Sample records for absolute reaction rates

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

    PubMed

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

    2012-12-27

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

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  3. 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.

  4. The Br+HO 2 reaction revisited: Absolute determination of the rate constant at 298 K

    NASA Astrophysics Data System (ADS)

    Laverdet, G.; Le Bras, G.; Mellouki, A.; Poulet, G.

    1990-09-01

    The absolute determination of the rate constant for the reaction Br+HO 2→HBr+O 2 has been done at 298 K using the discharge-flor EPR method. The value k1 = (1.5±0.2) × 10 -12 cm 3 molecule -1 s -1 was obtained. Previous indirect measurements of k1 from a discharge-flow, LIF/mass spectrometric study of the Br/H 2CO/O 2 system have been reinterpreted, leading to values for k1 ranging from 1.0 × 10 -12 to 2.2 × 10 -12 cm 3 molecule -1 s -1 at 298 K. These results are discussed and compared with other literature values.

  5. Validation of absolute axial neutron flux distribution calculations with MCNP with 197Au(n,γ)198Au reaction rate distribution measurements at the JSI TRIGA Mark II reactor.

    PubMed

    Radulović, Vladimir; Štancar, Žiga; Snoj, Luka; Trkov, Andrej

    2014-02-01

    The calculation of axial neutron flux distributions with the MCNP code at the JSI TRIGA Mark II reactor has been validated with experimental measurements of the (197)Au(n,γ)(198)Au reaction rate. The calculated absolute reaction rate values, scaled according to the reactor power and corrected for the flux redistribution effect, are in good agreement with the experimental results. The effect of different cross-section libraries on the calculations has been investigated and shown to be minor. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

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

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

    1987-04-23

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

  7. Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J.

    1980-01-01

    The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

  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. 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.

  10. Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

    Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

  11. Absolute rate of the reaction of C l(2P) with methane 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 methane have been measured from 200-500K using the flash photolysis-resonance fluorescence technique. When the results from fourteen equally spaced experimental determinations are plotted in Arrhenius form a definite curvature is noted. The results are compared to previous work and are theoretically discussed.

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

    PubMed

    Sashi, Pulikallu; Bhuyan, Abani K

    2015-07-28

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

  13. Absolute protein-protein association rate constants from flexible, coarse-grained Brownian dynamics simulations: the role of intermolecular hydrodynamic interactions in barnase-barstar association.

    PubMed

    Frembgen-Kesner, Tamara; Elcock, Adrian H

    2010-11-03

    Theory and computation have long been used to rationalize the experimental association rate constants of protein-protein complexes, and Brownian dynamics (BD) simulations, in particular, have been successful in reproducing the relative rate constants of wild-type and mutant protein pairs. Missing from previous BD studies of association kinetics, however, has been the description of hydrodynamic interactions (HIs) between, and within, the diffusing proteins. Here we address this issue by rigorously including HIs in BD simulations of the barnase-barstar association reaction. We first show that even very simplified representations of the proteins--involving approximately one pseudoatom for every three residues in the protein--can provide excellent reproduction of the absolute association rate constants of wild-type and mutant protein pairs. We then show that simulations that include intermolecular HIs also produce excellent estimates of association rate constants, but, for a given reaction criterion, yield values that are decreased by ∼35-80% relative to those obtained in the absence of intermolecular HIs. The neglect of intermolecular HIs in previous BD simulation studies, therefore, is likely to have contributed to the somewhat overestimated absolute rate constants previously obtained. Consequently, intermolecular HIs could be an important component to include in accurate modeling of the kinetics of macromolecular association events. Copyright © 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  14. Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

    Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

  15. 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.

  16. Direct and Absolute Quantification of over 1800 Yeast Proteins via Selected Reaction Monitoring*

    PubMed Central

    Lawless, Craig; Holman, Stephen W.; Brownridge, Philip; Lanthaler, Karin; Harman, Victoria M.; Watkins, Rachel; Hammond, Dean E.; Miller, Rebecca L.; Sims, Paul F. G.; Grant, Christopher M.; Eyers, Claire E.; Beynon, Robert J.

    2016-01-01

    Defining intracellular protein concentration is critical in molecular systems biology. Although strategies for determining relative protein changes are available, defining robust absolute values in copies per cell has proven significantly more challenging. Here we present a reference data set quantifying over 1800 Saccharomyces cerevisiae proteins by direct means using protein-specific stable-isotope labeled internal standards and selected reaction monitoring (SRM) mass spectrometry, far exceeding any previous study. This was achieved by careful design of over 100 QconCAT recombinant proteins as standards, defining 1167 proteins in terms of copies per cell and upper limits on a further 668, with robust CVs routinely less than 20%. The selected reaction monitoring-derived proteome is compared with existing quantitative data sets, highlighting the disparities between methodologies. Coupled with a quantification of the transcriptome by RNA-seq taken from the same cells, these data support revised estimates of several fundamental molecular parameters: a total protein count of ∼100 million molecules-per-cell, a median of ∼1000 proteins-per-transcript, and a linear model of protein translation explaining 70% of the variance in translation rate. This work contributes a “gold-standard” reference yeast proteome (including 532 values based on high quality, dual peptide quantification) that can be widely used in systems models and for other comparative studies. PMID:26750110

  17. 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.

  18. Can the analyte-triggered asymmetric autocatalytic Soai reaction serve as a universal analytical tool for measuring enantiopurity and assigning absolute configuration?

    PubMed

    Welch, Christopher J; Zawatzky, Kerstin; Makarov, Alexey A; Fujiwara, Satoshi; Matsumoto, Arimasa; Soai, Kenso

    2016-12-20

    An investigation is reported on the use of the autocatalytic enantioselective Soai reaction, known to be influenced by the presence of a wide variety of chiral materials, as a generic tool for measuring the enantiopurity and absolute configuration of any substance. Good generality for the reaction across a small group of test analytes was observed, consistent with literature reports suggesting a diversity of compound types that can influence the stereochemical outcome of this reaction. Some trends in the absolute sense of stereochemical enrichment were noted, suggesting the possible utility of the approach for assigning absolute configuration to unknown compounds, by analogy to closely related species with known outcomes. Considerable variation was observed in the triggering strength of different enantiopure materials, an undesirable characteristic when dealing with mixtures containing minor impurities with strong triggering strength in the presence of major components with weak triggering strength. A strong tendency of the reaction toward an 'all or none' type of behavior makes the reaction most sensitive for detecting enantioenrichment close to zero. Consequently, the ability to discern modest from excellent enantioselectivity was relatively poor. While these properties limit the ability to obtain precise enantiopurity measurements in a simple single addition experiment, prospects may exist for more complex experimental setups that may potentially offer improved performance.

