 kb to 38 kb irradiated in aerobic aqueous solution in the presence of the hydroxyl radical scavenger dimethyl sulfoxide (DMSO). Under these conditions DNA SSBs are caused mainly by the hydroxyl radical. Using the competition between DMSO and DNA for the hydroxyl radical, we have estimated the rate coefficient for the reaction of the hydroxyl radical with DNA. The results cannot be characterized by conventional steady-state competition kinetics. However, it is possible to describe the second-order rate constant for the reaction as a function of the scavenging capacity of the solution. The second-order rate constant increases with increasing scavenging capacity, rising from about 5x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 5} s{sup -1} to about 10{sup 10} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 10} s{sup -1}. This dependence of the second-order rate constant on the scavenging capacity appears to be more pronounced for larger plasmids. 17 refs., 4 figs.

  20. Equation of state and reaction rate for condensed-phase explosives

    NASA Astrophysics Data System (ADS)

    Wescott, B. L.; Stewart, D. Scott; Davis, W. C.

    2005-09-01

    The wide-ranging equation of state is a nonideal equation of state based on empirical fitting forms argued from thermodynamic considerations that yield the proper physical features of detonation. The complete equation of state forms are presented and the equation of state and a reaction rate are calibrated for the condensed-phase explosive PBX-9502. Experimental overdriven Hugoniot data are used to calibrate the products equation of state off the principal isentrope passing through the Chapman-Jouguet state. Shock Hugoniot data are used to calibrate the reactants equation of state. The normal detonation shock speed-shock curvature data (Dn-κ) from rate-stick measurements and shock initiation data from wedge tests are used to calibrate the reaction rate. Simulations are carried out that predict detailed particle velocity transients that are measured experimentally with embedded electromagnetic gauge measurements from gas-gun experiments. Multidimensional simulations of steady detonation in a right circular cylinder rate stick are carried out and compared with experiment.

  1. Nova Nucleosynthesis with a New 18F(p,alpha) Reaction Rate

    NASA Astrophysics Data System (ADS)

    Smith, Michael; Kozub, Raymond; Brune, Carl; Starrfield, Sumner

    2005-04-01

    The long-lived radionuclide ^18F is synthesized in nova outbursts and its decay may serve as an observational tracer of the explosion mechanism. Because the ^18F(p,α)^15O reaction is the dominant destruction mechanism for ^18F, the flux of gamma rays from ^18F decay is very sensitive to the rate of this reaction. A revised ^18F(p,α)^15O rate was determined from recent ORNL measurements of ^1H(^18F,p)^18F and ^2H(^18F,p)^19F, combined with a reanalysis of archival ^15N(α,α)^15N data. We used this new rate in nova element synthesis calculations and compared new predictions of the synthesized abundance ^18F (and other nuclides) to that obtained using the two most recent (p,α) rates. We used a post- processing approach with temperature and density histories of 28 zones of ejected material determined from separate hydrodynamics calculations. The implications for satellite observations of novae will be discussed. These calculations were performed and visualized with the Computational Infrastructure for Nuclear Astrophysics, an online suite of codes available at nucastrodata.org.

  2. 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.

  3. Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

    NASA Technical Reports Server (NTRS)

    DeMore, W.B.

    1996-01-01

    Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

  4. Reaction kinetics, P-T-t paths and rates of tectonic processes

    SciTech Connect

    Bohlen, S.R.; Hankins, W.B.; Eckert, J.O. Jr.; Kirby, S.H.; Liu, J. ); Hacker, B.R.; Mosenfelder, J.L. . Dept. of Geology)

    1992-01-01

    The interpretation of portions of P-T-time (t) paths in metamorphic rocks assumes that continuous and discontinuous reactions record local equilibrium as P-T conditions change, implying that the kinetics of many reactions are rapid relative to dT/dt and dP/dt. Occurrence of eclogite veins in granulites from Bergen, Norway as well as occurrences of coesite and diamond in crustal rocks imply that, under certain conditions, this assumption is wrong. Knowledge of the kinetics of important reactions under appropriate conditions would provide limits on the duration of relatively narrowly defined P-T conditions, allow inference of the rates of exhumation of rocks containing high-pressure phases, and allow the calculation of the time required for the conversion of gabbro to eclogite in the lower crust as a function of P-T-t. The authors are currently assessing the rates of key phase transformations: calcite to aragonite, albite to jadeite + quartz, coesite to quartz, opx[sub Fs[sup 80

  5. Effective reaction rate for porous surfaces under strong shear: Beyond Damkohler

    NASA Astrophysics Data System (ADS)

    Shaqfeh, Eric S. G.; Shah, Preyas

    2014-11-01

    Traditonally, surface reactive porous media are modeled via an effective reaction/mass transfer rate based on the original ansatz of Damkohler, i.e, reaction limited transport at the microscale in the absence of flow. We are interested in modeling the microscale mass transfer to porous surfaces occuring in leaky tumor vasculature, where the Damkohler number can be O(1) and the Peclet number may be large. We model it as a uniform bath of a species in unbound shear flow over a wall with first order reactive circular patches (pores). We analyze the flux through a single pore using both analytic and boundary element simulations and observe the formation of a 3-D depletion region (wake) downstream of the pore. Wake sharing between adjacent pores in a multibody setting such as 2 pores aligned in the shear direction leads to a smaller flux per pore. Obtaining this interaction length scale and using the renormalized periodic Green's function, we study the flux through a periodic and disordered distribution of pores. This flux appears as the reaction rate in an effective boundary condition, valid up to non-dilute pore area fractions, and applicable at a wall-normal effective slip distance. It replaces the details of the surface and can be used directly in large scale physics simulations.

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

    SciTech Connect

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

    1987-04-23

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

  7. Contribution of 19F resonances on 18O( p, α)15N reaction rate

    NASA Astrophysics Data System (ADS)

    Benmeslem, Meriem; Chafa, Azzedine; Barhoumi, Slimane; Tribeche, Mouloud

    2014-08-01

    The 18O( p, α)15N reaction influences the isotopes production such as 19F, 18O, and 15N which can be used to test the models of stellar evolution. 19F is synthesized in both asymptotic giant branch (AGB) and metal-rich Wolf-Rayet (WR) stars. Using R-matrix theory we allow new values of resonances parameters in 19F. We show that the most important contribution to the differential and total cross section at low energies, comes from the levels in 19F situated at resonances energies E R =151, 680 and 840 keV with spin and parity 1/2+. The total width of the 680 keV resonance is badly known. So, we have focused on this broad resonance corresponding to the 8.65 MeV level in 19F. We delimit the temperature range in which each resonance contribution to the total reaction rate occurs by analyzing the ratio ( N A < σν> i / N A < σν>). This allowed us to show that the 680 and 840 keV broad resonances strongly dominate the reaction rate over the stellar temperature range T 9=0.02-0.06 and T 9=0.5-5. Finally, these results were compared to NACRE and Iliadis astrophysical compilations.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

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

    PubMed

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

    2010-01-01

    A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal. PMID:22163620

  10. Development of the GEM-MSTPC for studies of astrophysical nuclear reaction rates

    SciTech Connect

    Yamaguchi, K.; Arai, I.; Ishiyama, H.; Watanabe, Y. X.; Tanaka, M. H.; Miyatake, H.; Hirayama, Y.; Imai, N.; Fuchi, Y.; Jeong, S. C.; Nomura, T.; Mizoi, Y.; Das, S. K.; Fukuda, T.; Hashimoto, T.; Yamaguchi, H.; Kubono, S.; Hayakawa, S.; Makii, H.; Mitsuoka, S.

    2010-08-12

    We have developed an active-target type gas-detector, a Gas Electron Multiplier Multiple-Sampling and Tracking Proportional Chamber (GEM-MSTPC) operating with low-pressure He-base mixed gas, where He is used as a target for studies of astrophysical nuclear reaction rates. Different kinds of 400 {mu}m thick GEMs were examined. The gain stability was examined with a configuration of GEMs of 400 {mu}m in thickness fabricated in different ways, against the injection rate of low-energy heavy ions of 10{sup 5} particles per second. The gain of GEM with Cu electrodes coated by Au was observed to be stable up to the injection rate of 10{sup 5} particles per second.

  11. The rate constant for the reaction of oxygen /3P/ atoms with dichlorine monoxide

    NASA Technical Reports Server (NTRS)

    Miziolek, A. W.; Molina, M. J.

    1978-01-01

    A fast flow discharge apparatus was used to measure the rate constant for the reaction of ground state oxygen atoms with dichlorine monoxide in the temperature range 236-295 K. The air afterflow technique (NO2 chemiluminescence) was used for detection of oxygen atoms. The Arrhenius expression for the rate constant was found to be 2.7 plus or minus 0.3 times 10 to the -11th power exp(-560 plus or minus 80/T) cu cm per molecule per sec. At 295 K the rate constant is 4.1 plus or minus 0.5 times 10 to the -12th power cu cm per molecule per sec.

  12. Channel specific rate constants for reactions of O(1D) with HCl and HBr

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Wells, J. R.; Ravishankara, A. R.

    1986-01-01

    The absolute rate coefficients and product yields for reactions of O(1D) with HCl(1) and HBr(2) at 287 K are presently determined by means of the time-resolved resonance fluorescence detection of O(3P) and H(2S) in conjunction with pulsed laser photolysis of O3/HX/He mixtures. Total rate coefficients for O(1D) removal are found to be, in units of 10 to the -10th cu cm/molecule per sec, k(1) = 1.50 + or - 0.18 and k(2) 1.48 + or - 0.16; the absolute accuracy of these rate coefficients is estimated to be + or - 20 percent.

  13. CNO and 6Li from big-bang nucleosynthesis-Impact of unmeasured reaction rates

    NASA Astrophysics Data System (ADS)

    Madsen, Jes

    1990-04-01

    Rates for a number of nuclear reactions not studied in the laboratory are crucial for predicting the outcome of big-bang nucleosynthesis. It is shown in the present investigation that the mass fraction of CNO elements produced in neutron-rich zones in inhomogeneous nucleosynthesis (other parameters fixed) spans almost 3 orders of magnitude depending on the unmeasured rate of 8Li(α,n)11B. The possibility of producing observable quantities of primordial 6Li via 3H(3He,γ)6Li is discussed for the first time, and finally it is reported that helium production through 2H(2H, γ)4He is negligible in all nucleosynthesis scenarios, in spite of recent measurements increasing the low-energy rate by a factor 32.

  14. A Reaction-Diffusion-Based Coding Rate Control Mechanism for Camera Sensor Networks

    PubMed Central

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

    2010-01-01

    A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal. PMID:22163620

  15. Internal Thermodynamical Equilibrium And Consequences For Rate Law Expressions For Elementary Chemical And Physical Reactions

    NASA Astrophysics Data System (ADS)

    Jesudason, Christopher G.

    2009-07-01

    By viewing reactant species to be in a state of thermodynamical equilibrium with its various members which constitutes a set within a set of topological parameters various states of internal equilibrium within the same species would exist subject to the Gibbs thermodynamical criteria. Some examples from actual ab initio computer simulations show that there exists an empirical relationship between the activity coefficient ratio and the so-called reactivity coefficients, defined as a measure of departure of the rate constant with varying concentration of reactants in a system at equilibrium, where forward and backward rates can still be measured. These ideas are applied to charged reaction dynamics where a generalization of the Brönsted and Bjerrum rate expression is obtained.

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

    PubMed

    Minakata, Daisuke; Crittenden, John

    2011-04-15

    The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs. PMID:21410278

  17. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

    PubMed

    Gallis, Michael A; Bond, Ryan B; Torczynski, John R

    2009-09-28

    Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases. PMID:19791885

  18. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows

    NASA Astrophysics Data System (ADS)

    Gallis, Michael A.; Bond, Ryan B.; Torczynski, John R.

    2009-09-01

    Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.

  19. 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.

  20. 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.

  1. Size dependence of surface thermodynamic properties of nanoparticles and its determination method by reaction rate constant

    NASA Astrophysics Data System (ADS)

    Li, Wenjiao; Xue, Yongqiang; Cui, Zixiang

    2016-08-01

    Surface thermodynamic properties are the fundamental properties of nanomaterials, and these properties depend on the size of nanoparticles. In this paper, relations of molar surface thermodynamic properties and surface heat capacity at constant pressure of nanoparticles with particle size were derived theoretically, and the method of obtaining the surface thermodynamic properties by reaction rate constant was put forward. The reaction of nano-MgO with sodium bisulfate solution was taken as a research system. The influence regularities of the particle size on the surface thermodynamic properties were discussed theoretically and experimentally, which show that the experimental regularities are in accordance with the corresponding theoretical relations. With the decreasing of nanoparticle size, the molar surface thermodynamic properties increase, while the surface heat capacity decreases (the absolute value increases). In addition, the surface thermodynamic properties are linearly related to the reciprocal of nanoparticle diameter, respectively.

  2. Rate of reaction of the hydrogen atom with nitrous oxide in ambient water

    NASA Astrophysics Data System (ADS)

    Kazmierczak, Lukasz; Swiatla-Wojcik, Dorota; Szala-Bilnik, Joanna; Wolszczak, Marian

    2016-08-01

    The reaction of the hydrogen atom with nitrous oxide has been investigated by pulse radiolysis of N2O-saturated 0.1 M HCl solution at room temperature (24±1 °C). The value of (9±2)×104 M-1 s-1 obtained for the reaction rate constant is between the early estimates 1×104 M-1 s-1 by Czapski and Jortner (1960) and 4.3×105 M-1 s-1 by Thomas (1969), and is much lower than 2×106 M-1 s-1 used recently (Janik et al., 2007; Ismail et al., 2013; Liu et al., 2015; Meesungnoen et al., 2015).

  3. Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers

    SciTech Connect

    Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

    1993-08-03

    A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

  4. Estimates of neutron reaction rates in three portable He-3 proportional counters

    SciTech Connect

    Descalle, M; Labov, S

    2007-03-01

    The goal of this study is to obtain Monte Carlo estimates of neutron reaction rates for the {sup 3}He(n,p){sup 3}H reaction in two portable He-3 proportional counters in several configurations to quantify contributions from the environment, and optimize the tube characteristics. The smallest tube (0.5-inch diameter, 2-inch long, P = 10 atm) will not meet requirements. The largest tube (1-inch diameter, 4-inch long, P = 6 or 10 atm) will meet requirements and the tube length could be decreased to 2-inch at 6 atm and 1-inch at 10 atm. The 'medium' tube (3/4-inch diameter, 2-inch long, P = 10 atm) will meet requirements for the parallelepiped body, but will not for the cylindrical body.

  5. Structural and dynamical control of the reaction rate in protein electron transfer

    NASA Astrophysics Data System (ADS)

    Balabin, Ilya A.

    Electron transfer (ET) reactions in proteins are key steps in many vital bioenergetic processes, and the reaction rate is known to be highly sensitive to the protein structure in some cases. For most bioenergetic reactions, as described by the Fermi Golden rule, the rate is proportional to a product of the average square of the effective electronic donor to acceptor coupling and a Franck-Condon factor, which accounts for the nuclear control of the energy gap. The nuclear factor is reasonably well described in Marcus theory and its modifications, and this work is focused on the mechanisms that control the effective coupling. About ten years ago, the Pathways model described for the first time how protein environment may control the effective coupling. In this work, a novel theoretical approach is developed to explore the mechanisms of structural and dynamical control beyond the qualitative level of the Pathways model. In Chapter 1, the assumptions of the Pathways model, its limitations and effects of the structure and the electronic Hamiltonian are investigated for model chain-like bridges using the Dyson's equations. In Chapter II, the framework to explore the sensitivity of the effective coupling to quality of the electronic Hamiltonian, the interference among the dominant pathways and the bridge dynamics is presented. This analysis employs the Green's function technique and includes combined molecular dynamics and electronic structure calculations. Finally, in Chapter III, this framework is tested on the bacterial photosynthetic reaction center, and the mechanisms of the structural and dynamical control for different ET steps are discussed.