  19. Separation of Betti Reaction Product Enantiomers: Absolute Configuration and Inhibition of Botulinum Neurotoxin A

    DTIC Science & Technology

    2011-03-01

    of Betti Reaction Product Enantiomers : Absolute Configuration and Inhibition of Botulinum Neurotoxin A John H. Cardellina II,† Rebecca C. Vieira...observing sufficient resolution of the two enantiomers on a Chiralcel OD column to permit semipreparative purification of adequate quantities of (þ)-1...comparison of the botulinum neurotoxin serotype A (BoNT/A) inhibitory activity of the (þ) and () enantiomers of 1 was accomplished via an HPLC-based assay

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  1. Loss Process for the C2H5 Radical in the Atmospheres of Jupiter and Saturn: First Direct, Absolute Measurement of the Rate Constant for the Reaction H + C2H5 at Low Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Stief, L. J.; Pimentel, A. S.; Payne, W. A.; Nesbitt, F. L.; Cody, R. J.

    2003-05-01

    Photochemical models of the atmospheres of Jupiter and Saturn predict the reaction H + C2H5 to be the most important loss process for C2H5 in these atmospheres. In addition, the reaction channel H + C2H5 -> 2 CH3 is a significant source of the methyl radical. There are only two relatively modern studies of the H + C2H5 reaction, both of which depend on extensive modeling involving eight elementary reactions. The motivation for the present study is the lack of direct, absolute measurements of the rate constant for the H + C2H5 reaction at low pressures and temperatures appropriate for outer planet models. In the present experiments the reactants H and C2H5 are rapidly and simultaneously generated by reaction of F with appropriate mixtures of H2 and C2H6. Using the technique of discharge-flow with collision-free sampling to a mass spectrometer, we monitor the decay of C2H5 in excess H. In contrast to previous studies of this reaction, the primary H + C2H5 reaction is isolated and the radical decays only by reaction with H and by loss at the wall. Secondary reactions such as the self-reaction of C2H5 are negligible. At P = 1 Torr He we measure k (298K) = 1.13 x 10-10 cm3 molecule-1 s-1 and k (202K) = 1.18 x 10-10 cm3 molecule-1 s-1. Experiments at T = 155 K are in progress. The reaction is temperature independent as expected based on studies of other atom-radical reactions. Our result at T = 298 K lies between those of the two relatively modern but complex studies of this reaction. The present total rate constant data and planned product yield studies at low pressures and temperatures will then be available for use in future photochemical models of the atmospheres of the outer planets. The Planetary Atmospheres Program of NASA Headquarters is supporting this research.

  2. Reaction rates for mesoscopic reaction-diffusion kinetics

    DOE PAGES

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-23

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

  3. Reaction rates for mesoscopic reaction-diffusion kinetics

    PubMed Central

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2016-01-01

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

  4. Solid-state track recorder dosimetry device to measure absolute reaction rates and neutron fluence as a function of time

    DOEpatents

    Gold, Raymond; Roberts, James H.

    1989-01-01

    A solid state track recording type dosimeter is disclosed to measure the time dependence of the absolute fission rates of nuclides or neutron fluence over a period of time. In a primary species an inner recording drum is rotatably contained within an exterior housing drum that defines a series of collimating slit apertures overlying windows defined in the stationary drum through which radiation can enter. Film type solid state track recorders are positioned circumferentially about the surface of the internal recording drum to record such radiation or its secondary products during relative rotation of the two elements. In another species both the recording element and the aperture element assume the configuration of adjacent disks. Based on slit size of apertures and relative rotational velocity of the inner drum, radiation parameters within a test area may be measured as a function of time and spectra deduced therefrom.

  5. 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.

  6. 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.

  7. 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…

  8. Absolute Density Calibration Cell for Laser Induced Fluorescence Erosion Rate Measurements

    NASA Technical Reports Server (NTRS)

    Domonkos, Matthew T.; Stevens, Richard E.

    2001-01-01

    Flight qualification of ion thrusters typically requires testing on the order of 10,000 hours. Extensive knowledge of wear mechanisms and rates is necessary to establish design confidence prior to long duration tests. Consequently, real-time erosion rate measurements offer the potential both to reduce development costs and to enhance knowledge of the dependency of component wear on operating conditions. Several previous studies have used laser-induced fluorescence (LIF) to measure real-time, in situ erosion rates of ion thruster accelerator grids. Those studies provided only relative measurements of the erosion rate. In the present investigation, a molybdenum tube was resistively heated such that the evaporation rate yielded densities within the tube on the order of those expected from accelerator grid erosion. This work examines the suitability of the density cell as an absolute calibration source for LIF measurements, and the intrinsic error was evaluated.

  9. 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.

  10. Detection of medically important Candida species by absolute quantitation real-time polymerase chain reaction.

    PubMed

    Than, Leslie Thian Lung; Chong, Pei Pei; Ng, Kee Peng; Seow, Heng Fong

    2015-01-01

    The number of invasive candidiasis cases has risen especially with an increase in the number of immunosuppressed and immunocom promised patients. The early detection of Candida species which is specific and sensitive is important in determining the correct administration of antifungal drugs to patients. This study aims to develop a method for the detection, identification and quantitation of medically important Candida species through quantitative polymerase chain reaction (qPCR). The isocitrate lyase (ICL) gene which is not found in mammals was chosen as the target gene of real-time PCR. Absolute quantitation of the gene copy number was achieved by constructing the plasmid containing the ICL gene which is used to generate standard curve. Twenty fungal species, two bacterial species and human DNA were tested to check the specificity of the detection method. All eight Candida species were successfully detected, identified and quantitated based on the ICL gene. A seven-log range of the gene copy number and a minimum detection limit of 10(3) copies were achieved. A one-tube absolute quantification real-time PCR that differentiates medically important Candida species via individual unique melting temperature was achieved. Analytical sensitivity and specificity were not compromised.

  11. 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…

  12. Absolute and Relative Reliability of Percentage of Syllables Stuttered and Severity Rating Scales

    ERIC Educational Resources Information Center

    Karimi, Hamid; O'Brian, Sue; Onslow, Mark; Jones, Mark

    2014-01-01

    Purpose: Percentage of syllables stuttered (%SS) and severity rating (SR) scales are measures in common use to quantify stuttering severity and its changes during basic and clinical research conditions. However, their reliability has not been assessed with indices measuring both relative and absolute reliability. This study was designed to provide…

  13. Non-equilibrium reaction rates in chemical kinetic equations

    NASA Astrophysics Data System (ADS)

    Gorbachev, Yuriy

    2018-05-01

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

  14. Correlated uncertainties in Monte Carlo reaction rate calculations

    NASA Astrophysics Data System (ADS)

    Longland, Richard

    2017-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Burkholder, J. B.; Feierabend, K.

    2010-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  17. Bayesian Estimation of Thermonuclear Reaction Rates for Deuterium+Deuterium Reactions

    NASA Astrophysics Data System (ADS)

    Gómez Iñesta, Á.; Iliadis, C.; Coc, A.

    2017-11-01

    The study of d+d reactions is of major interest since their reaction rates affect the predicted abundances of D, 3He, and 7Li. In particular, recent measurements of primordial D/H ratios call for reduced uncertainties in the theoretical abundances predicted by Big Bang nucleosynthesis (BBN). Different authors have studied reactions involved in BBN by incorporating new experimental data and a careful treatment of systematic and probabilistic uncertainties. To analyze the experimental data, Coc et al. used results of ab initio models for the theoretical calculation of the energy dependence of S-factors in conjunction with traditional statistical methods based on χ 2 minimization. Bayesian methods have now spread to many scientific fields and provide numerous advantages in data analysis. Astrophysical S-factors and reaction rates using Bayesian statistics were calculated by Iliadis et al. Here we present a similar analysis for two d+d reactions, d(d, n)3He and d(d, p)3H, that has been translated into a total decrease of the predicted D/H value by 0.16%.

  18. Accessibility of Nitroxide Side Chains: Absolute Heisenberg Exchange Rates from Power Saturation EPR

    PubMed Central

    Altenbach, Christian; Froncisz, Wojciech; Hemker, Roy; Mchaourab, Hassane; Hubbell, Wayne L.

    2005-01-01

    In site-directed spin labeling, the relative solvent accessibility of spin-labeled side chains is taken to be proportional to the Heisenberg exchange rate (Wex) of the nitroxide with a paramagnetic reagent in solution. In turn, relative values of Wex are determined by continuous wave power saturation methods and expressed as a proportional and dimensionless parameter Π. In the experiments presented here, NiEDDA is characterized as a paramagnetic reagent for solvent accessibility studies, and it is shown that absolute values of Wex can be determined from Π, and that the proportionality constant relating them is independent of the paramagnetic reagent and mobility of the nitroxide. Based on absolute exchange rates, an accessibility factor is defined (0 < ρ < 1) that serves as a quantitative measure of side-chain solvent accessibility. The accessibility factors for a nitroxide side chain at 14 different sites in T4 lysozyme are shown to correlate with a structure-based accessibility parameter derived from the crystal structure of the protein. These results provide a useful means for relating crystallographic and site-directed spin labeling data, and hence comparing crystal and solution structures. PMID:15994891

  19. Absolute cross sections of the 86Sr(α,n)89Zr reaction at energies of astrophysical interest

    NASA Astrophysics Data System (ADS)

    Oprea, Andreea; Glodariu, Tudor; Filipescu, Dan; Gheorghe, Ioana; Mitu, Andreea; Boromiza, Marian; Bucurescu, Dorel; Costache, Cristian; Cata-Danil, Irina; Florea, Nicoleta; Ghita, Dan Gabriel; Ionescu, Alina; Marginean, Nicolae; Marginean, Raluca; Mihai, Constantin; Mihai, Radu; Negret, Alexandru; Nita, Cristina; Olacel, Adina; Pascu, Sorin; Sotty, Cristophe; Suvaila, Rares; Stan, Lucian; Stroe, Lucian; Serban, Andreea; Stiru, Irina; Toma, Sebastian; Turturica, Andrei; Ujeniuc, Sorin

    2017-09-01

    Absolute cross sections for the 86Sr(α,n)89Zr reaction at energies close to the Gamow window are reported. Three thin SrF2 targets were irradiated using the 9 MV Tandem facility in IFIN-HH Bucharest that delivered α beams for the activation process. Two high-purity Germanium detectors were used to measure the induced activity of 89Zr in a low background environment. The experimental results are in very good agreement with Hauser-Feshbach statistical model calculations performed with the TALYS code.

  20. 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.

  1. Temperature-dependent rate coefficients for the reactions of the hydroxyl radical with the atmospheric biogenics isoprene, alpha-pinene and delta-3-carene

    NASA Astrophysics Data System (ADS)

    Dillon, Terry J.; Dulitz, Katrin; Groß, Christoph B. M.; Crowley, John N.

    2017-12-01

    Pulsed laser methods for OH generation and detection were used to study atmospheric degradation reactions for three important biogenic gases: OH + isoprene (Reaction R1), OH +α-pinene (Reaction R2) and OH + Δ-3-carene (Reaction R3). Gas-phase rate coefficients were characterized by non-Arrhenius kinetics for all three reactions. For (R1), k1 (241-356 K) = (1.93±0.08) × 10-11exp{(466±12)/T} cm3 molecule-1 s-1 was determined, with a room temperature value of k1 (297 K) = (9.3±0.4) × 10-11 cm3 molecule-1 s-1, independent of bath-gas pressure (5-200 Torr) and composition (M = N2 or air). Accuracy and precision were enhanced by online optical monitoring of isoprene, with absolute concentrations obtained via an absorption cross section, σisoprene = (1.28±0.06) × 10-17 cm2 molecule-1 at λ = 184.95 nm, determined in this work. These results indicate that significant discrepancies between previous absolute and relative-rate determinations of k1 result in part from σ values used to derive the isoprene concentration in high-precision absolute determinations.

    Similar methods were used to determine rate coefficients (in 10-11 cm3 molecule-1 s-1) for (R2)-(R3): k2 (238-357 K) = (1.83±0.04) × exp{(330±6)/T} and k3 (235-357 K) = (2.48±0.14) × exp{(357±17)/T}. This is the first temperature-dependent dataset for (R3) and enables the calculation of reliable atmospheric lifetimes with respect to OH removal for e.g. boreal forest springtime conditions. Room temperature values of k2 (296 K) = (5.4±0.2) × 10-11 cm3 molecule-1 s-1 and k3 (297 K) = (8.1±0.3) × 10-11 cm3 molecule-1 s-1 were independent of bath-gas pressure (7-200 Torr, N2 or air) and in good agreement with previously reported values. In the course of this work, 184.95 nm absorption cross sections were determined: σ = (1.54±0.08) × 10-17 cm2 molecule-1 for α-pinene and (2.40±0.12) × 10-17 cm2 molecule-1 for Δ-3-carene.

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

    NASA Technical Reports Server (NTRS)

    Bangert, L. H.

    1975-01-01

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

  3. Determination of absolute chemiluminescence quantum yields for reactions of bis-(pentachlorophenyl) oxalate, hydrogen peroxide and fluorescent compounds.

    PubMed

    Catherall, C L; Palmer, T F; Cundall, R B

    1989-01-01

    Absolute chemiluminescence quantum yields (phi CL) for reactions of bis-(pentachlorophenyl) oxalate (PCPO), hydrogen peroxide (H2O2) and 9:10 diphenyl anthracene (DPA) have been determined. A fully corrected chemiluminescence monitoring spectrometer was calibrated for spectral sensitivity using the chemiluminescence of the bis-(pentachlorophenyl) oxalate system as a liquid light source, the total photon output of which had previously been determined by chemical actinometry. At high (PCPO)/(H2O2) ratios phi CL was found to be independent of PCPO and H2O2 concentrations.

  4. Statistical methods for thermonuclear reaction rates and nucleosynthesis simulations

    NASA Astrophysics Data System (ADS)

    Iliadis, Christian; Longland, Richard; Coc, Alain; Timmes, F. X.; Champagne, Art E.

    2015-03-01

    Rigorous statistical methods for estimating thermonuclear reaction rates and nucleosynthesis are becoming increasingly established in nuclear astrophysics. The main challenge being faced is that experimental reaction rates are highly complex quantities derived from a multitude of different measured nuclear parameters (e.g., astrophysical S-factors, resonance energies and strengths, particle and γ-ray partial widths). We discuss the application of the Monte Carlo method to two distinct, but related, questions. First, given a set of measured nuclear parameters, how can one best estimate the resulting thermonuclear reaction rates and associated uncertainties? Second, given a set of appropriate reaction rates, how can one best estimate the abundances from nucleosynthesis (i.e., reaction network) calculations? The techniques described here provide probability density functions that can be used to derive statistically meaningful reaction rates and final abundances for any desired coverage probability. Examples are given for applications to s-process neutron sources, core-collapse supernovae, classical novae, and Big Bang nucleosynthesis.