  6. Effects of arsenic incorporation on jarosite dissolution rates and reaction products

    NASA Astrophysics Data System (ADS)

    Kendall, Matthew R.; Madden, Andrew S.; Elwood Madden, Megan E.; Hu, Qinhong

    2013-07-01

    Batch dissolution experiments were undertaken on synthetic arsenojarosites at pH 2, pH 8, and in ultra-pure water to better understand the influence of As incorporation on the kinetics and reaction products of jarosite dissolution. Incongruent jarosite dissolution was observed in all experiments. Arsenojarosite lacks the pH dependency observed in K-jarosite dissolution, likely the result of surface arsenate-iron complexes preventing protonation at low pH and repelling hydroxyls at high pH. The stronger bonding of arsenate to iron, compared to sulfate to iron, leads to an enrichment of surface layer arsenate-iron complex sites, inhibiting the dissolution of jarosite with time. The secondary reaction products formed during the dissolution of arsenojarosite include maghemite, goethite, and hematite in ultra-pure water, and ferrihydrite in pH 8 Tris buffered solution. Maghemite initially forms and transitions to hematite with time in ultra-pure water, but increasing arsenic concentrations slow this transition. At pH >3.5, arsenic from the dissolution of arsenojarosite adsorbs onto newly formed reaction products. Arsenic also inhibits the formation of goethite and reduces the crystallinity of the observed maghemite reaction products. The coprecipitation of iron oxides with increasing amounts of arsenic results in a change from spherical to "worm-like" aggregate morphology and provides a sink for arsenic released during arsenojarosite dissolution. This study shows that in open systems with a flush of fresh solution, arsenic incorporation in jarosite results in an increase in dissolution rates. In closed systems, however, increasing surface arsenate-iron complexes inhibit further dissolution of the underlying bulk material, causing a reduction in dissolution rates as arsenic incorporation increases.

  7. Rate Equations and Kinetic Parameters of the Reactions Involved in Pyrite Oxidation by Thiobacillus ferrooxidans.

    PubMed

    Lizama, H M; Suzuki, I

    1989-11-01

    Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 muM Fe per min per FeS(2) percent pulp density for the spontaneous pyrite dissolution, 10 muM Fe per min per mM Fe for the indirect leaching with Fe, 90 muM O(2) per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 muM O(2) per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The K(m) values for pyrite concentration were similar and were 1.9, 2.5, and 2.75% pulp density for indirect leaching, washed pyrite oxidation by T. ferrooxidans, and unwashed pyrite oxidation by T. ferrooxidans, respectively. The last reaction was competitively inhibited by increasing concentrations of cells, with a K(i) value of 0.13 mg of wet cells per ml. T. ferrooxidans cells also increased the rate of Fe production from Fe plus pyrite. PMID:16348054

  8. Temperature dependent rate coefficients for the reaction of OH radicals with dimethylbenzoquinones

    NASA Astrophysics Data System (ADS)

    Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Wenger, John C.

    2015-10-01

    Rate coefficients for the gas-phase reaction of hydroxyl (OH) radicals with two methylated benzoquinones have been measured at atmospheric pressure over the temperature range 284-313 K using the relative rate method. The following Arrhenius expressions (in cm3 molecule-1 s-1) have been obtained: k(25DMBQ) = (8.59 ± 4.70) × 10-12exp[(228 ± 163)/T] and k(26DMBQ) = (5.11 ± 2.79) × 10-12exp[(399 ± 165)/T] for 2,5-dimethylbenzoquinone (2,5DMBQ) and 2,6-dimethylbenzoquinone (2,6DMBQ), respectively, with corresponding values at 298 K: k(25DMBQ) = (2.05 ± 0.46) × 10-11 and k(26DMBQ) = (1.93 ± 0.12) × 10-11. The rate coefficients are compared to those reported for similar compounds and discussed in terms of structure-activity relationships. The results are also used to calculate atmospheric lifetimes for 2,5DMBQ and 2,6DMBQ with respect to reaction with OH radicals.

  9. Nuclear reaction rates and their influence on nucleosynthesis in the neutrino-p-process

    NASA Astrophysics Data System (ADS)

    Hatcher, Daniel; Frohlich, Carla; Perdikakis, Georgios

    2015-10-01

    The synthesis of elements heavier than iron in the early stages of galactic evolution is commonly attributed to Type II (core collapse) supernova explosions. However, the currently accepted mechanisms of heavy element synthesis through neutron capture processes (r-process and s-process) cannot explain the abundance patterns seen in very old galactic halo stars. A proposed solution to this problem is the neutrino-p-process, which takes place in the strong neutrino winds of core-collapse supernovae. In the neutrino-p-process, antineutrinos absorbed by protons yield neutrons that are quickly captured by the surrounding, proton-rich nuclei through (n,p) reactions. Such interactions allow for the nucleosynthesis of elements with atomic mass numbers greater than 64 (this includes Sr, Y, Zr and others possibly up to Sn). We study the sensitivity of the νp-process abundance pattern to (n,p), (p, γ), and (n, γ) rates for nuclei between Ni and Sn. We illustrate our findings for three different initial electron fractions and two representative trajectories. We discuss how these rates influence the abundance pattern and the nuclear flow. We observe the effects of predicted reaction rates on the abundance pattern and nuclear flow.

  10. Test of the quantum instanton approximation for thermal rate constants for some collinear reactions.

    PubMed

    Ceotto, Michele; Miller, William H

    2004-04-01

    Two variants of the recently developed quantum instanton (QI) model for calculating thermal rate constants of chemical reactions are applied to several collinear atom-diatom reactions with various skew angles. The results show that the original QI version of the model is consistently more accurate than the "simplest" quantum instanton version (both being applied here with one "dividing surface") and thus to be preferred. Also, for these examples (as with other earlier applications) the QI results agree well with the correct quantum rates (to within approximately 20% or better) for all temperatures >200 K, except for situations where dynamical corrections to transition state theory (i.e., "re-crossing" dynamics) are evident. (Since re-crossing effects are substantially reduced in higher dimensionality, this is not a cause for serious concern.) A procedure is also described which facilitates use of the METROPOLIS algorithm for evaluating all quantities that appear in the QI rate expression by Monte Carlo path integral methods. PMID:15267524

  11. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation.

    PubMed

    Andersen, M S; Larsen, F; Postma, D

    2001-10-15

    The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4 x 10(-10) mol FeS2/g x s are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase. The reaction scheme predicts the volume of O2 gas consumed to be larger than of CO2 produced. In addition the solubility of CO2 in water is about 30 times larger than of O2 causing a further decrease in total gas volume. The change in total gas volume therefore also depends on the gas/water volume ratio and the lower the ratio the more pronounced the loss of volume will be. Under field conditions the change in total volume may amount up to 20% in the absence of calcite and over 10% in the presence of calcite. Such changes in gas volume during the oxidation of pyrite are expected to result in pressure gradients causing advective transport of gaseous oxygen. PMID:11686369

  12. Redox reaction rates in shallow aquifers: Implications for nitrate transport in groundwater and streams

    USGS Publications Warehouse

    Tesoriero, Anthony J.

    2012-01-01

    Groundwater age and water chemistry data along flow paths from recharge areas to streams were used to evaluate the trends and transformations of agricultural chemicals. Results from this analysis indicate that median nitrate recharge concentrations in these agricultural areas have increased markedly over the last 50 years from 4 mg N/L in samples collected prior to 1983 to 7.5 mg N/L in samples collected since 1983. The effect that nitrate accumulation in shallow aquifers will have on drinking water quality and stream ecosystems is dependent on the rate of redox reactions along flow paths and on the age distribution of nitrate discharging to supply wells and streams.

  13. Novel technique for constraining r-process (n, γ) reaction rates.

    PubMed

    Spyrou, A; Liddick, S N; Larsen, A C; Guttormsen, M; Cooper, K; Dombos, A C; Morrissey, D J; Naqvi, F; Perdikakis, G; Quinn, S J; Renstrøm, T; Rodriguez, J A; Simon, A; Sumithrarachchi, C S; Zegers, R G T

    2014-12-01

    A novel technique has been developed, which will open exciting new opportunities for studying the very neutron-rich nuclei involved in the r process. As a proof of principle, the γ spectra from the β decay of ^{76}Ga have been measured with the SuN detector at the National Superconducting Cyclotron Laboratory. The nuclear level density and γ-ray strength function are extracted and used as input to Hauser-Feshbach calculations. The present technique is shown to strongly constrain the ^{75}Ge(n,γ)^{76}Ge cross section and reaction rate. PMID:25526121

  14. Optimal choice of dividing surface for the computation of quantum reaction rates.

    PubMed

    Predescu, Cristian; Miller, William H

    2005-04-14

    We consider the calculation of quantum mechanical rate constants for chemical reactions via algorithms that utilize short-time values of the symmetrized flux-flux correlation function. We argue that the dividing surface that makes optimal use of the short-time quantum information is the surface that minimizes the value at the origin of the symmetrized flux-flux correlation function. We also demonstrate that, in the classical limit, this quantum variational criterion produces the same dividing surface as Wigner's variational principle. Finally, we argue that the quantum variational criterion behaves in a nearly optimal fashion with respect to the minimization of the extent of re-crossing flux. PMID:16851728

  15. First Results of Reaction Propagation Rates in HMX at High Pressure

    SciTech Connect

    Farber, D L; Esposito, A; Zaug, J M; Aracne-Ruddle, C

    2001-06-15

    The authors have measured the reaction propagation rate (RPR) in weapons-grade, ultrafine octahydro-1,3,57-tetranitro-1,3,5,7-tetrazocine (HMX) powder in a diamond anvil cell over the pressure range 0.7-35 GPa. In order to have a cross-comparison of their experiments, they carried out a series of experiments on nitromethane (NM) up to 15 GPa. The results on NM are indistinguishable from previous measurements of Rice and Folz. In comparison to high-pressure, NM, the burn process for solid HMX is not spatially uniform.

  16. First Results of Reaction Propagation Rates in HMX at High Pressure

    SciTech Connect

    Farber, D L; Esposito, A; Zaug, J M; Aracne-Ruddle, C

    2001-06-15

    The authors have measured the reaction propagation rate (RPR) in weapons-grade, ultrafine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) powder in a diamond anvil cell over the pressure range 0.7-35 GPa. In order to have a cross-comparison of their experiments, they carried out a series of experiments on nitromethane (NM) up to 15 GPa. The results on NM are indistinguishable from previous measurements of Rice and Folz. In comparison to high-pressure NM, the burn process for solid HMX is between 5-10 times faster at pressures above 10 GPa.

  17. Chemical reaction rates using the semiclassical Van-Vleck initialvalue representation

    SciTech Connect

    Venkataraman, Charulatha; Miller, William H.

    2006-11-29

    A semiclassical IVR formulation using the Van-Vleck propagator has been used to calculate the flux correlation function and thereby reaction rate constants. This Van-Vleck formulation of the flux-flux correlation function is computationally as simple as the classical Wigner model. However unlike the latter, it has the ability to capture quantum interference/coherence effects. Classical trajectories are evolved starting from the dividing surface that separates reactants and products, and are evolved negatively in time. This formulation has been tested on model problems ranging from the Eckart barrier, double well to the collinear H + H{sub 2}.

  18. Measurement of (α,n) reaction cross sections of erbium isotopes for testing astrophysical rate predictions

    NASA Astrophysics Data System (ADS)

    Kiss, G. G.; Szücs, T.; Rauscher, T.; Török, Zs; Csedreki, L.; Fülöp, Zs; Gyürky, Gy; Halász, Z.

    2015-05-01

    The γ-process in core-collapse and/or type Ia supernova explosions is thought to explain the origin of the majority of the so-called p nuclei (the 35 proton-rich isotopes between Se and Hg). Reaction rates for γ-process reaction network studies have to be predicted using Hauser-Feshbach statistical model calculations. Recent investigations have shown problems in the prediction of α-widths at astrophysical energies which are an essential input for the statistical model. It has an impact on the reliability of abundance predictions in the upper mass range of the p nuclei. With the measurement of the 164,166Er(α,n)167,169Yb reaction cross sections at energies close to the astrophysically relevant energy range we tested the recently suggested low energy modification of the α+nucleus optical potential in a mass region where γ-process calculations exhibit an underproduction of the p nuclei. Using the same optical potential for the α-width which was derived from combined 162Er(α,n) and 162Er(α,γ) measurement makes it plausible that a low-energy modification of the optical α+nucleus potential is needed.

  19. 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.

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

    SciTech Connect

    Comstock, Jennifer M.; Protat, Alain; McFarlane, Sally A.; Delanoe, Julien; Deng, Min

    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 the 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.

  1. Noise-induced convergence of the low flow rate chaos in the Belousov-Zhabotinsky reaction

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Minoru; Nakaiwa, Masaru; Akiya, Takaji; Ohmori, Takao; Yamaguchi, Tomohiko

    The effect of noise on the low flow-rate chaos in the Belousov-Zhabotinsky (BZ) reaction was studied. The chaos was simulated using the three-variable model of Györgyi and Field. Gaussian white noise was imposed on the flow-rate of the reactant solutions fed into CSTR to simulate the so-called type P noise. The range of average noise amplitudes was chosen between 0.01% and 1% related to the inverse residence time. The calculated time series were analyzed on the basis of their Fourier spectra, maximum Lyapunov exponent, Kolmogorov entropies, return maps and invariant density. We found that the noise induces partial order of the period-3-like oscillations in the low flowrate chaos.

  2. Absolute rate constants for the reaction of atomic hydrogen with ketene from 298 to 500 K

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

    Rate constants for the reaction of atomic hydrogen with ketene have been measured at room temperature by two techniques, flash photolysis-resonance fluorescence and discharge flow-resonance fluorescence. The measured values are (6.19 + or - 1.68) x 10 to the -14th and (7.3 + or - 1.3) x 10 to the -14th cu cm/molecule/s, respectively. In addition, rate constants as a function of temperature have been measured over the range 298-500 K using the FP-RF technique. The results are best represented by the Arrhenius expression k = (1.88 + or - 1.12) x 10 to the -11th exp(-1725 + or - 190/T) cu cm/molecule/s, where the indicated errors are at the two standard deviation level.

  3. Elementary reaction rate measurements at high temperatures by tunable-laser flash-absorption

    SciTech Connect

    Hessler, J.P.

    1993-12-01

    The major objective of this program is to measure thermal rate coefficients and branching ratios of elementary reactions. To perform these measurements, the authors constructed an ultrahigh-purity shock tube to generate temperatures between 1000 and 5500 K. The tunable-laser flash-absorption technique is used to measure the rate of change of the concentration of species which absorb below 50,000 cm{sup {minus}1} e.g.: OH, CH, and CH{sub 3}. This technique is being extended into the vacuum-ultraviolet spectral region where one can measure atomic species e.g.: H, D, C, O, and N; and diatomic species e.g.: O{sub 2}, CO, and OH.

  4. Solvent effects on the rate constants for reaction of trichloromethylperoxyl radicals with organic reductants

    SciTech Connect

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

    1993-07-15

    Absolute rate constants for the reactions of trichloromethylperoxyl radicals with chloropromazine and trolox have been determined by pulse radiolysis in 16 different solvents. The rate constants were found to vary over two orders of magnitude (10[sup 7]-10[sup 9] L mol[sup [minus]1] s[sup [minus]1]) and to correlate with the Hildebrand solubility parameter (cohesive energy density) of the solvent better than with any other single solvent parameter. The correlation was satisfactory for ClPz and did not improve significantly by including additional parameters. For trolox, however, the correlation was relatively poor but was improved considerably by taking into account the basicity of the solvent. This effect is due to the transfer of a proton upon the oxidation of trolox. 21 refs., 3 figs., 2 tabs.