  5. Raman Spectral Determination of Chemical Reaction Rate Characteristics

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

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

  6. Some Nuclear Reaction Rates of Importance for Nucleosynthesis around Mass 45

    NASA Astrophysics Data System (ADS)

    Mitchell, Leon William

    1985-06-01

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

  7. Calibrating reaction rates for the CREST model

    NASA Astrophysics Data System (ADS)

    Handley, Caroline A.; Christie, Michael A.

    2017-01-01

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

  8. Reaction rates of the 113In(γ,n)112mIn and 115In(γ,n)114mIn

    NASA Astrophysics Data System (ADS)

    Skakun, Ye; Semisalov, I.; Kasilov, V.; Popov, V.; Kochetov, S.; Maslyuk, V.; Mazur, V.; Parlag, O.; Gajnish, I.

    2016-01-01

    The integral yields of the 113In(γ,n)112mIn (Jπ=9/2+→Jπ=4+) and 115In(γ,n)114mIn (Jπ=9/2+→Jπ=5+) photonuclear reactions were measured in the bremsstrahlung end-point energy range from the respective thresholds up to 14 MeV by a conventional activation/decay technique using the 197Au(γ,n)196Au reaction cross sections as the standard for the absolute photon intensity determination. The metallic indium samples of the natural and enriched compositions were irradiated by the bremsstrahlung beams from thin tantalum converters of the electron linear accelerator of NSC KIPT (Kharkiv) and the microtron of IEP (Ughhorod). The integral reaction yields were determined from the activities of the nuclei-products measured by the high resolution γ-ray spectrometry technique with Ge(Li)- and HPGe-detectors. The reaction rates for the Planck spectrum of a thermal photon bath were derived for the ground state target nuclei and compared to the predictions of the statistical model of nuclear reactions.

  9. 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…

  10. 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.

  11. Hypochlorous acid-mediated oxidation of lipid components and antioxidants present in low-density lipoproteins: absolute rate constants, product analysis, and computational modeling.

    PubMed

    Pattison, David I; Hawkins, Clare L; Davies, Michael J

    2003-04-01

    Oxidation of low-density lipoproteins (LDL) is believed to contribute to the increased uptake of LDL by macrophages, which is an early event in atherosclerosis. Hypochlorous acid (HOCl) has been implicated as one of the major oxidants involved in these processes. In a previous study, the rates of reaction of HOCl with the reactive sites in proteins were investigated (Pattison, D. I., and Davies, M. J. (2001) Chem. Res. Toxicol. 14, 1453-1464). The work presented here expands on those studies to determine absolute second-order rate constants for the reactions of HOCl with various lipid components and antioxidants in aqueous solution (pH 7.4). The reactions of HOCl with phosphoryl-serine and phosphoryl-ethanolamine are rapid (k approximately 10(5) M(-)(1) s(-)(1)) and of comparable reactivity to many of the protein sites. The major products formed in these reactions are chloramines, which decay to give both nitrogen- and carbon-centered radicals. Subsequent reactions of these species may induce oxidation of the LDL lipid component. In contrast, phosphoryl-choline reacted much more slowly (k < 10(-)(2) M(-)(1) s(-)(1)). Reaction of HOCl with 3-pentenoic acid was used as a model of lipid double bonds and yielded k = 9 M(-)(1) s(-)(1). The reactions of the lipid-soluble antioxidants, alpha-tocopherol and ubiquinol-10, with HOCl were investigated with model compounds. For the reactions of HOCl with both Trolox and ubiquinol-0, k = 1.3 x 10(3) M(-)(1) s(-)(1); thus, these lipid soluble antioxidants are relatively ineffective as direct scavengers for HOCl as compared to water soluble antioxidants (e.g., ascorbate, k ca. 10(6) M(-)(1) s(-)(1)). The reaction of HOCl with hydroquinone (a simple model for ubiquinol-10) was also investigated both in aqueous solution (k = 45 M(-)(1) s(-)(1)) and in a less polar environment (k approximately 0.5 M(-)(1) s(-)(1) in THF). A computational model was developed using these kinetic parameters to predict which LDL targets are oxidized

  12. Study on improving the turbidity measurement of the absolute coagulation rate constant.

    PubMed

    Sun, Zhiwei; Liu, Jie; Xu, Shenghua

    2006-05-23

    The existing theories dealing with the evaluation of the absolute coagulation rate constant by turbidity measurement were experimentally tested for different particle-sized (radius = a) suspensions at incident wavelengths (lambda) ranging from near-infrared to ultraviolet light. When the size parameter alpha = 2pi a/lambda > 3, the rate constant data from previous theories for fixed-sized particles show significant inconsistencies at different light wavelengths. We attribute this problem to the imperfection of these theories in describing the light scattering from doublets through their evaluation of the extinction cross section. The evaluations of the rate constants by all previous theories become untenable as the size parameter increases and therefore hampers the applicable range of the turbidity measurement. By using the T-matrix method, we present a robust solution for evaluating the extinction cross section of doublets formed in the aggregation. Our experiments show that this new approach is effective in extending the applicability range of the turbidity methodology and increasing measurement accuracy.

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

    DOE PAGES

    Hellander, Stefan; Petzold, Linda

    2016-01-19

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

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

    PubMed 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

  15. Ozone-Induced Dissociation of Conjugated Lipids Reveals Significant Reaction Rate Enhancements and Characteristic Odd-Electron Product Ions

    NASA Astrophysics Data System (ADS)

    Pham, Huong T.; Maccarone, Alan T.; Campbell, J. Larry; Mitchell, Todd W.; Blanksby, Stephen J.

    2013-02-01

    Ozone-induced dissociation (OzID) is an alternative ion activation method that relies on the gas phase ion-molecule reaction between a mass-selected target ion and ozone in an ion trap mass spectrometer. Herein, we evaluated the performance of OzID for both the structural elucidation and selective detection of conjugated carbon-carbon double bond motifs within lipids. The relative reactivity trends for [M + X]+ ions (where X = Li, Na, K) formed via electrospray ionization (ESI) of conjugated versus nonconjugated fatty acid methyl esters (FAMEs) were examined using two different OzID-enabled linear ion-trap mass spectrometers. Compared with nonconjugated analogues, FAMEs derived from conjugated linoleic acids were found to react up to 200 times faster and to yield characteristic radical cations. The significantly enhanced reactivity of conjugated isomers means that OzID product ions can be observed without invoking a reaction delay in the experimental sequence (i.e., trapping of ions in the presence of ozone is not required). This possibility has been exploited to undertake neutral-loss scans on a triple quadrupole mass spectrometer targeting characteristic OzID transitions. Such analyses reveal the presence of conjugated double bonds in lipids extracted from selected foodstuffs. Finally, by benchmarking of the absolute ozone concentration inside the ion trap, second order rate constants for the gas phase reactions between unsaturated organic ions and ozone were obtained. These results demonstrate a significant influence of the adducting metal on reaction rate constants in the fashion Li > Na > K.