  5. Informing Neutron-Capture Rates through (d,p) Reactions on Neutron-Rich Tin Isotopes

    NASA Astrophysics Data System (ADS)

    Manning, B.; Cizewski, J. A.; Kozub, R. L.; Ahn, S.; Allmond, J. M.; Bardayan, D. W.; Chae, K. Y.; Chipps, K. A.; Howard, M. E.; Jones, K. L.; Liang, J. F.; Matos, M.; Nunes, F. M.; Nesaraja, C. D.; O'Malley, P. D.; Pain, S. D.; Peters, W. A.; Pittman, S. T.; Ratkiewicz, A.; Schmitt, K. T.; Shapira, D.; Smith, M. S.; Titus, L.

    2014-03-01

    Level energies and spectroscopic information for neutron-rich nuclei provide important input for r-process nucleosynthesis calculations; specifically, the location and strength of single-neutron l = 1 states when calculating neutron-capture rates. Surman and collaborators have performed sensitivity studies to show that varying neutron-capture rates can significantly alter final r-process abundances. However, there are many nuclei important to the r-process that cannot be studied. Extending studies to more neutron-rich nuclei will help constrain the nuclear shell-model in extrapolating to nuclei even further from stability. The (d,p) reaction has been measured with radioactive ion beams of 126Sn and 128Sn to complete the set of (d,p) studies on even mass tin isotopes from doubly-magic 132 to stable 124Sn. Work supported in part by the U.S. Department of Energy and National Science Foundation.

  6. PH-dependence of the steady-state rate of a two-step enzymic reaction.

    PubMed

    Brocklehurst, K; Dixon, H B

    1976-04-01

    1. The pH-dependence is considered of a reaction between E and S that proceeds through an intermediate ES under "Briggs-Haldane' conditions, i.e. there is a steady state in ES and [S]o greater than [E]T, where [S]o is the initial concentration of S and [E]T is the total concentration of all forms of E. Reactants and intermediates are assumed to interconvert in three protonic states (E equilibrium ES; EH equilibrium EHS; EH2 equilibrium EH2S), but only EHS provides products by an irreversible reaction whose rate constant is kcat. Protonations are assumed to be so fast that they are all at equilibrium. 2. The rate equation for this model is shown to be v = d[P]/dt = (kcat.[E]T[S]o/A)/[(KmBC/DA) + [S]o], where Km is the usual assembly of rate constants around EHS and A-D are functions of the form (1 + [H]/K1 + K2/[H]), in which K1 and K2 are: in A, the molecular ionization constants of ES; in B, the analogous constants of E; in C and D, apparent ionization constants composed of molecular ionization constants (of E or ES) and assemblies of rate constants. 3. As in earlier treatments of this type of reaction which involve either the assumption that the reactants and intermediate are in equilibrium or the assumption of Peller & Alberty [(1959) J. Am. Chem. Soc. 81, 5907-5914] that only EH and EHS interconvert directly, the pH-dependence of kcat. is determined only by A. 4. The pH-dependence of Km is determined in general by B-C/A-D, but when reactants and intermediate are in equilibrium, C identical to D and this expression simplifies to B/A. 5. The pH-dependence of kcat./Km, i.e. of the rate when [S]o less than Km, is not necessarily a simple bell-shaped curve characterized only by the ionization constants of B, but is a complex curve characterized by D/B-C. 6. Various situations are discussed in which the pH-dependence of kcat./Km is determined by assemblies simpler than D/B-C. The special situation in which a kcat./Km-pH profile provides the molecular pKa values of

  7. A Monte Carlo evaluation for effects of probable dimensional uncertainties of low dose rate brachytherapy seeds on dose

    PubMed Central

    Camgöz, Berkay; Kumru, Mehmet N.

    2014-01-01

    The aim of this study is to determine effects of size deviations of brachytherapy seeds on two dimensional dose distributions around the seed. Although many uncertainties are well known, the uncertainties which stem from geometric features of radiation sources are weakly considered and predicted. Neither TG-43 report which is not completely in common consensus, nor individual scientific MC and experimental studies include sufficient data for geometric uncertainties. Sizes of seed and its components can vary in a manufacturing deviation. This causes geometrical uncertainties, too. In this study, three seeds which have different geometrical properties were modeled using EGSnrc-Code Packages. Seeds were designed with all their details using the geometry package. 5% deviations of seed sizes were assumed. Modified seeds were derived from original seed by changing sizes by 5%. Normalizations of doses which were calculated from three kinds of brachytherapy seed and their derivations were found to be about 3%–20%. It was shown that manufacturing differences of brachytherapy seed cause considerable changes in dose distribution. PMID:25184054

  8. Variability and epistemic uncertainty in water ingestion rates and pharmacokinetic parameters, and impact on the association between perfluorooctanoate and preeclampsia in the C8 Health Project population.

    PubMed

    Avanasi, Raghavendhran; Shin, Hyeong-Moo; Vieira, Veronica M; Bartell, Scott M

    2016-04-01

    We recently utilized a suite of environmental fate and transport models and an integrated exposure and pharmacokinetic model to estimate individual perfluorooctanoate (PFOA) serum concentrations, and also assessed the association of those concentrations with preeclampsia for participants in the C8 Health Project (a cross-sectional study of over 69,000 people who were environmentally exposed to PFOA near a major U.S. fluoropolymer production facility located in West Virginia). However, the exposure estimates from this integrated model relied on default values for key independent exposure parameters including water ingestion rates, the serum PFOA half-life, and the volume of distribution for PFOA. The aim of the present study is to assess the impact of inter-individual variability and epistemic uncertainty in these parameters on the exposure estimates and subsequently, the epidemiological association between PFOA exposure and preeclampsia. We used Monte Carlo simulation to propagate inter-individual variability/epistemic uncertainty in the exposure assessment and reanalyzed the epidemiological association. Inter-individual variability in these parameters mildly impacted the serum PFOA concentration predictions (the lowest mean rank correlation between the estimated serum concentrations in our study and the original predicted serum concentrations was 0.95) and there was a negligible impact on the epidemiological association with preeclampsia (no change in the mean adjusted odds ratio (AOR) and the contribution of exposure uncertainty to the total uncertainty including sampling variability was 7%). However, when epistemic uncertainty was added along with the inter-individual variability, serum PFOA concentration predictions and their association with preeclampsia were moderately impacted (the mean AOR of preeclampsia occurrence was reduced from 1.12 to 1.09, and the contribution of exposure uncertainty to the total uncertainty was increased up to 33%). In conclusion

  9. Scanning electrochemical microscopy of metallic biomaterials: reaction rate and ion release imaging modes.

    PubMed

    Gilbert, J L; Smith, S M; Lautenschlager, E P

    1993-11-01

    The Scanning Electrochemical Microscope (SECM) is a nonoptical scanning microscopic instrument capable of imaging highly localized electrical currents associated with charge transfer reactions on metallic biomaterials surfaces. The SECM operates as an aqueous electrochemical cell under bipotentiostatic control with a microelectrode and sample independently biased as working electrodes. Microelectrode current and position is recorded as it is scanned very near a metallurgically polished planar sample surface. To date, the SECM has imaged metallic biomaterials surfaces in oxygen reaction rate imaging (ORRI) and ion release and deposition imaging (IRDI) modes. In ORRI, sample and microelectrode are biased at sufficiently negative potentials to reduce absorbed oxygen. As the microelectrode scans areas of active oxygen reduction, localized diffusion fields with decreased oxygen solution concentrations are encountered and resultant decrements in microelectrode current are observed. In IRDI mode the sample is positively biased and the microelectrode is negatively biased. The microelectrode detects anodic dissolution products with highest currents being observed over the most active areas. Performance of the SECM has been evaluated on Ni minigrids, gamma-1 Hg-Ag dental amalgam crystals, and sintered beads of Co-Cr-Mo alloy which represent significantly different geometries and corrosion processes to help demonstrate the potential of this instrument. The SECM is a valuable tool for imaging microelectrochemical processes on the surfaces of metallurgically polished metallic biomaterials samples and a wide variety of other surfaces of biological interest where charge transfer reactions occur. The SECM allows selective biasing of metallic biomaterials surfaces and Faradaic reactions can be selectively imaged while the surface is in the active, passive, or transpassive state. PMID:8262998

  10. Reaction Rate Theory of Radiation Exposure and Scaling Hypothesis in Mutation Frequency

    NASA Astrophysics Data System (ADS)

    Manabe, Yuichiro; Nakamura, Issei; Bando, Masako

    2014-11-01

    We have developed a kinetic reaction model for cells with irradiated DNA molecules due to ionizing radiation exposure. Our theory simultaneously accounts for the time-dependent reactions of DNA damage, DNA mutation and DNA repair, and the proliferation and apoptosis of cells in a tissue with a minimal set of model parameters. In contrast to existing theories of radiation exposition, we do not assume the relationships between the total dose and the induced mutation frequency. Our theory provides a universal scaling function that reasonably explains the mega-mouse experiments by Russell and Kelly [Proc. Natl. Acad. Sci. U.S.A. 79, 542 (1982)] with different dose rates. Furthermore, we have estimated the effective dose rate, which is biologically equivalent to the ionizing effects other than those caused by artificial irradiation. This value is 1.11 × 10-3 Gy/h, which is significantly larger than the effect caused by natural background radiation.

  11. The application of the Reaction Rate Analyser LKB 8600 as an automatic coagulometer.

    PubMed

    Andersen, I; Thorsen, S

    1977-02-01

    The application of the Reaction Rate Analyser LKB 8600 (RRA) as an automatic coagulometer is described. The RRA was slightly modified without interfering with its function as an enzyme reaction rate analyser. The endpoint of coagulation was recorded when the increase in absorbance exceeded 0.047 at lambda = 340 nm. The coagulation time was monitored by a counter with automatic print-out or by a recorder. The analytical dispersion, s(x)x, ranged between 0.01 and 0.05. Results (x, y) of the determination of the quantity of plasma coagulation factors (II + VII + X) by RRA and manually by visual recording could be expressed by y = 0.93x + 0.04, r = 0.96, n = 66 (method of Owren & Aas) or by y = 1.00x + 0.02, r = 0.98, n = 49 (Normotest). Similarly, plasma activated partial thromboplastin time (Activated Thrombofax) could be expressed by y = 0.99x + 5.00, r = 0.99, n = 23. PMID:616030

  12. Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR.

    PubMed

    Balzan, Riccardo; Fernandes, Laetitia; Comment, Arnaud; Pidial, Laetitia; Tavitian, Bertrand; Vasos, Paul R

    2016-01-01

    The main limitation of NMR-based investigations is low sensitivity. This prompts for long acquisition times, thus preventing real-time NMR measurements of metabolic transformations. Hyperpolarization via dissolution DNP circumvents part of the sensitivity issues thanks to the large out-of-equilibrium nuclear magnetization stemming from the electron-to-nucleus spin polarization transfer. The high NMR signal obtained can be used to monitor chemical reactions in real time. The downside of hyperpolarized NMR resides in the limited time window available for signal acquisition, which is usually on the order of the nuclear spin longitudinal relaxation time constant, T1, or, in favorable cases, on the order of the relaxation time constant associated with the singlet-state of coupled nuclei, TLLS. Cellular uptake of endogenous molecules and metabolic rates can provide essential information on tumor development and drug response. Numerous previous hyperpolarized NMR studies have demonstrated the relevancy of pyruvate as a metabolic substrate for monitoring enzymatic activity in vivo. This work provides a detailed description of the experimental setup and methods required for the study of enzymatic reactions, in particular the pyruvate-to-lactate conversion rate in presence of lactate dehydrogenase (LDH), by hyperpolarized NMR. PMID:26967906

  13. Reaction Rate Measurement at the Californium User Facility (CUF) for unfolding the neutron spectrum

    NASA Astrophysics Data System (ADS)

    Hannan, Mohammad; Ortega, Ruben

    2011-03-01

    Neutron Activation Analysis was used to determine Reaction Rate measurement of several activation detectors at the ORNL Californium User Facility (CUF). The irradiations were performed with 34 mg Cf 252 neutron source strength.. Ten source capsules > 34 mgwerepositionedconcentricallyaroundasamplecavity . Wehavedeterminedabsoluteactivityperatomof 9 detectors : Au 197 (n , γ) Au 198 , Al 27 (n , α) Na 24 , Al 27 (n , p) Mg 27 , Fe 56 (n , p) Mn 5 , Fe 54 (n , p) Mn 54 , In 115 (n , γ) In 116 , Ti 46 (n , p) Sc 46 , Ni 60 (n , p) Co 60 , Fe 58 (n , γ) Fe 59 . Theerrorsarewithin 1.5 - 8 60 and Fe 58 have errors of 46% and 32 %. These high errors may be attributed to the counting statistics. These reaction rate values will be used to unfold the neutron spectrum of the CUF using the MAXED 2000, a computer code for the de convolution of multi sphere neutron spectrometer data and the results are discussed. The authors acknowledge help, advise, and using facility at ORNL-CUF to Dr. Rodger martin and Mr. David C. Galsgow.

  14. Relationship between the surface coverage of spectator species and the rate of electrocatalytic reactions.

    SciTech Connect

    Strmcnik, D. S.; Rebec, P.; Gaberscek, M.; Tripkovic, D.; Stamenkovic, V.; Lucas, C.; Markovic, N. M.; Materials Science Division; Univ. of Chicago; National Inst. of Chemistry; Univ. of Liverpool

    2007-12-20

    Relationships between the surface coverage of spectator (blocking) species and the rate of the hydrogen oxidation reaction (HOR), the oxygen reduction reaction (ORR), and the bulk oxidation of dissolved CO on Pt(100) and Pt(111) single crystals in acidic electrolytes has been probed by cyclic voltammetry, in situ surface X-ray scattering (SXS), and ex situ scanning tunneling microscopy (STM) techniques. It is shown that the surface coverage by spectator species during the HOR and the ORR are the same as for the corresponding coverage obtained in the inert (Ar-saturated) environment. This observation is consistent with the proposition that the availability of active sites for H{sub 2} and O{sub 2} is determined almost entirely by the coverage of adsorbates from the supporting electrolyte and not by the active intermediates. Related electrochemical-SXS studies undertaken for bulk CO oxidation reveal that the maximum rate above the ignition potential is reached on a surface that is covered by {approx}90% of an ordered CO adlayer. The nature of the active sites in this case is determined by a combination of electrochemical and STM results. It is found that the active sites in this potential region are steps, which appear to be active sites for OH adsorption. To get insight into the relationship between the diffusion-limiting current and the surface coverage by the inactive CO adlayer, we introduce the concept of a partially blocked electrode surface with active and inactive areas. On the basis of the calculations and experimental results, it is proposed that the active sites for given electrochemical reactions on Pt electrodes are arrays of adsorbate-free nanoscale patches embedded in an inactive adlayer of nonreactive molecular species.

  15. Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study

    SciTech Connect

    Vasu, Subith; Huynh, Lam; Davidson, David F.; Hanson, Ronald K.; Golden, David

    2011-03-09

    Reactions of hydroxyl (OH) radicals with 1-butene (k1), trans-2-butene (k2), and cis-2-butene (k3) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH3)3-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C5 oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.

  16. Thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates of BTATz-CMDB propellant.

    PubMed

    Yi, Jian-Hua; Zhao, Feng-Qi; Wang, Bo-Zhou; Liu, Qian; Zhou, Cheng; Hu, Rong-Zu; Ren, Ying-Hui; Xu, Si-Yu; Xu, Kang-Zhen; Ren, Xiao-Ning

    2010-09-15

    The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f(alpha)=(1-alpha)(2), and the kinetic equations are dalpha/dt = 10(19.24)(1-alpha)(2)e(-2.32x10(4)/T) and dalpha/dt = 10(20.32)(1-alpha)(2)e(-2.32x10(4)/T). The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa. PMID:20542638

  17. Product distributions and rate constants for ion-molecule reactions in water, hydrogen sulfide, ammonia, and methane

    NASA Technical Reports Server (NTRS)

    Huntress, W. T., Jr.; Pinizzotto, R. F., Jr.

    1973-01-01

    The thermal energy, bimolecular ion-molecule reactions occurring in gaseous water, hydrogen sulfide, ammonia, and methane have been identified and their rate constants determined using ion cyclotron resonance methods. Absolute rate constants were determined for the disappearance of the primary ions by using the trapped ion method, and product distributions were determined for these reactions by using the cyclotron ejection method. Previous measurements are reviewed and compared with the results using the present methods. The relative rate constants for hydrogen-atom abstraction, proton transfer, and charge transfer are also determined for reactions of the parent ions.

  18. Ground reaction forces and loading rates associated with parkour and traditional drop landing techniques.

    PubMed

    Puddle, Damien L; Maulder, Peter S

    2013-01-01

    Due to the relative infancy of Parkour there is currently a lack of empirical evidence on which to base specific technique instruction upon. The purpose of this study was to compare the ground reaction forces and loading rates involved in two Parkour landing techniques encouraged by local Parkour instructors and a traditional landing technique recommended in the literature. Ten male participants performed three different drop landing techniques (Parkour precision, Parkour roll, and traditional) onto a force plate. Compared to the traditional technique the Parkour precision technique demonstrated significantly less maximal vertical landing force (38%, p < 0.01, ES = 1.76) and landing loading rate (54%, p < 0.01, ES = 1.22). Similarly, less maximal vertical landing force (43%, p < 0.01, ES = 2.04) and landing loading rate (63%, p < 0.01, ES = 1.54) were observed in the Parkour roll technique compared to the traditional technique. It is unclear whether or not the Parkour precision technique produced lower landing forces and loading rates than the Parkour roll technique as no significant differences were found. The landing techniques encouraged by local Parkour instructors such as the precision and roll appear to be more appropriate for Parkour practitioners to perform than a traditional landing technique due to the lower landing forces and loading rates experienced. Key pointsParkour precision and Parkour roll landings were found to be safer than a traditional landing technique, resulting in lower maximal vertical forces, slower times to maximal vertical force and ultimately lesser loading rates.Parkour roll may be more appropriate (safer) to utilize than the Parkour precision during Parkour landing scenarios.The Parkour landing techniques investigated n this study may be beneficial for landing by non-Parkour practitioners in everyday life. PMID:24149735

  19. Ground Reaction Forces and Loading Rates Associated with Parkour and Traditional Drop Landing Techniques

    PubMed Central

    Puddle, Damien L.; Maulder, Peter S.

    2013-01-01

    Due to the relative infancy of Parkour there is currently a lack of empirical evidence on which to base specific technique instruction upon. The purpose of this study was to compare the ground reaction forces and loading rates involved in two Parkour landing techniques encouraged by local Parkour instructors and a traditional landing technique recommended in the literature. Ten male participants performed three different drop landing techniques (Parkour precision, Parkour roll, and traditional) onto a force plate. Compared to the traditional technique the Parkour precision technique demonstrated significantly less maximal vertical landing force (38%, p < 0.01, ES = 1.76) and landing loading rate (54%, p < 0.01, ES = 1.22). Similarly, less maximal vertical landing force (43%, p < 0.01, ES = 2.04) and landing loading rate (63%, p < 0.01, ES = 1.54) were observed in the Parkour roll technique compared to the traditional technique. It is unclear whether or not the Parkour precision technique produced lower landing forces and loading rates than the Parkour roll technique as no significant differences were found. The landing techniques encouraged by local Parkour instructors such as the precision and roll appear to be more appropriate for Parkour practitioners to perform than a traditional landing technique due to the lower landing forces and loading rates experienced. Key points Parkour precision and Parkour roll landings were found to be safer than a traditional landing technique, resulting in lower maximal vertical forces, slower times to maximal vertical force and ultimately lesser loading rates. Parkour roll may be more appropriate (safer) to utilize than the Parkour precision during Parkour landing scenarios. The Parkour landing techniques investigated n this study may be beneficial for landing by non-Parkour practitioners in everyday life. PMID:24149735

  20. 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.

  1. Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1974-01-01

    Rate constants of two elementary bimolecular reactions involved in the oxidation of methane have been determined by monitoring the exponential growth of CO flame band emission behind incident shocks in three suitably chosen gas mixtures. The data do not support a mechanism which invokes the four center process CH3 + O2 yields CH2O + OH for the reaction of methyl with oxygen.

  2. Stress-associated cardiovascular reaction masks heart rate dependence on physical load in mice.

    PubMed

    Andreev-Andrievskiy, A A; Popova, A S; Borovik, A S; Dolgov, O N; Tsvirkun, D V; Custaud, M; Vinogradova, O L

    2014-06-10

    When tested on the treadmill mice do not display a graded increase of heart rate (HR), but rather a sharp shift of cardiovascular indices to high levels at the onset of locomotion. We hypothesized that under test conditions cardiovascular reaction to physical load in mice is masked with stress-associated HR increase. To test this hypothesis we monitored mean arterial pressure (MAP) and heart rate in C57BL/6 mice after exposure to stressful stimuli, during spontaneous locomotion in the open-field test, treadmill running or running in a wheel installed in the home cage. Mice were treated with β1-adrenoblocker atenolol (2mg/kg ip, A), cholinolytic ipratropium bromide (2mg/kg ip, I), combination of blockers (A+I), anxiolytic diazepam (5mg/kg ip, D) or saline (control trials, SAL). MAP and HR in mice increased sharply after handling, despite 3weeks of habituation to the procedure. Under stressful conditions of open field test cardiovascular parameters in mice were elevated and did not depend on movement speed. HR values did not differ in I and SAL groups and were reduced with A or A+I. HR was lower at rest in D pretreated mice. In the treadmill test HR increase over speeds of 6, 12 and 18m/min was roughly 1/7-1/10 of HR increase observed after placing the mice on the treadmill. HR could not be increased with cholinolytic (I), but was reduced after sympatholytic (A) or A+I treatment. Anxiolytic (D) reduced heart rate at lower speeds of movement and its overall effect was to unmask the dependency of HR on running speed. During voluntary running in non-stressful conditions of the home cage HR in mice linearly increased with increasing running speeds. We conclude that in test situations cardiovascular reactions in mice are governed predominantly by stress-associated sympathetic activation, rendering efforts to evaluate HR and MAP reactions to workload unreliable. PMID:24802359

  3. The role of advanced reactive surface area characterization in improving predictions of mineral reaction rates

    NASA Astrophysics Data System (ADS)

    Beckingham, L. E.; Zhang, S.; Mitnick, E.; Cole, D. R.; Yang, L.; Anovitz, L. M.; Sheets, J.; Swift, A.; Kneafsey, T. J.; Landrot, G.; Mito, S.; Xue, Z.; Steefel, C. I.; DePaolo, D. J.; Ajo Franklin, J. B.

    2014-12-01

    Geologic sequestration of CO2 in deep sedimentary formations is a promising means of mitigating carbon emissions from coal-fired power plants but the long-term fate of injected CO2 is challenging to predict. Reactive transport models are used to gain insight over long times but rely on laboratory determined mineral reaction rates that have been difficult to extrapolate to field systems. This, in part, is due to a lack of understanding of mineral reactive surface area. Many models use an arbitrary approximation of reactive surface area, applying orders of magnitude scaling factors to measured BET or geometric surface areas. Recently, a few more sophisticated approaches have used 2D and 3D image analyses to determine mineral-specific reactive surface areas that account for the accessibility of minerals. However, the ability of these advanced surface area estimates to improve predictions of mineral reaction rates has yet to be determined. In this study, we fuse X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB analysis to determine mineral-specific accessible reactive surface areas for a core sample from the Nagaoka pilot CO2 injection site (Japan). This sample is primarily quartz, plagioclase, smectite, K-feldspar, and pyroxene. SEM imaging shows abundant smectite cement and grain coatings that decrease the fluid accessibility of other minerals. However, analysis of FIB-SEM images reveals that smectite nano-pores are well connected such that access to underlying minerals is not occluded by smectite coatings. Mineral-specific accessible surfaces are determined, accounting for the connectivity of the pore space with and without connected smectite nano-pores. The large-scale impact of variations in accessibility and dissolution rates are then determined through continuum scale modeling using grid-cell specific information on accessible surface areas. This approach will be compared with a traditional continuum scale model using mineral abundances and common surface area

  4. Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes

    SciTech Connect

    Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang

    2014-05-07

    We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula.

  5. Mixed quantum classical calculation of proton transfer reaction rates: from deep tunneling to over the barrier regimes.

    PubMed

    Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang

    2014-05-01

    We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula. PMID:24811623

  6. The interplay between transport and reaction rates as controls on nitrate attenuation in permeable, streambed sediments

    NASA Astrophysics Data System (ADS)

    Lansdown, K.; Heppell, C. M.; Trimmer, M.; Binley, A.; Heathwaite, A. L.; Byrne, P.; Zhang, H.

    2015-06-01

    Anthropogenic nitrogen fixation and subsequent use of this nitrogen as fertilizer have greatly disturbed the global nitrogen cycle. Rivers are recognized hot spots of nitrogen removal in the landscape as interaction between surface water and sediments creates heterogeneous redox environments conducive for nitrogen transformations. Our understanding of riverbed nitrogen dynamics to date comes mainly from shallow sediments or hyporheic exchange flow pathways with comparatively little attention paid to groundwater-fed, gaining reaches. We have used 15N techniques to quantify in situ rates of nitrate removal to 1 m depth within a groundwater-fed riverbed where subsurface hydrology ranged from strong upwelling to predominantly horizontal water fluxes. We combine these rates with detailed hydrologic measurements to investigate the interplay between biogeochemical activity and water transport in controlling nitrogen attenuation along upwelling flow pathways. Nitrate attenuation occurred via denitrification rather than dissimilatory nitrate reduction to ammonium or anammox (range = 12 to >17,000 nmol 15N L-1 h-1). Overall, nitrate removal within the upwelling groundwater was controlled by water flux rather than reaction rate (i.e., Damköhler numbers <1) with the exception of two hot spots of biogeochemical activity. Deep sediments were as important a nitrate sink as shallow sediments with fast rates of denitrification and short water residence time close to the riverbed surface balanced by slower rates of denitrification and water flux at depth. Within this permeable riverbed >80% of nitrate removal occurs within sediments not exposed to hyporheic exchange flows under base flow conditions, illustrating the importance of deep sediments as nitrate sinks in upwelling systems.

  7. Shock tube measurements of specific reaction rates in branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1974-01-01

    Rate constants of two elementary bimolecular reactions involved in the oxidation of methane were determined by monitoring the exponential growth of CO flame band emission behind incident shocks in three suitably chosen gas mixtures.

  8. 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.

  9. Revised Production Rates for Na-22 and Mn-54 in Meteorites Using Cross Sections Measured for Neutron-induced Reactions

    NASA Technical Reports Server (NTRS)

    Sisterson, J. M.; Kim, K. J.; Reedy, R. C.

    2004-01-01

    The interactions of galactic cosmic rays (GCR) with extraterrestrial bodies produce small amounts of radionuclides and stable isotopes. The production rates of many relatively short-lived radionuclides, including 2.6-year Na-22 and 312-day Mn-54, have been measured in several meteorites collected very soon after they fell. Theoretical models used to calculate production rates for comparison with the measured values rely on input data containing good cross section measurements for all relevant reactions. Most GCR particles are protons, but secondary neutrons make most cosmogenic nuclides. Calculated production rates using only cross sections for proton-induced reactions do not agree well with measurements. One possible explanation is that the contribution to the production rate from reactions initiated by secondary neutrons produced in primary GCR interactions should be included explicitly. This, however, is difficult to do because so few of the relevant cross sections for neutron-induced reactions have been measured.

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

    NASA Technical Reports Server (NTRS)

    Sislian, J. P.

    1978-01-01

    The nonequilibrium flow field resulting from the turbulent mixing and combustion of a supersonic axisymmetric hydrogen jet in a supersonic parallel coflowing air stream is analyzed. Effective turbulent transport properties are determined using the (K-epsilon) model. The finite-rate chemistry model considers eight reactions between six chemical species, H, O, H2O, OH, O2, and H2. The governing set of nonlinear partial differential equations is solved by an implicit finite-difference procedure. Radial distributions are obtained at two downstream locations of variables such as turbulent kinetic energy, turbulent dissipation rate, turbulent scale length, and viscosity. The results show that these variables attain peak values at the axis of symmetry. Computed distributions of velocity, temperature, and mass fraction are also given. A direct analytical approach to account for the effect of species concentration fluctuations on the mean production rate of species (the phenomenon of unmixedness) is also presented. However, the use of the method does not seem justified in view of the excessive computer time required to solve the resulting system of equations.

  11. Early diagenetic processes, fluxes, and reaction rates in sediments of the South Atlantic

    SciTech Connect

    Schulz, H.D.; Dahmke, A.; Schinzel, U.; Wallmann, K.; Zabel, M. )

    1994-05-01

    Porewaters recovered from sediment cores (gravity corers, box corers, and multicorers) from various subregions of the South Atlantic (Amazon River mouth, equatorial upwelling, Congo River mouth, Benguela coastal upwelling area, and Angola Basin) were investigated geochemically. Objectives included determination of Eh, pH, oxygen, nitrate, sulfate, alkalinity, phosphate, ammonium, fluoride, sulfide, Ca, Mg, Sr, Fe, Mn, and Si, in order to quantify organic matter diagenesis and related mineral precipitation and dissolution processes. Porewater profiles from the eastern upwelling areas of the South Atlantic suggest that sulfate reduction in the deeper parts of the sediment may be attributed mainly to methane oxidation, whereas organic matter degradation by sulfate reduction is restricted to the near-surface sediments. Further, a prominent concentration gradient change of sulfate and related mineralization products occurred typically in the upwelling sediments at a depth of 4 to 8 m, far below the zone of bioturbation or bioirrigation. Because other sedimentological reasons seem to fail as explanations, an early diagenetic sulfide oxidation to sulfate within the anoxic environment is discussed. Porewater profiles from the sediments of the Amazon fan area are mainly influenced by reactions with Fe(III)-phases. The remarkable linearity of the concentration gradients of sulfate supports the idea of distinct reaction layers in these sediments. In contrast to the upwelling sediments, the sulfate gradient develops from the sediment surface to a sulfate reduction zone at a depth of 5.3 m, probably because a reoxidation of sulfide is prevented by the reaction with iron oxides and the formation of iron sulfide minerals. A comparison of organic matter degradation rates from the different areas of the South Atlantic show the expected relationship to primary productivity.

  12. 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.

  13. Analytical Solution of Steady State Equations for Chemical Reaction Networks with Bilinear Rate Laws

    PubMed Central

    Halász, Ádám M.; Lai, Hong-Jian; McCabe, Meghan M.; Radhakrishnan, Krishnan; Edwards, Jeremy S.