  16. Rate constant for reaction of atomic hydrogen with germane

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  17. A review of reaction rates in high temperature air

    NASA Technical Reports Server (NTRS)

    Park, Chul

    1989-01-01

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

  18. Computationally Aided Absolute Stereochemical Determination of Enantioenriched Amines.

    PubMed

    Zhang, Jun; Gholami, Hadi; Ding, Xinliang; Chun, Minji; Vasileiou, Chrysoula; Nehira, Tatsuo; Borhan, Babak

    2017-03-17

    A simple and efficient protocol for sensing the absolute stereochemistry and enantiomeric excess of chiral monoamines is reported. Preparation of the sample requires a single-step reaction of the 1,1'-(bromomethylene)dinaphthalene (BDN) with the chiral amine. Analysis of the exciton coupled circular dichroism generated from the BDN-derivatized chiral amine sample, along with comparison to conformational analysis performed computationally, yields the absolute stereochemistry of the parent chiral monoamine.

  19. Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

  20. The absolute counting of red cell-derived microparticles with red cell bead by flow rate based assay.

    PubMed

    Nantakomol, Duangdao; Imwong, Malika; Soontarawirat, Ingfar; Kotjanya, Duangporn; Khakhai, Chulalak; Ohashi, Jun; Nuchnoi, Pornlada

    2009-05-01

    Activation of red blood cell is associated with the formation of red cell-derived microparticles (RMPs). Analysis of circulating RMPs is becoming more refined and clinically useful. A quantitative Trucount tube method is the conventional method uses for quantitating RMPs. In this study, we validated a quantitative method called "flow rate based assay using red cell bead (FCB)" to measure circulating RMPs in the peripheral blood of healthy subjects. Citrated blood samples collected from 30 cases of healthy subjects were determined the RMPs count by using double labeling of annexin V-FITC and anti-glycophorin A-PE. The absolute RMPs numbers were measured by FCB, and the results were compared with the Trucount or with flow rate based calibration (FR). Statistical correlation and agreement were analyzed using linear regression and Bland-Altman analysis. There was no significant difference in the absolute number of RMPs quantitated by FCB when compared with those two reference methods including the Trucount tube and FR method. The absolute RMPs count obtained from FCB method was highly correlated with those obtained from Trucount tube (r(2) = 0.98, mean bias 4 cell/microl, limit of agreement [LOA] -20.3 to 28.3 cell/microl), and FR method (r(2) = 1, mean bias 10.3 cell/microl, and LOA -5.5 to 26.2 cell/microl). This study demonstrates that FCB is suitable and more affordable for RMPs quantitation in the clinical samples. This method is a low cost and interchangeable to latex bead-based method for generating the absolute counts in the resource-limited areas. (c) 2008 Clinical Cytometry Society.

  1. BAYESIAN ESTIMATION OF THERMONUCLEAR REACTION RATES

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

    Iliadis, C.; Anderson, K. S.; Coc, A.

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

  2. Absolute empirical rate coefficient for the excitation of the 117.6 nm line in C III

    NASA Astrophysics Data System (ADS)

    Gardner, L. D.; Daw, A. N.; Janzen, P. H.; Atkins, N.; Kohl, J. L.

    2005-05-01

    We have measured the absolute cross sections for electron impact excitation (EIE) of C2+ (2s2p 3P° - 2p2 3P) for energies from below threshold to 17 eV above and derived EIE rate coefficients required for astrophysical applications. The uncertainty in the rate coefficient at a typical solar temperature of formation of C2+ is less than ± 6 %. Ions are produced in a 5 GHz Electron Cyclotron Resonance (ECR) ion source, extracted, formed into a beam, and transported to a collision chamber where they collide with electrons from an electron beam inclined at 45 degrees. The beams are modulated and the radiation from the decay of the excited ions at λ 117.6 nm is detected synchronously using an absolutely calibrated optical system that subtends slightly over π steradians. The fractional population of the C2+ metastable state in the incident ion beam has been determined experimentally to be 0.42 ± 0.03 (1.65 σ). At the reported ± 15 % total experimental uncertainty level (1.65 σ), the measured structure and absolute scale of the cross section are in fairly good agreement with 6-term close-coupling R-matrix calculations and 90-term R-matrix with pseudo-states calculations, although some minor differences are seen just above threshold. As density-sensitive line intensity ratios vary by only about a factor of 5 as the density changes by nearly a factor of 100, even a 30 % uncertainty in the excitation rate can lead to a factor of 3 error in density. This work is supported by NASA Supporting Research and Technology grants NAG5- 9516 and NAG5-12863 in Solar and Heliospheric Physics and by the Smithsonian Astrophysical Observatory.

  3. Direct Determination of the Rate Coefficient for the Reaction of OH Radicals with Monoethanol Amine (MEA) from 296 to 510 K.

    PubMed

    Onel, L; Blitz, M A; Seakins, P W

    2012-04-05

    Monoethanol amine (H2NCH2CH2OH, MEA) has been proposed for large-scale use in carbon capture and storage. We present the first absolute, temperature-dependent determination of the rate coefficient for the reaction of OH with MEA using laser flash photolysis for OH generation, monitoring OH removal by laser-induced fluorescence. The room-temperature rate coefficient is determined to be (7.61 ± 0.76) × 10(-11) cm(3) molecule(-1) s(-1), and the rate coefficient decreases by about 40% by 510 K. The temperature dependence of the rate coefficient is given by k1= (7.73 ± 0.24) × 10(-11)(T/295)(-(0.79±0.11)) cm(3) molecule(-1) s(-1). The high rate coefficient shows that gas-phase processing in the atmosphere will be competitive with uptake onto aerosols.

  4. Ignition delays, heats of combustion, and reaction rates of aluminum alkyl derivatives used as ignition and combustion enhancers for supersonic combustors

    NASA Technical Reports Server (NTRS)

    Ryan, T. W., III; Harlowe, W. W.; Schwab, S.

    1992-01-01

    The work was based on adapting an apparatus and procedure developed at Southwest Research Institute for rating the ignition quality of fuels for diesel engines. Aluminum alkyls and various Lewis-base adducts of these materials, both neat and mixed 50/50 with pure JP-10 hydrocarbon, were injected into the combustion bomb using a high-pressure injection system. The bomb was pre-charged with air that was set at various initial temperatures and pressures for constant oxygen density. The ignition delay times were determined for the test materials at these different initial conditions. The data are presented in absolute terms as well as comparisons with the parent alkyls. The relative heats of reaction of the various test materials were estimated based on a computation of the heat release, using the pressure data recorded during combustion in the bomb. In addition, the global reaction rates for each material were compared at a selected tmperature and pressure.

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

    PubMed

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

    2016-07-13

    If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Absolute configuration of a chiral CHD group via neutron diffraction: confirmation of the absolute stereochemistry of the enzymatic formation of malic acid

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

    Bau, R.; Brewer, I.; Chiang, M.Y.