    2014-01-01

    True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher dimensional space. We show that the linearized version of the steady state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1. PMID:24334389

  14. Path-integral virial estimator for reaction rate calculation basedon the quantum instanton aproximation

    SciTech Connect

    Yang, Sandy; Yamamoto, Takeshi; Miller, William H.

    2005-11-28

    The quantum instanton approximation is a type of quantum transition state theory that calculates the chemical reaction rate using the reactive flux correlation function and its low order derivatives at time zero. Here we present several path-integral estimators for the latter quantities, which characterize the initial decay profile of the flux correlation function. As with the internal energy or heat capacity calculation, different estimators yield different variances (and therefore different convergence properties) in a Monte Carlo calculation. Here we obtain a virial(-type) estimator by using a coordinate scaling procedure rather than integration by parts, which allows more computational benefits. We also consider two different methods for treating the flux operator, i.e., local-path and global-path approaches, in which the latter achieves a smaller variance at the cost of using second-order potential derivatives. Numerical tests are performed for a one-dimensional Eckart barrier and a model proton transfer reaction in a polar solvent, which illustrates the reduced variance of the virial estimator over the corresponding thermodynamic estimator.

  15. Pressure dependence on the reaction propagation rate of PETN at high pressure

    SciTech Connect

    Foltz, M.F.

    1993-04-01

    The reaction propagation rate (RPR) of the sensitive high explosive pentaerythritol tetranitrate (PETN) was measured in a diamond anvil cell (DAC) over the pressure range of 2--20 GPa. The experimental technique used is the same as that previously reported. The RPR data shows that it burns one to two orders of magnitude faster in the DAC than 1,3,5,-triamino-2,4,6-trinitrobenzene (TATB) and nitromethane (CH{sub 3}NO{sub 2}) respectively. The PETN RPR curve did not show sample pressure-dependent behavior like that of nitromethane, but instead varied abruptly like the RPR curve of TATB. In order to interpret these changes, static-pressure DAC mid-IR FTIR spectra were taken of micro-pellets of PETN embedded in KBr. The relationship between changes in the spectra, the RPR curve, and published single crystal PETN wedge test data are discussed.

  16. Temperature dependence of the NO + O3 reaction rate from 195 to 369 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Allen, J. E., Jr.; Brobst, W. D.

    1981-01-01

    The temperature dependence of the NO + O3 reaction rate was examined by means of the fast flow technique. Several different experimental conditions and detection schemes were employed. With excess NO or excess O3, NO2 chemiluminescence was monitored. In addition, with excess O3, NO was followed by fluorescence induced by an NO microwave discharge lamp. The results of the three independent sets of data are compared and found to agree within experimental error, indicating the absence of secondary chemistry which might complicate the kinetics. The data exhibit curvature on an Arrhenius plot; however, the simple Arrhenius expression k = (2.6 + or - 0.8) x 10 to the -12th exp(-1435 + or - 64/T) cu cm/molecule s is an adequate description for T between 195 and 369 K. This result is compared to earlier determinations.

  17. Relative rate constants for the reactions of atomic oxygen with HO2 anad OH radicals

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1983-01-01

    Relative rate constants for the reactions O + HO2 - OH + O2 (1) and O + OH - H + O2 (2) were obtained by using the discharge-flow resonance fluorescence technique at 2 torr total pressure and 299 K. HO2 radicals were generated by reacting atomic hydrogen with an excess of O2. Quasi-steady-state concentrations of OH and HO2 were established in the presence of excess atomic oxygen. Observed concentration ratios, namely the ratio of the OH concentration to the HO2 concentration, resulted in a value of 1.7 + or 0.2 for k1/k2. The error limits are twice the standard deviation obtained from the data analysis. Overall experimental error is estimated to be + or - 25 percent. This result confirms earlier direct measurements of k1 and k2 which required knowledge of absolute radical or atomic oxygen concentrations.

  18. Partial reactions of the Na,K-ATPase: determination of rate constants

    PubMed Central

    1994-01-01

    Experiments were designed to characterize several partial reactions of the Na,K-ATPase and to demonstrate that a model can be defined that reproduces most of the transport features of the pump with a single set of kientic parameters. We used the fluorescence label 5- iodoacetamidofluorescein, which is thought to be sensitive to conformational changes, and the styryl dye RH 421, which can be applied to detect ion-binding and -release reactions. In addition transient electric currents were measured, which are associated mainly with the E1-->E2 conformational transition. Numerical simulations were performed on the basis of a reaction model, that has been developed from the Post- Albers cycle. Analysis of the experimental data allows the determination of several rate constants of the pump cycle. Our conclusions may be summarized as follows: (a) binding of one Na+ ion at the cytoplasmic face is electrogenic. This Na+ ion is specifically bound to a neutral binding site with an affinity of 8 mM in the presence of 10 mM Mg2+. In the absence of divalent cations, the intrinsic binding affinity was found to be 0.7 mM. (b) The analysis of fluorescence experiments with the cardiotonic steroid strophanthidin indicates that the 5-iodoacetamidofluorescein label monitors the conformational transition (Na3)E1-P-->P-E2(Na2), which is accompanied by the release of one Na+ ion. 5-IAF does not respond to the release of the subsequent two Na+ ions, which can be monitored by the RH 421 dye. These experiments indicate further that the conformational transition E1P-->P-E2 is the rate limiting process of the Na+ translocation. The corresponding rate constant was determined to be 22 s-1 at 20 degrees C. From competition experiments with cardiotonic steroids, we estimated that the remaining 2 Na+ ions are released subsequently with a rate constant of at least 5,000 s-1 from their negatively charged binding sites. (c) Comparing the fluorescence experiments with electric current transients

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

    PubMed

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

    2015-11-01

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

  20. 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

    SciTech Connect

    Pritychenko, B.; Mughabghab, S.F.

    2012-12-15

    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.

  1. 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.

  2. High-precision {sup 28}Si(p,t){sup 26}Si reaction to determine {sup 22}Mg({alpha},p){sup 25}Al reaction rates

    SciTech Connect

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

    2011-08-15

    The rise time of stellar x-ray bursts is a signature of thermonuclear runaway processes in the atmosphere of neutron stars and is highly sensitive to a series of ({alpha},p) reactions via high-lying resonances in sd-shell nuclei. Lacking data for the relevant resonance levels, the stellar reaction rates have been calculated using statistical, Hauser-Feshbach models, assuming a high-level density. This assumption may not be correct in view of the selectivity of the ({alpha},p) reaction to natural parity states. We measured the {sup 28}Si(p,t){sup 26}Si reaction with a high-resolution spectrometer to identify resonance levels in {sup 26}Si above the {alpha}-emission threshold at 9.164 MeV excitation energy. These resonance levels are used to calculate the stellar reaction rate of the {sup 22}Mg({alpha},p){sup 25}Al reaction and to test the validity of the statistical assumption.

  3. Helium effects on microstructural change in RAFM steel under irradiation: Reaction rate theory modeling

    NASA Astrophysics Data System (ADS)

    Watanabe, Y.; Morishita, K.; Nakasuji, T.; Ando, M.; Tanigawa, H.

    2015-06-01

    Reaction rate theory analysis has been conducted to investigate helium effects on the formation kinetics of interstitial type dislocation loops (I-loops) and helium bubbles in reduced-activation-ferritic/martensitic steel during irradiation, by focusing on the nucleation and growth processes of the defect clusters. The rate theory model employs the size and chemical composition dependence of thermal dissociation of point defects from defect clusters. In the calculations, the temperature and the production rate of Frenkel pairs are fixed to be T = 723 K and PV = 10-6 dpa/s, respectively. And then, only the production rate of helium atoms was changed into the following three cases: PHe = 0, 10-7 and 10-5 appm He/s. The calculation results show that helium effect on I-loop formation quite differs from that on bubble formation. As to I-loops, the loop formation hardly depends on the existence of helium, where the number density of I-loops is almost the same for the three cases of PHe. This is because helium atoms trapped in vacancies are easily emitted into the matrix due to the recombination between the vacancies and SIAs, which induces no pronounced increase or decrease of vacancies and SIAs in the matrix, leading to no remarkable impact on the I-loop nucleation. On the other hand, the bubble formation depends much on the existence of helium, in which the number density of bubbles for PHe = 10-7 and 10-5 appm He/s is much higher than that for PHe = 0. This is because helium atoms trapped in a bubble increase the vacancy binding energy, and suppress the vacancy dissociation from the bubble, resulting in a promotion of the bubble nucleation. And then, the helium effect on the promotion of bubble nucleation is very strong, even the number of helium atoms in a bubble is not so large.

  4. Reaction rates, depositional history and sources of indium in sediments from Appalachian and Canadian Shield lakes

    NASA Astrophysics Data System (ADS)

    Tessier, André; Gobeil, Charles; Laforte, Lucie

    2014-07-01

    Sediment cores were collected at the deepest site of twelve headwater lakes from the Province of Québec, Canada that receive contaminants only from atmospheric deposition, either directly to the lake surface or indirectly from the watershed. Several of the lakes are located within relatively short distance (<40 km) and others at more than 200 km from potential sources of contamination. The sediments were dated and analyzed for In and other elements including Fe, Mn, Al and organic C. Fe-rich authigenic material was collected on Teflon sheets inserted vertically into the sediments at the only study site whose hypolimnion remains perennially oxic. Porewater samples collected at the coring site of four of the lakes were also analyzed for In and other solutes including sulfide, sulfate, Fe, Mn, inorganic and organic C and major ions. The porewater In profiles display concentration gradients at or below the sediment-water interface. Modeling these profiles with a one-dimensional transport-reaction equation assuming steady state allows definition of depth intervals (zones) where In is either released to or removed from porewater and quantification of net In reactions rates in each zone. The position of the In consumption zones, the shape of the vertical profiles of dissolved In, sulfide and iron, as well as thermodynamic calculations of saturation states collectively suggest that In(OH)3(s) and In2S3(s) do not precipitate in the sediments and that adsorption of In onto sedimentary FeS(s) does not occur. However, similarities in the In and Fe porewater profiles, and the presence of In in the authigenic Fe-rich solids, reveal that part of the In becomes associated with authigenic Fe oxyhydroxides in the perennially oxic lake and is coupled to the Fe redox cycling. Comparison of the In/Corg and In/Fe molar ratios in the authigenic Fe-rich material and in surface sediments (0-0.5 cm) of this lake suggests that most non-lithogenic In was bound to humic substances. From the

  5. 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.

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

    PubMed

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

    2016-03-01

    The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error. PMID:26484648

  7. Ab initio calculation of transition state normal mode properties and rate constants for the H(T)+CH4(CD4) abstraction and exchange reactions

    NASA Astrophysics Data System (ADS)

    Schatz, George C.; Walch, Stephen P.; Wagner, Albert F.

    1980-11-01

    We present ab initio (GVB-POL-CI) calculations for enough of the region about the abstraction and exchange saddle points for H(T)+CH4(CD4) to perform a full normal mode analysis of the transition states. The resulting normal mode frequencies are compared to four other published surfaces: an ab initio UHF-SCF calculation by Carsky and Zahradnik, a semiempirical surface by Raff, and two semiempirical surfaces by Kurylo, Hollinden, and Timmons. Significant quantitative and qualitative differences exist between the POL-CI results and those of the other surfaces. Transition state theory rate constants and vibrationally adiabatic reaction threshold energies were computed for all surfaces and compared to available experimental values. For abstraction, the POL-CI rates are in good agreement with experimental rates and in better agreement than are the rates of any of the other surfaces. For exchange, uncertainties in the experimental values and in the importance of vibrationally nonadiabatic effects cloud the comparison of theory to experiment. Tentative conclusions are that the POL-CI barrier is too low by several kcal. Unless vibrationaly nonadiabatic effects are severe, the POL-CI surface is still in better agreement with experiment than are the other surfaces. The rates for a simple 3-atom transition state theory model (where CH3 is treated as an atom) are compared to the rates for the full 6-atom model. The kinetic energy coupling of reaction coordinate modes to methyl group modes is identified as being of primary importance in determining the accuracy of the 3-atom model for this system. Substantial coupling in abstraction, but not exchange, causes the model to fail for abstraction but succeed for exchange.

  8. Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

    1984-01-01

    Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

  9. The influence of the reaction rate of explosives on blast effects

    NASA Astrophysics Data System (ADS)

    Williams, Pharis E.

    1996-05-01

    Many of the tools developed for the study of shock physics for weapons related work have direct application in industry. For example, instrumentation developed in the study of shock physics has been used to good advantage in the commercial explosives industry. The development of additional sensors is ongoing, though the manner in which these sensors are used and the data analyzed are slightly different because of the application. On the other hand, some of the tools, procedures, and methodologies need some changes in order to provide the best utility to the industrial community. Take reactive hydrocode modeling as an example. The use of reaction rate laws which are very good at modeling the ideal explosives used in shock physics are not universally applicable to industry uses of explosives because of the need to use the energy release rates to tailor the explosive to the job at hand. For example, warheads typically use ideal explosives which release their energy very rapidly and under shock conditions while the commercial composite explosives needed for open pit mining must release the major part of their energy very slowly in order to allow time to over come the inertia of the overburden in heaving it off the ore body. These, and other applications of shock physics techniques will be discussed.

  10. The effect of particle size on hydrolysis reaction rates and rheological properties in cellulosic slurries.

    PubMed

    Dasari, Rajesh K; Eric Berson, R

    2007-04-01

    The effect of varying initial particle sizes on enzymatic hydrolysis rates and rheological properties of sawdust slurries is investigated. Slurries with four particle size ranges (33 microm < x < or = 75 microm, 150 microm < x < or = 180 microm, 295 microm < x < or = 425 microm, and 590 microm < x < or = 850 microm) were subjected to enzymatic hydrolysis using an enzyme dosage of 15 filter paper units per gram of cellulose at 50 degrees C and 250 rpm in shaker flasks. At lower initial particle sizes, higher enzymatic reaction rates and conversions of cellulose to glucose were observed. After 72 h 50 and 55% more glucose was produced from the smallest size particles than the largest size ones, for initial solids concentration of 10 and 13% (w/w), respectively. The effect of initial particle size on viscosity over a range of shear was also investigated. For equivalent initial solids concentration, smaller particle sizes result in lower viscosities such that at a concentration of 10% (w/w), the viscosity decreased from 3000 cP for 150 microm < x < or = 180 microm particle size slurries to 61.4 cP for 33 microm < x < or = 75 microm particle size slurries. Results indicate particle size reduction may provide a means for reducing the long residence time required for the enzymatic hydrolysis step in the conversion of biomass to ethanol. Furthermore, the corresponding reduction in viscosity may allow for higher solids loading and reduced reactor sizes during large-scale processing. PMID:18478396

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

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

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

  12. Evaporation Rate Study and NDMA Formation from UDMH/NO2 Reaction Products

    NASA Technical Reports Server (NTRS)

    Buchanan, Vanessa D.; Dee, Louis A.; Baker, David L.

    2003-01-01

    Laboratory samples of uns-dimethylhydrazine (UDMH) fuel/oxidizer (nitrogen dioxide) non-combustion reaction products (UFORP) were prepared using a unique permeation tube technology. Also, a synthetic UFORP was prepared from UDMH, N-nitrosodimethylamine (NDMA), dimethylammonium nitrate, sodium nitrite and purified water. The evaporation rate of UFORP and synthetic UFORP was determined under space vacuum (approx 10(exp -3) Torr) at -40 ?C and 0 ?C. The material remaining was analyzed and showed that the UFORP weight and NDMA concentration decreased over time; however, NDMA had not completely evaporated. Over 85% of the weight was removed by subjecting the UFORP to 10(-3) Torr for 7 hours at -40 ?C and 4 hours at 0 ?C. A mixture of dimethylammonium nitrate and sodium nitrite formed NDMA at a rapid rate in a moist air environment. A sample of UFORP residue was analyzed for formation of NDMA under various conditions. It was found that NDMA was not formed unless nitrite was added.