    Neutron diffraction has been used to monitor the absolute stereochemistry of an enzymatic reaction. (-)(2S)malic-3-d acid was prepared by the action of fumarase on fumaric acid in D/sub 2/O. After a large number of cations were screened, it was found that (+)(R)..cap alpha..-phenylethylamine forms the large crystals necessary for a neutron diffraction analysis. The subsequent structure determination showed that (+)(R)..cap alpha..-phenylethylammonium (-)(2S)malate-3-d has an absolute configuration of R at the CHD site. This result confirms the absolute stereochemistry of fumarate-to-malate transformation as catalyzed by the enzyme fumarase.

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

    PubMed Central

    Motagamwala, Ali Hussain; Dumesic, James A.

    2016-01-01

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

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

    PubMed

    Liebermeister, Wolfram; Uhlendorf, Jannis; Klipp, Edda

    2010-06-15

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

  9. Rate Change Graph Technology: Absolute Value Point Methodology

    NASA Astrophysics Data System (ADS)

    Strickland, Ken; Duvernois, Michael

    2011-10-01

    Absolute Value Point Methodology (AVPM) is a new theoretical tool for science research centered on Rate Change Graph Technology (RCGT). The modeling techniques of AVPM surpass conventional methods by extending the geometrical rules of mathematics. Exact geometrical structures of matter and energy become clearer revealing new ways to compile advanced data. RCGT mechanics is realized from geometrical intersections that are the result of plotting changing value vs. changing geometry. RCGT methods ignore size and value to perform an objective analysis in geometry. Value and size are then re-introduced back into the analytical system for a clear and concise solution. Available AVPM applications reveal that a massive amount of data from the Big Bang to vast super-clusters is untouched by human thought. Once scientists learn to design tools from RCGT Mechanics, new and formidable approaches to experimentation and theory may lead to new discoveries. In the creation of AVPM, it has become apparent there is a particle-world that exists between strings and our familiar universe. These unrealized particles in their own nature exhibit inflation like properties and may be the progenitor of the implements of our universe. Thus space, time, energy, motion, space-time and gravity are born from its existence and decay. This announcement will be the beginning of many new ideas from the study of RCGT mechanics.

  10. Astrophysical Nuclear Reaction Rates in the Dense Metallic Environments

    NASA Astrophysics Data System (ADS)

    Kilic, Ali Ihsan

    2017-09-01

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

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

    PubMed

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

    2011-01-20

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

  12. Calculation of kinetic rate constants from thermodynamic data

    NASA Technical Reports Server (NTRS)

    Marek, C. John

    1995-01-01

    A new scheme for relating the absolute value for the kinetic rate constant k to the thermodynamic constant Kp is developed for gases. In this report the forward and reverse rate constants are individually related to the thermodynamic data. The kinetic rate constants computed from thermodynamics compare well with the current kinetic rate constants. This method is self consistent and does not have extensive rules. It is first demonstrated and calibrated by computing the HBr reaction from H2 and Br2. This method then is used on other reactions.

  13. Reaction rate for carbon burning in massive stars

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

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

    DOE PAGES

    Motagamwala, Ali Hussain; Dumesic, James A.

    2016-05-09

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  16. Reaction rate for carbon burning in massive stars

    DOE PAGES

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

    2018-01-10

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

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

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

  19. 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)

  20. Control of serpentinisation rate by reaction-induced cracking

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

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

    DOE PAGES

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

    2017-03-08

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

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

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

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

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

  3. Absolute Humidity and the Seasonality of Influenza (Invited)

    NASA Astrophysics Data System (ADS)

    Shaman, J. L.; Pitzer, V.; Viboud, C.; Grenfell, B.; Goldstein, E.; Lipsitch, M.

    2010-12-01

    Much of the observed wintertime increase of mortality in temperate regions is attributed to seasonal influenza. A recent re-analysis of laboratory experiments indicates that absolute humidity strongly modulates the airborne survival and transmission of the influenza virus. Here we show that the onset of increased wintertime influenza-related mortality in the United States is associated with anomalously low absolute humidity levels during the prior weeks. We then use an epidemiological model, in which observed absolute humidity conditions temper influenza transmission rates, to successfully simulate the seasonal cycle of observed influenza-related mortality. The model results indicate that direct modulation of influenza transmissibility by absolute humidity alone is sufficient to produce this observed seasonality. These findings provide epidemiological support for the hypothesis that absolute humidity drives seasonal variations of influenza transmission in temperate regions. In addition, we show that variations of the basic and effective reproductive numbers for influenza, caused by seasonal changes in absolute humidity, are consistent with the general timing of pandemic influenza outbreaks observed for 2009 A/H1N1 in temperate regions. Indeed, absolute humidity conditions correctly identify the region of the United States vulnerable to a third, wintertime wave of pandemic influenza. These findings suggest that the timing of pandemic influenza outbreaks is controlled by a combination of absolute humidity conditions, levels of susceptibility and changes in population mixing and contact rates.

  4. Influence of reaction-induced fracturing on serpentinisation rate

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

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

  5. The reaction of peroxy radicals with OH: rate constants and HO2 yields

    NASA Astrophysics Data System (ADS)

    Fittschen, C. M.; Assaf, E.; Schoemaecker, C.; Vereecken, L.

    2017-12-01

    Peroxy radicals, RO2, are key species in the atmosphere. They are formed from a reaction of OH radicals with hydrocarbon: RH + OH + O2 → RO2 + H2O In polluted environments, RO2 radicals react predominantly with NO, leading to formation of NO2 and eventually through photolysis of NO2 to formation of O3. At low NOx concentrations such as in the marine boundary layer or the background troposphere, the lifetime of RO2 radicals increases and other reaction pathways become competitive. Atmospheric chemistry models have considered until recently only the self- and cross reaction with other RO2 radicals or with HO2 radicals as the major fate for RO2 radicals under low NOx conditions. Recently, the rate constants for the reaction of peroxy radicals with OH radicals RO2 + OH → products has been measured for CH3O2 [1, 2] and C2H5O2 [3] and it was shown to become competitive to other sinks [4]. However, in order to evaluate the impact of this so far neglected sink for peroxy radicals on the composition of remote atmospheres, the reaction products must be known. A recently improved experimental set-up combining laser photolysis with two simultaneous cw-CRDS detections in the near IR allowing for a time resolved, absolute quantification of OH and RO2 radicals has been used for a further investigation of this class of reactions. High-repetition rate LIF is used for determining relative OH profiles. For CH3O2 radicals, HO2 has been determined as major product recently [5]. Currently, we study the next larger perxoy, C2H5O2, using different radical precursors (C2H5I, (COCl)2/C2H6, XeF2/C2H6) and also deuterated C2D5I in order to elucidate the product yield. Preliminary results show a much lower HO2 yield for C2H5O2 compared to CH3O2. The most recent results will be presented at the conference. [1] A. Bossolasco, E. Faragó, C. Schoemaecker, and C. Fittschen, CPL, 593, 7, (2014). [2] E. Assaf, B. Song, A. Tomas, C. Schoemaecker, C. Fittschen, JPC A, 120, 8923 (2016) [3] Eszter

  6. Preparation of an oakmoss absolute with reduced allergenic potential.

    PubMed

    Ehret, C; Maupetit, P; Petrzilka, M; Klecak, G

    1992-06-01

    Synopsis Oakmoss absolute, an extract of the lichen Evernia prunastri, is known to cause allergenic skin reactions due to the presence of certain aromatic aldehydes such as atranorin, chloratranorin, ethyl hematommate and ethyl chlorohematommate. In this paper it is shown that treatment of Oakmoss absolute with amino acids such as lysine and/or leucine, lowers considerably the content of these allergenic constituents including atranol and chloratranol. The resulting Oakmoss absolute, which exhibits an excellent olfactive quality, was tested extensively in comparative studies on guinea pigs and on man. The results of the Guinea Pig Maximization Test (GPMT) and Human Repeated Insult Patch Test (HRIPT) indicate that, in comparison with the commercial test sample, the allergenicity of this new quality of Oakmoss absolute was considerably reduced, and consequently better skin tolerance of this fragrance for man was achieved.