  13. Potential chlorofluorocarbon replacements: OH reaction rate constants between 250 and 315 K and infrared absorption spectra

    SciTech Connect

    Garland, N.L.; Medhurst, L.J.; Nelson, H.H.

    1993-12-20

    The authors measured the rate constant for reactions of the OH radical with several potential chlorofluorocarbon replacements over the temperature range 251-314 K using laser photolysis laser-induced fluorescence techniques. The compounds studied and Arrhenius parameters determined from fits to the measured rate constants are as follows: CHF{sub 2}OCHF{sub 2} (E 134), k(T) = (5.4 {+-} 3.5) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}3.1 {+-} 0.4 kcal mol{sup {minus}1})/RT]; CF{sub 3}CH{sub 2}CF{sub 3} (FC 236fa), k(T) = (2.0 {+-} 1.0) x 10{sup {minus}14} cm{sup 3} s{sup {minus}1} exp [({minus}1.8 {+-} 0.3 kcal mol{sup {minus}1})/RT]; CF{sub 3}CHFCHF{sub 2} (FC 236ea), k(T) = (2.0 {+-} 0.9) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.0 {+-} 0.3 kcal mol{sup {minus}1})/RT]; and CF{sub 3}CF{sub 2}CH{sub 2}F (FC 236cb), k(T) = (2.6 {+-} 1.6) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.2 {+-} 0.4 kcal mol{sup {minus}1})/RT]. The measured activation energies (2-3 kcal mol{sup {minus}1}) are consistent with a mechanism of H atom abstraction. The tropospheric lifetimes, estimated from the measured OH reaction rates, and measured integrated infrared absorption cross sections over the range 770 to 1430 cm{sup {minus}1} suggest that E 134 and FC 236fa may have significant global warming potential, while FC 236ea and FC 236cb do not. 17 refs., 4 figs., 3 tabs.

  14. The TDF System for Thermonuclear Plasma Reaction Rates, Mean Energies and Two-Body Final State Particle Spectra

    SciTech Connect

    Warshaw, S I

    2001-07-11

    The rate of thermonuclear reactions in hot plasmas as a function of local plasma temperature determines the way in which thermonuclear ignition and burning proceeds in the plasma. The conventional model approach to calculating these rates is to assume that the reacting nuclei in the plasma are in Maxwellian equilibrium at some well-defined plasma temperature, over which the statistical average of the reaction rate quantity {sigma}v is calculated, where {sigma} is the cross-section for the reaction to proceed at the relative velocity v between the reacting particles. This approach is well-understood and is the basis for much nuclear fusion and astrophysical nuclear reaction rate data. The Thermonuclear Data File (TDF) system developed at the Lawrence Livermore National Laboratory (Warshaw 1991), which is the topic of this report, contains data on the Maxwellian-averaged thermonuclear reaction rates for various light nuclear reactions and the correspondingly Maxwellian-averaged energy spectra of the particles in the final state of those reactions as well. This spectral information closely models the output particle and energy distributions in a burning plasma, and therefore leads to more accurate computational treatments of thermonuclear burn, output particle energy deposition and diagnostics, in various contexts. In this report we review and derive the theoretical basis for calculating Maxwellian-averaged thermonuclear reaction rates, mean particle energies, and output particle spectral energy distributions for these reactions in the TDF system. The treatment of the kinematics is non-relativistic. The current version of the TDF system provides exit particle energy spectrum distributions for two-body final state reactions only. In a future report we will discuss and describe how output particle energy spectra for three- and four-body final states can be developed for the TDF system. We also include in this report a description of the algorithmic implementation of the

  15. Critical Evaluation of Chemical Reaction Rates and Collision Cross Sections of Importance in the Earth's Upper Atmosphere and the Atmospheres of Other Planets, Moons, and Comets

    NASA Astrophysics Data System (ADS)

    Huestis, D. L.

    2005-05-01

    We recommend establishment of a long-term program of critical evaluation by domain experts of the rates and cross sections of atomic and molecular processes that are needed for understanding and modeling the atmospheres in the solar system. We envision products resembling those from the ongoing JPL/NASA Panel for Data Evaluation and the efforts of the international combustion modeling community funded by US DOE and its European counterpart. Both of these endeavors already provide some important inputs for modeling the atmospheres of the Earth, planets, moons, and comets. However, their applications restrict the choice of which processes to evaluate and the temperature and pressure ranges to cover, thus leaving large gaps that need to be filled. Interestingly, an older evaluation program once filled some of these gaps. Funded by the US DoD in the 1960s-1980s, the DNA Reaction Rate Handbook provided a thorough treatment of numerous types of collisions and reactions that are important in the Earth's lower ionosphere, and the program even provided funding for new laboratory measurements. Other examples could be given, with the on-line resources at NIST being among the best, but most provide a narrower scope or less critical evaluation. What is needed is not a just a list of processes and numbers (i.e., a "database"), but rather serious comparison of the available information and specific statements from independent expert laboratory/theory data providers about what should be believed, what uncertainty to assign, and what is most in need of redetermination. The major topic areas would include the following: 1. Chemical reactions of neutral atoms and molecules in their ground electronic states 2. Ion-molecule reactions 3. Chemistry, relaxation, and radiation of electronically excited atoms and molecules 4. Vibrational and rotational relaxation and radiation 5. Photoabsorption, photodissociation, and photoionization 6. Electron-impact excitation, dissociation, ionization

  16. Evaluating rates and yields of second-order, photoinitiated reactions under conditons of Gaussian-profile excitation

    SciTech Connect

    Cambron, R.T.; Zhu, X.R.; Harris, J.M.

    1994-09-01

    Under conditions of Gaussian radial profile excitation, a mixed-order kinetic model is used to interpret the rates and yields of photoinitiated reactions. This model is used to determine the triplet-triplet annihilation rate constant for benzophenone in acetonitrile and anthracene at room temperature. 34 refs., 9 figs.

  17. Bimolecular electron transfer reactions in coumarin amine systems: Donor acceptor orientational effect on diffusion-controlled reaction rates

    NASA Astrophysics Data System (ADS)

    Satpati, A. K.; Nath, S.; Kumbhakar, M.; Maity, D. K.; Senthilkumar, S.; Pal, H.

    2008-04-01

    Electron transfer (ET) reactions between excited coumarin dyes and different aliphatic amine (AlA) and aromatic amine (ArA) donors have been investigated in acetonitrile solution using steady-state (SS) and time-resolved (TR) fluorescence quenching measurements. No ground state complex or emissive exciplex formation has been indicated in these systems. SS and TR measurements give similar quenching constants ( kq) for each of the coumarin-amine pairs, suggesting dynamic nature of interaction in these systems. On correlating kq values with the free energy changes (Δ G0) of the ET reactions show the typical Rehm-Weller type of behavior as expected for bimolecular ET reactions under diffusive condition, where kq increases with -Δ G0 at the lower exergonicity (-Δ G0) region but ultimately saturate to a diffusion-limited value (kqDC) at the higher exergonicity region. It is, however, interestingly observed that the kqDC values vary largely depending on the type of the amines used. Thus, kqDC is much higher with ArAs than AlAs. Similarly, the kqDC for cyclic monoamine 1-azabicyclo-[2,2,2]-octane (ABCO) is distinctly lower and that for cyclic diamine 1,4-diazabicyclo-[2,2,2]-octane (DABCO) is distinctly higher than the kqDC value obtained for other noncyclic AlAs. These differences in the kqDC values have been rationalized on the basis of the differences in the orientational restrictions involved in the ET reactions with different types of amines. As understood, n-type donors (AlAs) introduce large orientational restriction and thus significantly reduces the ET efficiency in comparison to the π-type donors (ArAs). Structural constrains are inferred to be the reason for the differences in the kqDC values involving ABCO, DABCO donors in comparison to other noncyclic AlAs. Supportive evidence for the orientational restrictions involving different types of amines donors has also been obtained from DFT based quantum chemical calculations on the molecular orbitals of

  18. Early diagenetic processes, fluxes, and reaction rates in sediments of the South Atlantic

    NASA Astrophysics Data System (ADS)

    Schulz, Horst D.; Dahmke, Andreas; Schinzel, Uwe; Wallmann, Klaus; Zabel, Matthias

    1994-05-01

    Porewaters recovered from sediment cores (gravity corers, box corers, and multicorers) from various subrogions of the South Atlantic (Amazon River mouth, equatorial upwelling, Congo River mouth, Benguela coastal upwelling area, and Angola Basin) were investigated geochemically. Objectives included determination of Eh, pH, oxygen, nitrate, sulfate, alkalinity, phosphate, ammonium, fluoride, sulfide, Cal, Mg, Sr, Fe, Mn, and Si, in order to quantify organic matter diagenesis and related mineral precipitation and dissolution processes. Porewater profiles from the eastern upwelling areas of the South Atlantic suggest that sulfate reduction in the deeper parts of the sediment may be attributed mainly to methane oxidation, whereas organic matter degradation by sulfate reduction is restricted to the near-surface sediments. Further, a prominent concentration gradient change of sulfate and related mineralization products occurred typically in the upwelling sediments at a depth of 4 to 8 m, far below the zone of bioturbation or bioirrigation. Because other sedimentological reasons seem to fail as explanations, an early diagenetic sulfide oxidation to sulfate within the anoxic environment is discussed. Porewater profiles from the sediments of the Amazon fan area are mainly influenced by reactions with Fe(III)-phases. The remarkable linearity of the concentration gradients of sulfate supports the idea of distinct reaction layers in these sediments. In contrast to the upwelling sediments, the sulfate gradient develops from the sediment surface to a sulfate reduction zone at a depth of 5.3 m, probably because a reoxidation of sulfide is prevented by the reaction with iron oxides and the formation of iron sulfide minerals. A comparison of organic matter degradation rates from the different areas of the South Atlantic show the expected relationship to primary productivity. Oxygen is the dominating oxidant, whereas organic matter degradation by nitrate, Mn(IV)- and probably also Fe

  19. Quantum mechanical reaction rate constants by vibrational configuration interaction: the OH + H2->H2O + H reaction as a function of temperature.

    PubMed

    Chakraborty, Arindam; Truhlar, Donald G

    2005-05-10

    The thermal rate constant of the 3D OH + H(2)-->H(2)O + H reaction was computed by using the flux autocorrelation function, with a time-independent square-integrable basis set. Two modes that actively participate in bond making and bond breaking were treated by using 2D distributed Gaussian functions, and the remaining (nonreactive) modes were treated by using harmonic oscillator functions. The finite-basis eigenvalues and eigenvectors of the Hamiltonian were obtained by solving the resulting generalized eigenvalue equation, and the flux autocorrelation function for a dividing surface optimized in reduced-dimensionality calculations was represented in the basis formed by the eigenvectors of the Hamiltonian. The rate constant was obtained by integrating the flux autocorrelation function. The choice of the final time to which the integration is carried was determined by a plateau criterion. The potential energy surface was from Wu, Schatz, Lendvay, Fang, and Harding (WSLFH). We also studied the collinear H + H(2) reaction by using the Liu-Siegbahn-Truhlar-Horowitz (LSTH) potential energy surface. The calculated thermal rate constant results were compared with reported values on the same surfaces. The success of these calculations demonstrates that time-independent vibrational configuration interaction can be a very convenient way to calculate converged quantum mechanical rate constants, and it opens the possibility of calculating converged rate constants for much larger reactions than have been treated until now. PMID:15774583

  20. Selective determination of rate constants of reactions of atomic hydrogen with various functional groups of a complex molecule

    NASA Astrophysics Data System (ADS)

    Brauer, G. B.; Pugachev, D. V.; Azatyan, V. V.

    2016-05-01

    The possibility of determining absolute values of the rate constants of reactions of active intermediate species with different functional groups of molecules is demonstrated by measuring macrokinetic combustion characteristics. The Arrhenius parameters of the rate constant of the reaction between atomic hydrogen with the methylene group of ethanol and molecular oxygen within the temperature range of 830-970 K are determined. The reasons for the differences between the rate constants of reactions with the methylene and methyl groups of an ethanol molecule are discussed using thermochemical data. It is found that the obtained values of activation energies and preexponential factors of rate constants are in good agreement with the literature data on the region of lower temperatures.

  1. 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. PMID:24156502

  2. Experimental measurements of low temperature rate coefficients for neutral-neutral reactions of interest for atmospheric chemistry of Titan, Pluto and Triton: reactions of the CN radical.

    PubMed

    Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R

    2010-01-01

    The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere. PMID:21302546

  3. Direct Measurement of the Effective Rate Constant for Primary Charge Separation in Isolated Photosystem II Reaction Centers

    SciTech Connect

    Greenfield, S. R.; Seibert, M.; Govindjee; Wasielewski, M. R.

    1997-03-27

    Transient absorption measurements of the pheophytin a anion band and Qx band bleach region using preferential excitation of P680 are performed on isolated photosystem II reaction centers to determine the effective rate constant for charge separtion. A novel analysis of the Qx band bleach region explicity takes the changing background into account in order to directly measure the rate of growth of the bleach. Both spectral regions reveal biphasic kinetics, with a ca. (8 ps)-1 rate constant for the faster component, and a ca. (50 ps)-1 rate constant for the slower component. We propose that the fster component corresponds to the effective rate constant for charge separation from within the equilibrated reaction center core and provides a lower limit for the intrinsic rate constant for charge separation. The slower component corresponds to charge separation that is limited by slow energy transfer from a long-wavelength accessory chlorophyll a.

  4. On the time dependence of rate coefficients of irreversible reactions between reactants with anisotropic reactivity in liquid solutions

    NASA Astrophysics Data System (ADS)

    Ivanov, Konstantin L.; Lukzen, Nikita N.; Doktorov, Alexander B.

    2016-08-01

    Time dependence of the rate coefficients of sterically specific reactions is analyzed theoretically. Generally, such reactions exhibit a non-trivial dependence of their rate constant on the steric factor, f < 1, which is defined as the fraction of reactive surface area. Notably, the rate constant of a diffusion-controlled reaction is proportional not to f but, counter-intuitively, to √{ f } due to partial averaging of the reaction anisotropy by translational diffusion. Here we demonstrate that the effective steric factor of a diffusion-influenced reaction is strongly time-dependent, increasing from f to √{ f } . When reactants have several active sites, these sites "interfere" each other in the sense that the rate constant depends on their relative positions. We demonstrate that such an interference effect is strongly time-dependent as well: it is absent at t = 0 but builds up with time. We argue that the outlined effects are also of importance for calculating the fluorescence quenching rate constants.

  5. Effect of Buddhist meditation on serum cortisol and total protein levels, blood pressure, pulse rate, lung volume and reaction time.