  7. 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.

  8. DEPENDENCE OF X-RAY BURST MODELS ON NUCLEAR REACTION RATES

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

    Cyburt, R. H.; Keek, L.; Schatz, H.

    2016-10-20

    X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars, and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p, γ ), ( α , γ ), and ( α , p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to matchmore » calculations with a state-of-the-art 1D multi-zone model based on the Kepler stellar evolution code. All relevant reaction rates on neutron-deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 changes in reaction rate with the highest impact were then repeated in the 1D multi-zone model. We find a number of uncertain reaction rates that affect predictions of light curves and burst ashes significantly. The results provide insights into the nuclear processes that shape observables from X-ray bursts, and guidance for future nuclear physics work to reduce nuclear uncertainties in X-ray burst models.« less

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

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

    Yan, Zhifeng; Liu, Chongxuan; Liu, Yuanyuan

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

  10. 237Np absolute delayed neutron yield measurements

    NASA Astrophysics Data System (ADS)

    Doré, D.; Ledoux, X.; Nolte, R.; Gagnon-Moisan, F.; Thulliez, L.; Litaize, O.; Roettger, S.; Serot, O.

    2017-09-01

    237Np absolute delayed neutron yields have been measured at different incident neutron energies from 1.5 to 16 MeV. The experiment was performed at the Physikalisch-Technische Bundesanstalt (PTB) facility where the Van de Graaff accelerator and the cyclotron CV28 delivered 9 different neutron energy beams using p+T, d+D and d+T reactions. The detection system is made up of twelve 3He tubes inserted into a polyethylene cylinder. In this paper, the experimental setup and the data analysis method are described. The evolution of the absolute DN yields as a function of the neutron incident beam energies are presented and compared to experimental data found in the literature and data from the libraries.

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

    PubMed

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

    2011-09-29

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

  12. The fading American dream: Trends in absolute income mobility since 1940.

    PubMed

    Chetty, Raj; Grusky, David; Hell, Maximilian; Hendren, Nathaniel; Manduca, Robert; Narang, Jimmy

    2017-04-28

    We estimated rates of "absolute income mobility"-the fraction of children who earn more than their parents-by combining data from U.S. Census and Current Population Survey cross sections with panel data from de-identified tax records. We found that rates of absolute mobility have fallen from approximately 90% for children born in 1940 to 50% for children born in the 1980s. Increasing Gross Domestic Product (GDP) growth rates alone cannot restore absolute mobility to the rates experienced by children born in the 1940s. However, distributing current GDP growth more equally across income groups as in the 1940 birth cohort would reverse more than 70% of the decline in mobility. These results imply that reviving the "American dream" of high rates of absolute mobility would require economic growth that is shared more broadly across the income distribution. Copyright © 2017, American Association for the Advancement of Science.

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

    NASA Astrophysics Data System (ADS)

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

    2002-10-01

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

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

    PubMed

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

    2014-09-01

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

  15. Thermonuclear 19F(p, {{\\boldsymbol{\\alpha }}}_{0})16O reaction rate

    NASA Astrophysics Data System (ADS)

    He, Jian-Jun; Lombardo, Ivano; Dell'Aquila, Daniele; Xu, Yi; Zhang, Li-Yong; Liu, Wei-Ping

    2018-01-01

    The thermonuclear 19F(p, {{{α }}}0)16O reaction rate in the temperature region 0.007-10 GK has been derived by re-evaluating the available experimental data, together with the low-energy theoretical R-matrix extrapolations. Our new rate deviates by up to about 30% compared to the previous results, although all rates are consistent within the uncertainties. At very low temperature (e.g. 0.01 GK) our reaction rate is about 20% lower than the most recently published rate, because of a difference in the low energy extrapolated S-factor and a more accurate estimate of the reduced mass used in the calculation of the reaction rate. At temperatures above ˜1 GK, our rate is lower, for instance, by about 20% around 1.75 GK, because we have re-evaluated the previous data (Isoya et al., Nucl. Phys. 7, 116 (1958)) in a meticulous way. The present interpretation is supported by the direct experimental data. The uncertainties of the present evaluated rate are estimated to be about 20% in the temperature region below 0.2 GK, and are mainly caused by the lack of low-energy experimental data and the large uncertainties in the existing data. Asymptotic giant branch (AGB) stars evolve at temperatures below 0.2 GK, where the 19F(p, {{α }})16O reaction may play a very important role. However, the current accuracy of the reaction rate is insufficient to help to describe, in a careful way, the fluorine over-abundances observed in AGB stars. Precise cross section (or S factor) data in the low energy region are therefore needed for astrophysical nucleosynthesis studies. Supported by National Natural Science Foundation of China (11490562, 11490560, 11675229) and National Key Research and Development Program of China (2016YFA0400503)

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

    PubMed

    Zheng, Jingjing; Truhlar, Donald G

    2012-01-01

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

  17. 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.

  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

    2016-11-05

    The primary goal of this research is to develop a three-term mesoscopic reaction rate model that consists of a hot-spot ignition, a low-pressure slow burning and a high-pressure fast reaction terms for shock initiation of multi-component Plastic Bonded Explosives (PBX). Thereinto, based on the DZK hot-spot model for a single-component PBX explosive, the hot-spot ignition term as well as its reaction rate is obtained through a "mixing rule" of the explosive components; new expressions for both the low-pressure slow burning term and the high-pressure fast reaction term are also obtained by establishing the relationships between the reaction rate of the multi-component PBX explosive and that of its explosive components, based on the low-pressure slow burning term and the high-pressure fast reaction term of a mesoscopic reaction rate model. Furthermore, for verification, the new reaction rate model is incorporated into the DYNA2D code to simulate numerically the shock initiation process of the PBXC03 and the PBXC10 multi-component PBX explosives, and the numerical results of the pressure histories at different Lagrange locations in explosive are found to be in good agreements with previous experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Absolute emission cross sections for electron capture reactions of C2+, N3+, N4+ and O3+ ions in collisions with Li(2s) atoms

    NASA Astrophysics Data System (ADS)

    Rieger, G.; Pinnington, E. H.; Ciubotariu, C.