    PubMed

    Sudsuang, R; Chentanez, V; Veluvan, K

    1991-09-01

    Serum cortisol and total protein levels, blood pressure, heart rate, lung volume, and reaction time were studied in 52 males 20-25 years of age practicing Dhammakaya Buddhist meditation, and in 30 males of the same age group not practicing meditation. It was found that after meditation, serum cortisol levels were significantly reduced, serum total protein level significantly increased, and systolic pressure, diastolic pressure and pulse rate significantly reduced. Vital capacity, tidal volume and maximal voluntary ventilation were significantly lower after meditation than before. There were also significant decreases in reaction time after mediation practice. The percentage decrease in reaction time during meditation was 22%, while in subjects untrained in meditation, the percentage decrease was only 7%. Results from these studies indicate that practising Dhammakaya Buddhist meditation produces biochemical and physiological changes and reduces the reaction time. PMID:1801007

  6. Uncertainty quantification for the impact of injection rate fluctuation on the geomechanical response of geological carbon sequestration

    SciTech Connect

    Bao, Jie; Chu, Yanjun; Xu, Zhijie; Tartakovsky, Alexandre M.; Fang, Yilin

    2014-01-01

    We present an analysis of the geomechanical effects of injection rate fluctuations for geological sequestration of carbon dioxide (CO2). Initially, we present analytical solutions for the effects of injection rate fluctuations on CO2 fluid pressure spatial distribution and temporal evolution for a typical injection scenario. Numerical calculations are performed using a finite element method to investigate the effects of injection rate fluctuations on geomechanical deformation, stresses, and potential failure of the aquifer and caprock layers. The numerical method was first validated by the fluid pressure distribution’s good agreement with the analytical solution. It was shown that for any Gaussian fluctuations of injection rate Q with given mean Q and variance ε_Q, the coefficients of variance for fluid pressure (ϵ_p=ε_p ), deformation (ϵ_u=ε_u ), and stresses (ϵ_σ=ε_σ ) increase linearly with the coefficient of variance for injection rate (ϵ_Q=ε_Q ). The proportional constants are identified, and the fluctuations have the most pronounced effect on the geomechanical stresses, and, therefore, on the potential failure of the aquifer and caprock layers. Instead of expensive computational simulation, this study provides an efficient tool to estimate the geomechanical response variance to injection rate fluctuation. A failure analysis was presented based on the numerical results, where probability of failure was estimated for fluctuating injection rates with different mean and variance during the entire injection period. It was found that with increasing injection rate fluctuation, the failure probability increases significantly. Therefore, the risk associated with injection rate fluctuations should be carefully evaluated.

  7. Proteolysis inside the membrane is a rate-governed reaction not driven by substrate affinity

    PubMed Central

    Dickey, Seth W.; Baker, Rosanna P.; Cho, Sangwoo; Urban, Siniša

    2013-01-01

    SUMMARY Enzymatic cleavage of transmembrane anchors to release proteins from the membrane controls diverse signaling pathways and is implicated in over a dozen diseases. How catalysis works within the viscous, water-excluding, two-dimensional membrane is unknown. We developed an inducible reconstitution system to interrogate rhomboid proteolysis quantitatively within the membrane in real time. Remarkably, rhomboid proteases displayed no physiological affinity for substrates (Kd ~190 μM, or 0.1 mol%). Instead, ~10,000-fold differences in proteolytic efficiency with substrate mutants and diverse rhomboid proteases were reflected in kcat values alone. Analysis of gate-open mutant and solvent isotope effects revealed that substrate gating, not hydrolysis, is rate limiting. Ultimately a single proteolytic event within the membrane normally takes minutes. Rhomboid intramembrane proteolysis is thus a slow, kinetically controlled reaction not driven by transmembrane protein-protein affinity. These properties are unlike those of other studied proteases or membrane proteins but strikingly reminiscent of one subset of DNA-repair enzymes, raising important mechanistic and drug-design implications. PMID:24315097

  8. Astrophysical Reaction Rate for the Neutron-Generator Reaction {sup 13}C({alpha},n){sup 16}O in Asymptotic Giant Branch Stars

    SciTech Connect

    Johnson, E. D.; Rogachev, G. V.; Baby, L. T.; Cluff, W. T.; Crisp, A. M.; Diffenderfer, E.; Green, B. W.; Hinners, T.; Hoffman, C. R.; Kemper, K. W.; Momotyuk, O.; Peplowski, P.; Pipidis, A.; Reynolds, R.; Roeder, B. T.; Mukhamedzhanov, A. M.; Goldberg, V. Z.; Brown, S.

    2006-11-10

    The reaction {sup 13}C({alpha},n) is considered to be the main source of neutrons for the s process in asymptotic giant branch stars. At low energies, the cross section is dominated by the 1/2{sup +} 6.356 MeV subthreshold resonance in {sup 17}O whose contribution at stellar temperatures is uncertain by a factor of 10. In this work, we performed the most precise determination of the low-energy astrophysical S factor using the indirect asymptotic normalization (ANC) technique. The {alpha}-particle ANC for the subthreshold state has been measured using the sub-Coulomb {alpha}-transfer reaction ({sup 6}Li,d). Using the determined ANC, we calculated S(0), which turns out to be an order of magnitude smaller than in the nuclear astrophysics compilation of reaction rates.

  9. Absolute Rate Constants for the Reaction of OH with [|#11#|]Cyclopentane and Cycloheptane from 230-350 K

    NASA Astrophysics Data System (ADS)

    Dransfield, T. J.; Gennaco, M. M.; Huang, Y.; Hannun, R. A.

    2011-12-01

    We report absolute measurements of the rate constants of the reaction of hydroxyl radical (OH) with cyclopentane and cycloheptane in 6-8 Torr of nitrogen from 230-350 K using Harvard's High Pressure Flow System. Ethane's reactivity was simultaneously measured as a test of experimental performance. Hydroxyl concentrations were measured using Laser-Induced Fluorescence, and alkane concentrations were measured using Fourier-Transform Infrared Spectroscopy. Recent work on this flow system has suggested that cyclohexane has a significantly higher activation energy to reaction with OH than does cyclo-octane, a result which is not suggested by our understanding of hydrocarbon reactivity nor predicted by structure-activity relationships. This work examines the temperature dependent rates for two other similarly-sized cycloalkanes to determine whether they behave as cyclohexane or as cyclooctane. While several previous experiments have studied the reaction with cyclopentane, there is significant scatter in the room temperature rates, and only four absolute rate measurements are available at non-ambient temperatures. There are only two absolute rate measurements available for the reaction with cycloheptane; only one of these reports a temperature dependence, and that study is limited to temperatures above 298 K. Thus, this work significantly expands the available data set for both reactions. The data for the reactions of OH with ethane, cyclopentane, cyclohexane, and cycloheptane are all modeled using a simple Arrhenius fit, and also with a modified Arrhenius equation based on transition state theory, ignoring tunneling. Results from the latter fit indicate that the activation barriers for both title reactions are greater than that of OH + cyclo-octane. The measured activation energy for OH + cyclopentane actually exceeds that of OH + cyclohexane.

  10. Asn-150 of Murine Erythroid 5-Aminolevulinate Synthase Modulates the Catalytic Balance between the Rates of the Reversible Reaction.

    PubMed

    Stojanovski, Bosko M; Ferreira, Gloria C

    2015-12-25

    5-Aminolevulinate synthase (ALAS) catalyzes the first step in mammalian heme biosynthesis, the pyridoxal 5'-phosphate (PLP)-dependent and reversible reaction between glycine and succinyl-CoA to generate CoA, CO2, and 5-aminolevulinate (ALA). Apart from coordinating the positioning of succinyl-CoA, Rhodobacter capsulatus ALAS Asn-85 has a proposed role in regulating the opening of an active site channel. Here, we constructed a library of murine erythroid ALAS variants with substitutions at the position occupied by the analogous bacterial asparagine, screened for ALAS function, and characterized the catalytic properties of the N150H and N150F variants. Quinonoid intermediate formation occurred with a significantly reduced rate for either the N150H- or N150F-catalyzed condensation of glycine with succinyl-CoA during a single turnover. The introduced mutations caused modifications in the ALAS active site such that the resulting variants tipped the balance between the forward- and reverse-catalyzed reactions. Although wild-type ALAS catalyzes the conversion of ALA into the quinonoid intermediate at a rate 6.3-fold slower than the formation of the same quinonoid intermediate from glycine and succinyl-CoA, the N150F variant catalyzes the forward reaction at a mere 1.2-fold faster rate than that of the reverse reaction, and the N150H variant reverses the rate values with a 1.7-fold faster rate for the reverse reaction than that for the forward reaction. We conclude that the evolutionary selection of Asn-150 was significant for optimizing the forward enzymatic reaction at the expense of the reverse, thus ensuring that ALA is predominantly available for heme biosynthesis. PMID:26511319

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

    NASA Astrophysics Data System (ADS)

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

    1986-04-01

    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.

  12. Rate-promoting vibrations and coupled hydrogen-electron transfer reactions in the condensed phase: A model for enzymatic catalysis

    NASA Astrophysics Data System (ADS)

    Mincer, Joshua S.; Schwartz, Steven D.

    2004-04-01

    A model is presented for coupled hydrogen-electron transfer reactions in condensed phase in the presence of a rate promoting vibration. Large kinetic isotope effects (KIEs) are found when the hydrogen is substituted with deuterium. While these KIEs are essentially temperature independent, reaction rates do exhibit temperature dependence. These findings agree with recent experimental data for various enzyme-catalyzed reactions, such as the amine dehydrogenases and soybean lipoxygenase. Consistent with earlier results, turning off the promoting vibration results in an increased KIE. Increasing the barrier height increases the KIE, while increasing the rate of electron transfer decreases it. These results are discussed in light of other views of vibrationally enhanced tunneling in enzymes.

  13. Shell Model Based Reaction Rates for rp-PROCESS Nuclei in the Mass Range A=44-63

    NASA Astrophysics Data System (ADS)

    Fisker, J. L.; Barnard, V.; Görres, J.; Langanke, K.; Martínez-Pinedo, G.; Wiescher, M. C.

    2001-11-01

    We have used large-scale shell-model diagonalization calculations to determine the level spectra, proton spectroscopic factors, and electromagnetic transition probabilities for proton rich nuclei in the mass range A=44-63. Based on these results and the available experimental data, we calculated the resonances for proton capture reactions on neutron deficient nuclei in this mass range. We also calculated the direct capture processes on these nuclei in the framework of a Woods-Saxon potential model. Taking into account both resonant and direct contributions, we determined the ground-state proton capture reaction rates for these nuclei under hot hydrogen burning conditions for temperatures between 108 and 1010 K. The calculated compound-nucleus level properties and the reaction rates are presented here; the rates are also available in computer-readable format from the authors.

  14. Determination of the astrophysical 12N(p,γ)13O reaction rate from the 2H(12N,13O)n reaction and its astrophysical implications

    NASA Astrophysics Data System (ADS)

    Guo, B.; Su, J.; Li, Z. H.; Wang, Y. B.; Yan, S. Q.; Li, Y. J.; Shu, N. C.; Han, Y. L.; Bai, X. X.; Chen, Y. S.; Liu, W. P.; Yamaguchi, H.; Binh, D. N.; Hashimoto, T.; Hayakawa, S.; Kahl, D.; Kubono, S.; He, J. J.; Hu, J.; Xu, S. W.; Iwasa, N.; Kume, N.; Li, Z. H.

    2013-01-01

    The evolution of massive stars with very low-metallicities depends critically on the amount of CNO nuclides which they produce. The 12N(p,γ)13O reaction is an important branching point in the rap processes, which are believed to be alternative paths to the slow 3α process for producing CNO seed nuclei and thus could change the fate of massive stars. In the present work, the angular distribution of the 2H(12N, 13O)n proton transfer reaction at Ec.m.=8.4 MeV has been measured for the first time. Based on the Johnson-Soper approach, the square of the asymptotic normalization coefficient (ANC) for the virtual decay of 13Og.s. → 12N+p was extracted to be 3.92±1.47 fm-1 from the measured angular distribution and utilized to compute the direct component in the 12N(p,γ)13O reaction. The direct astrophysical S factor at zero energy was then found to be 0.39±0.15 keV b. By considering the direct capture into the ground state of 13O, the resonant capture via the first excited state of 13O and their interference, we determined the total astrophysical S factors and rates of the 12N(p,γ)13O reaction. The new rate is two orders of magnitude slower than that from the REACLIB compilation. Our reaction network calculations with the present rate imply that 12N(p,γ)13O will only compete successfully with the β+ decay of 12N at higher (˜2 orders of magnitude) densities than initially predicted.

  15. Uncertainties in slip-rate estimates for the Mission Creek strand of the southern San Andreas fault at Biskra Palms Oasis, southern California

    USGS Publications Warehouse

    Behr, W.M.; Rood, D.H.; Fletcher, K.E.; Guzman, N.; Finkel, R.; Hanks, T.C.; Hudnut, K.W.; Kendrick, K.J.; Platt, J.P.; Sharp, W.D.; Weldon, R.J.; Yule, J.D.

    2010-01-01

    This study focuses on uncertainties in estimates of the geologic slip rate along the Mission Creek strand of the southern San Andreas fault where it offsets an alluvial fan (T2) at Biskra Palms Oasis in southern California. We provide new estimates of the amount of fault offset of the T2 fan based on trench excavations and new cosmogenic 10Be age determinations from the tops of 12 boulders on the fan surface. We present three alternative fan offset models: a minimum, a maximum, and a preferred offset of 660 m, 980 m, and 770 m, respectively. We assign an age of between 45 and 54 ka to the T2 fan from the 10Be data, which is significantly older than previously reported but is consistent with both the degree of soil development associated with this surface, and with ages from U-series geochronology on pedogenic carbonate from T2, described in a companion paper by Fletcher et al. (this volume). These new constraints suggest a range of slip rates between ~12 and 22 mm/yr with a preferred estimate of ~14-17 mm/yr for the Mission Creek strand of the southern San Andreas fault. Previous studies suggested that the geologic and geodetic slip-rate estimates at Biskra Palms differed. We find, however, that considerable uncertainty affects both the geologic and geodetic slip-rate estimates, such that if a real discrepancy between these rates exists for the southern San Andreas fault at Biskra Palms, it cannot be demonstrated with available data. ?? 2010 Geological Society of America.

  16. Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

    SciTech Connect

    Koretsky, A.P.

    1984-01-01

    /sup 31/P NMR is a unique tool to study bioenergetics in living cells. The application of magnetization transfer techniques to the measurement of steady-state enzyme reaction rates provides a new approach to understanding the regulation of high energy phosphate metabolism. This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate were compared to whole kidney oxygen consumption and Na/sup +/ reabsorption rates to derive ATP/O values. The problems associated with ATP synthesis rate measurements in kidney, e.g. the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed. In heart, the forward rate through creatine kinase was measured to be larger than the reverse rate. To account for the difference in forward and reverse rates a model is proposed based on the compartmentation of a small pool of ATP.

  17. EFFECTS OF PORE STRUCTURE CHANGE AND MULTI-SCALE HETEROGENEITY ON CONTAMINANT TRANSPORT AND REACTION RATE UPSCALING

    SciTech Connect

    Peters, Catherine A

    2013-05-15

    This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE legacy waste problems.

  18. Combining Bayesian methods and aircraft observations to constrain the HO. + NO2 reaction rate

    EPA Science Inventory

    Tropospheric ozone is the third strongest greenhouse gas, and has the highest uncertainty in radiative forcing of the top five greenhouse gases. Throughout the troposphere, ozone is produced by radical oxidation of nitrogen oxides (NO,x =NO+NO2). In the uppe...

  19. Voluntary Control of Human Heart Rate: Effect on Reaction to Aversive Stimulation: A Replication and Extension

    ERIC Educational Resources Information Center

    Sirota, Alan D.; And Others

    1976-01-01

    Hypothesized that biofeedback training for fear-relevant physiological changes might provide a useful therapeutic strategy to influence directly a person's reaction to anxiety-inducing situations. (Author)

  20. High-precision (p,t) reaction measurement to determine {sup 18}Ne({alpha},p){sup 21}Na reaction rates

    SciTech Connect

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

    2009-11-15

    x-ray bursts are identified as thermonuclear explosions in the outer atmosphere of accreting neutron stars. The thermonuclear runaway is fueled by the {alpha}p process that describes a sequence of ({alpha},p) reactions triggered by the {sup 18}Ne({alpha},p){sup 21}Na breakout reaction from the hot CNO cycles. We studied the level structure of the compound nucleus {sup 22}Mg by measuring the {sup 24}Mg(p,t){sup 22}Mg reaction at the Grand Raiden spectrometer at Research Center for Nuclear Physics, Osaka. A large number of {alpha}-unbound states was identified and precise excitation energies were determined. Based on shell model and {alpha}-cluster model calculations we predict the level parameters for determining the stellar reaction rate of {sup 18}Ne({alpha},p){sup 21}Na for a wide temperature range. x-ray burst simulations have been performed to study the impact of the reaction on the x-ray burst luminosity.

  1. Rate constant measurements for the reaction Cl + CH2O yields HCl + CHO Implications regarding the removal of stratospheric chlorine

    NASA Technical Reports Server (NTRS)

    Anderson, P. C.; Kurylo, M. J.

    1979-01-01

    The flash photolysis resonance fluorescence technique was employed to investigate the rate constant for the reaction Cl + CH2O yields HCl + CHO from 223 to 323 K. An Arrhenius fit of the data gives a rate constant equal to (1.09 + or - 0.40) x 10 to the -10th exp/-(131 + or - 98)/T/ in units of cu cm/molecule per sec. The results are compared to two very recent kinetic studies and are assessed in view of the reaction's role in disrupting the Cl-ClO stratospheric ozone depletion chain.

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

    SciTech Connect

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

    2009-02-25

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

  3. SU-E-J-116: Uncertainties Associated with Dose Summation of High-Dose Rate Brachytherapy and Intensity Modulated Radiotherapy for Gynecological Cases

    SciTech Connect

    Kauweloa, K; Bergamo, A; Gutierrez, A; Stathakis, S; Papanikolaou, N; Kirby, N; Mavroidis, P

    2015-06-15

    Purpose: Determining the cumulative dose distribution (CDD) for gynecological patients treated with both high-dose rate (HDR) brachytherapy and intensity-modulated radiotherapy (IMRT) is challenging. The purpose of this work is to study the uncertainty of performing this with a structure-guided deformable (SGD) approach in Velocity. Methods: For SGD, the Hounsfield units inside specified contours are overridden to set uniform values. Deformable image registration (DIR) is the run on these process images, which forces the DIR to focus on these contour boundaries. 18 gynecological cancer patients were used in this study. The original bladder and rectum planning contours for these patients were used to drive the SGD. A second set of contours were made of the bladder by the same person with the intent of carefully making them completely consistent with each other. This second set was utilized to evaluate the spatial accuracy of the SGD. The determined spatial accuracy was then multiplied by the local dose gradient to determine a dose uncertainty associated with the SGD dose warping. The normal tissue complication probability (NTCP) was then calculated for each dose volume histogram (DVH) that included four different probabilistic uncertainties associated with the spatial errors (e.g., 68.3% and 95.4%). Results: The NTCPs for each DVH (e.g., NTCP-−95.4%, NTCP-−68.3%, NTCP-68.3%, NTCP-95.4%) differed amongst patients. All patients had an NTCP-−95.4% close to 0%, while NTCP-95.4% ranged from 0.67% to 100%. Nine patients had an NTCP-−95.4% less than 50% while the remaining nine patients had NTCP-95.4% greater than 50%. Conclusion: The uncertainty associated with this CDD technique renders a large NTCP uncertainty. Thus, it is currently not practical for clinical use. The two ways to improve this would be to use more precise contours to drive the SGD and to use a more accurate DIR algorithm.

  4. 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

    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.

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

    SciTech Connect

    Hufnagel, Todd C.

    2014-06-09

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

  6. A methodology to reduce uncertainties in the high-flow portion of the rating curve for Goodwater Creek Watershed

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  7. Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

    1984-01-01

    The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

  8. A rate-determining proton relay in the pyruvate kinase reaction

    SciTech Connect

    Rose, I.A.; Kuo, D.J.; Warms, J.V.B. )

    1991-01-22

    This study ascribes the large steady-state D{sub 2}O isotope effect on k{sub cat} of pyruvate kinase (PEP + ADP {yields} pyruvate + ATP) to the reprotonation of the product form of the enzyme for use in forming pyruvate. Previous tritium trapping experiments with muscle pyruvate kinase showed that the proton used for ketonization of enolpyruvate is derived from an enzyme pool that contains three kinetically equivalent hydrogens that could be trapped in a nontritiated chase medium by high levels of ADP and PEP. The exchange of this pool with the medium was rapid in the free enzyme prior to addition of PEP, and apparently much less in the completed complex. The present study shows that the competition constant, K{sub 1/2}, is decreased by {approximately}5-fold in D{sub 2}O, the same effect seen on k{sub cat} under conditions where k{sub cat}/K{sub m}, measured in the steady state, is not changed. The common effect of D{sub 2}O on k{sub cat} in the steady state and k{sub off}{sup T} in pulse/chase suggests that the forward reaction rate is determined by hydrogen transfer to the enzyme. Further evidence indicates that the kinetically important proton in question is the proton used for ketonization of enolpyruvate, the substrate proton. With Co, roughly three T of the pool can be trapped. With Mg, only one T can be trapped from the same pulse solution at the highest concentrations of PEP. Apparently two positions, possibly from a bound water molecule, are rapidly exchanged with water of the chase. The inference that lysine NH{sub 3{sup +}} is the proton donor group on the basis of the three T trapped is open to question by evidence that one or two of these come from relay positions.

  9. Optimal reconstruction of concentrations, gradients and reaction rates from particle distributions

    NASA Astrophysics Data System (ADS)

    Fernàndez-Garcia, D.; Sanchez-Vila, X.

    2011-03-01

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

  10. An Interactive Classroom Activity Demonstrating Reaction Mechanisms and Rate-Determining Steps

    ERIC Educational Resources Information Center

    Jennings, Laura D.; Keller, Steven W.

    2005-01-01

    An interactive classroom activity that includes two-step reaction of unwrapping and eating chocolate candies is described which brings not only the reaction intermediate, but also the reactants and products into macroscopic view. The qualitative activation barriers of both steps can be adjusted independently.

  11. Charting an Alternate Pathway to Reaction Orders and Rate Laws in Introductory Chemistry Courses

    ERIC Educational Resources Information Center

    Rushton, Gregory T.; Criswell, Brett A.; McAllister, Nicole D.; Polizzi, Samuel J.; Moore, Lamesha A.; Pierre, Michelle S.

    2014-01-01

    Reaction kinetics is an axiomatic topic in chemistry that is often addressed as early as the high school course and serves as the foundation for more sophisticated conversations in college-level organic, physical, and biological chemistry courses. Despite the fundamental nature of reaction kinetics, students can struggle with transforming their…

  12. Determination of the reaction rate coefficient of sulphide mine tailings deposited under water.

    PubMed

    Awoh, Akué Sylvette; Mbonimpa, Mamert; Bussière, Bruno

    2013-10-15

    The efficiency of a water cover to limit dissolved oxygen (DO) availability to underlying acid-generating mine tailings can be assessed by calculating the DO flux at the tailings-water interface. Fick's equations, which are generally used to calculate this flux, require knowing the effective DO diffusion coefficient (Dw) and the reaction (consumption) rate coefficient (Kr) of the tailings, or the DO concentration profile. Whereas Dw can be accurately estimated, few studies have measured the parameter Kr for submerged sulphide tailings. The objective of this study was to determine Kr for underwater sulphide tailings in a laboratory experiment. Samples of sulphide mine tailings (an approximately 6 cm layer) were placed in a cell under a water cover (approximately 2 cm) maintained at constant DO concentration. Two tailings were studied: TA1 with high sulphide content (83% pyrite) and TA2 with low sulphide content (2.8% pyrite). DO concentration was measured with a microelectrode at various depths above and below the tailings-water interface at 1 mm intervals. Results indicate that steady-state condition was rapidly attained. As expected, a diffusive boundary layer (DBL) was observed in all cases. An iterative back-calculation process using the numerical code POLLUTEv6 and taking the DBL into account provided the Kr values used to match calculated and experimental concentration profiles. Kr obtained for tailings TA1 and TA2 was about 80 d(-1) and 6.5 d(-1), respectively. For comparison purposes, Kr obtained from cell tests on tailings TA1 was lower than Kr calculated from the sulphate production rate obtained from shake-flask tests. Steady-state DO flux at the water-tailings interface was then calculated with POLLUTEv6 using tailings characteristics Dw and Kr. For the tested conditions, DO flux ranged from 608 to 758 mg O2/m(2)/d for tailings TA1 and from 177 to 221 mg O2/m(2)/d for tailings TA2. The impact of placing a protective layer of inert material over

  13. Mapped interpolation scheme for single-point energy corrections in reaction rate calculations and a critical evaluation of dual-level reaction path dynamics methods

    SciTech Connect

    Chuang, Y.Y.; Truhlar, D.G.; Corchado, J.C.

    1999-02-25

    Three procedures for incorporating higher level electronic structure data into reaction path dynamics calculations are tested. In one procedure, variational transition state theory with interpolated single-point energies, which is denoted VTST-ISPE, a few extra energies calculated with a higher level theory along the lower level reaction path are used to correct the classical energetic profile of the reaction. In the second procedure, denoted variational transition state theory with interpolated optimized corrections (VTST-IOC), which the authors introduced earlier, higher level corrections to energies, frequencies, and moments of inertia are based on stationary-point geometries reoptimized at a higher level than the reaction path was calculated. The third procedure, called interpolated optimized energies (IOE), is like IOC except it omits the frequency correction. Three hydrogen-transfer reactions, CH{sub 3} + H{prime}H {r_arrow} CH{sub 3}H{prime} + H (R1), OH + H{prime}H {r_arrow} HOH{prime} + H (R2), and OH + H{prime}CH{sub 3} {r_arrow} HOH{prime} + CH{sub 3} (R3), are used to test and validate the procedures by comparing their predictions to the reaction rate evaluated with a full variational transition state theory calculation including multidimensional tunneling (VTST/MT) at the higher level. The authors present a very efficient scheme for carrying out VTST-ISPE calculations, which are popular due to their lower computational cost. They also show, on the basis of calculations of the reactions R1--R3 with eight pairs of higher and lower levels, that VTST-IOC with higher level data only at stationary points is a more reliable dual-level procedure than VTST-ISPE with higher level energies all along the reaction path. Although the frequencies along the reaction path are not corrected in the IOE scheme, the results are still better than those from VTST-ISPE; this indicates the importance of optimizing the geometry at the highest possible level.

  14. Measurements of the O+ plus N2 and O+ plus O2 reaction rates from 300 to 900 K

    NASA Technical Reports Server (NTRS)

    Chen, A.; Johnsen, R.; Biondi, M. A.

    1977-01-01

    Rate coefficients for the O(+) + N2 atom transfer and O(+) + O2 charge transfer reactions are determined at thermal energies between 300 K and 900 K difference in a heated drift tube mass spectrometer apparatus. At 300 K the values K(O(+) + N2) = (1.2 plus or minus 0.1) x 10 to the negative 12 power cubic cm/sec and k(O(+) + O2) = (2.1 plus or minus 0.2) x 10 to the negative 11 power cubic cm/sec were obtained, with a 50% difference decrease in the reaction rates upon heating to 700 K. These results are in good agreement with heated flowing afterglow results, but the O(+) + O2 thermal rate coefficients are systematically lower than equivalent Maxwellian rates inferred by conversion of nonthermal drift tube and flow drift data.

  15. Rate constants for the reactions OH + HOCl. -->. H/sub 2/O + ClO and H + HOCl. -->. products

    SciTech Connect

    Ennis, C.A.; Birks, J.W.

    1988-03-10

    A new laboratory source of gaseous hypochlorous acid (HOCl) has been used in two kinetics investigations in a mass spectrometry-resonance fluorescence discharge flow system. Two potential removal reactions of stratospheric HOCl were studied. The rate constant for the reaction OH + HOCl ..-->.. H/sub 2/O + ClO (1) at 298 K was found to be lower than the NASA estimate by a factor of about 2-12; a value in the range (1.7-9.5) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ s/sup -1/ for k/sub 1/ is reported here. The reaction of Cl/sub 2/O + OH interfered in the study of k/sub 1/ and was the subject of a preliminary investigation. Its rate constant was determined to be (9.4 +/- 1.0) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 298 K. The rate constant for the reaction H + HOCl ..-->.. products (2) was determined to be (5.0 +/- 1.4) x 298 K. Although branching ratios for three possible products channels could not be determined, OH was identified as a product. The results of this work imply that reactions 1 and 2 are not competitive with direct photolysis in the removal of HOCl from the stratosphere.

  16. EFFECTS OF REACTION PARAMETERS ON ELECTROCHEMICAL DECHLORINATION OF TRICHLOROETHYLENE RATE AND BY-PRODUCTS

    EPA Science Inventory

    Trichloroethylene (TCE) was electrochemically dechlorinated in aqueous environments using granular graphite cathode in a mixed reactor. Effects of pH, current, electrolyte type, and flow rate on TCE dechlorination rate were evaluated. TCE dechlorination rate constant and gas prod...

  17. 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.

  18. Absolute rate of the reaction of atomic hydrogen with ethylene from 198 to 320 K at high pressure

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

    The rate constant for the H+C2H4 reaction has been measured as a function of temperature. Experiments were performed with high pressures of Ar heat bath gas at seven temperatures from 198 to 320 K with the flash photolysis-resonance fluorescence (FP-RF) technique. Pressures were chosen so as to isolate the addition rate constant k1. The results are well represented by an Arrhenius expression. The results are compared with other studies and are theoretically discussed.

  19. Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1975-01-01

    Growth constants, obtained by measuring the blue CO flame band emission behind incident shock waves, were obtained for two elementary bimolecular reactions involved in the oxidation of methane. Gas mixtures containing small amounts of CH4 with varying amounts of CO, O2, and in one case CO2, diluted with argon, were investigated, and exponential growth constants were derived from plots of the logarithm of observed light intensity versus gas time. The rate constant for the reaction O + CH4 yields CH3 + OH was found to be 1.9 times 10 to the 14th exp(-5900/T) cu cm per mole per sec in the range 1300-2000 K; for the reaction CH3 + O2 yields CH3O + O, the rate constant was determined to be 2.4 times 10 to the 13th exp(-14,500/T) cu cm per mole per sec in the range 1200 to 1900 K.

  20. Improved 192,194,195,196Pt(n,γ) and 192Ir(n,γ) astrophysical reaction rates

    NASA Astrophysics Data System (ADS)

    Koehler, P. E.; Guber, K. H.

    2013-09-01

    192Pt is produced solely by the slow neutron capture (s) nucleosynthesis process and hence an accurate (n,γ) reaction rate for this nuclide would allow its use as an important calibration point near the termination of the s-process nucleosynthesis flow. For this reason, we have measured neutron capture and total cross sections for 192,194,195,196,natPt in the energy range from 10 eV to several hundred keV at the Oak Ridge Electron Linear Accelerator. Measurements on the other Pt isotopes were, in part, necessitated by the fact that only a relatively small 192Pt sample of modest enrichment was available. Astrophysical 192,194,195,196Pt(n,γ) reaction rates, accurate to approximately 3%-5%, were calculated from these data. No accurate reaction rates have been published previously for any of these isotopes. At s-process temperatures, previously recommended rates are larger (by as much as 35%) and have significantly different shapes as functions of temperature than our new rates. We used our new Pt results, together with 191,193Ir(n,γ) data, to calibrate nuclear statistical model calculations and hence obtain an improved rate for the unmeasured s-process branching-point isotope 192Ir.