    2000-12-01

    Absolute photon emission cross sections following electron capture reactions have been measured for C2+, N3+, N4+ and O3+ ions colliding with Li(2s) atoms at keV energies. The results are compared with calculations using the extended classical over-the-barrier model by Niehaus. We explore the limits of our experimental method and present a detailed discussion of experimental errors.

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

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

    PubMed

    Gehret, Austin U

    2017-03-04

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

  2. 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.

  3. CN radical reactions with hydrogen cyanide and cyanogen - Comparison of theory and experiment

    NASA Technical Reports Server (NTRS)

    Yang, D. L.; Yu, T.; Lin, M. C.; Melius, C. F.

    1992-01-01

    The method of laser photolysis/laser-induced fluorescence is used to obtain absolute rate constants for CN radical reactions with HCN and C2N2. The rate constants were found to be temperature-dependent in the range 300-740 K and pressure independent in the range 100-600 Torr. Rice-Remsperger-Kassel-Marcus theory for both reactions employing the transition state parameters obtained by the BAC-MP4 method are made. These calculations yielded reasonable results for the CN + HCN reaction, predicting both the temperature dependence and pressure independence. No pressure effect was observed in the pressure range 100-1000 Torr at temperatures below 900 K, confirming the experimental results.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

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

  6. Noninvasive optical quantification of absolute blood flow, blood oxygenation, and oxygen consumption rate in exercising skeletal muscle

    NASA Astrophysics Data System (ADS)

    Gurley, Katelyn; Shang, Yu; Yu, Guoqiang

    2012-07-01

    This study investigates a method using novel hybrid diffuse optical spectroscopies [near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS)] to obtain continuous, noninvasive measurement of absolute blood flow (BF), blood oxygenation, and oxygen consumption rate (\\Vdot O2) in exercising skeletal muscle. Healthy subjects (n=9) performed a handgrip exercise to increase BF and \\Vdot O2 in forearm flexor muscles, while a hybrid optical probe on the skin surface directly monitored oxy-, deoxy-, and total hemoglobin concentrations ([HbO2], [Hb], and THC), tissue oxygen saturation (StO2), relative BF (rBF), and relative oxygen consumption rate (r\\Vdot O2). The rBF and r\\Vdot O2 signals were calibrated with absolute baseline BF and \\Vdot O2 obtained through venous and arterial occlusions, respectively. Known problems with muscle-fiber motion artifacts in optical measurements during exercise were mitigated using a novel gating algorithm that determined muscle contraction status based on control signals from a dynamometer. Results were consistent with previous findings in the literature. This study supports the application of NIRS/DCS technology to quantitatively evaluate hemodynamic and metabolic parameters in exercising skeletal muscle and holds promise for improving diagnosis and treatment evaluation for patients suffering from diseases affecting skeletal muscle and advancing fundamental understanding of muscle and exercise physiology.

  7. Noninvasive optical quantification of absolute blood flow, blood oxygenation, and oxygen consumption rate in exercising skeletal muscle

    PubMed Central

    Gurley, Katelyn; Shang, Yu

    2012-01-01

    Abstract. This study investigates a method using novel hybrid diffuse optical spectroscopies [near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS)] to obtain continuous, noninvasive measurement of absolute blood flow (BF), blood oxygenation, and oxygen consumption rate (V˙O2) in exercising skeletal muscle. Healthy subjects (n=9) performed a handgrip exercise to increase BF and V˙O2 in forearm flexor muscles, while a hybrid optical probe on the skin surface directly monitored oxy-, deoxy-, and total hemoglobin concentrations ([HbO2], [Hb], and THC), tissue oxygen saturation (StO2), relative BF (rBF), and relative oxygen consumption rate (rV˙O2). The rBF and rV˙O2 signals were calibrated with absolute baseline BF and V˙O2 obtained through venous and arterial occlusions, respectively. Known problems with muscle-fiber motion artifacts in optical measurements during exercise were mitigated using a novel gating algorithm that determined muscle contraction status based on control signals from a dynamometer. Results were consistent with previous findings in the literature. This study supports the application of NIRS/DCS technology to quantitatively evaluate hemodynamic and metabolic parameters in exercising skeletal muscle and holds promise for improving diagnosis and treatment evaluation for patients suffering from diseases affecting skeletal muscle and advancing fundamental understanding of muscle and exercise physiology. PMID:22894482

  8. 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.

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

    ERIC Educational Resources Information Center

    Gehret, Austin U.

    2017-01-01

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

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

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

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

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

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-11-01

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

  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. Comparison of elicitation potential of chloroatranol and atranol--2 allergens in oak moss absolute.

    PubMed

    Johansen, Jeanne D; Bernard, Guillaume; Giménez-Arnau, Elena; Lepoittevin, Jean-Pierre; Bruze, Magnus; Andersen, Klaus E

    2006-04-01

    Chloroatranol and atranol are degradation products of chloroatranorin and atranorin, respectively, and have recently been identified as important contact allergens in the natural fragrance extract, oak moss absolute. Oak moss absolute is widely used in perfumery and is the cause of many cases of fragrance allergic contact dermatitis. Chloroatranol elicits reactions at very low levels of exposure. In oak moss absolute, chloroatranol and atranol are present together and both may contribute to the allergenicity and eliciting capacity of the natural extract. In this study, 10 eczema patients with known sensitization to chloroatranol and oak moss absolute were tested simultaneously to a serial dilution of chloroatranol and atranol in ethanol, in equimolar concentrations (0.0034-1072 microM). Dose-response curves were estimated and analysed by logistic regression. The estimated difference in elicitation potency of chloroatranol relative to atranol based on testing with equimolar concentrations was 217% (95% confidence interval 116-409%). Both substances elicited reactions at very low levels of exposure. It is concluded that the differences in elicitation capacity between the 2 substances are counterbalanced by exposure being greater to atranol than to chloroatranol and that both substances contribute to the clinical problems seen in oak moss absolute-sensitized individuals.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

    Kelly, Keegan John

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

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

    PubMed

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

    2017-09-01

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

  19. EXPERIMENTAL PROTOCOL FOR DETERMINING PROTOLYSIS REACTION RATE CONSTANTS

    EPA Science Inventory

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

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

    DTIC Science & Technology

    1981-09-01

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

  1. Age differences in emotional reactions: arousal and age-relevance count.

    PubMed

    Streubel, Berit; Kunzmann, Ute

    2011-12-01

    Recent findings suggest positivity effects in older adults' attention and memory, but few studies have examined such effects on the level of emotional reactivity. In this study, 52 young and 52 older adults rated 172 pictures of the International Affective Picture System, differing in arousal and age-relevance, in terms of valence and discrete emotions. Age differences in the ratio of pleasantness reactions to pleasant pictures vs. unpleasantness reactions to unpleasant pictures as well as age differences in absolute levels of unpleasantness and pleasantness reactions suggest that positivity effects in older adults' subjective emotional reactions are reduced under high arousal. There is also evidence that positivity effects may be restricted to stimuli with low relevance in old age.

  2. Observation of the isotope effect in sub-kelvin reactions

    NASA Astrophysics Data System (ADS)

    Lavert-Ofir, Etay; Shagam, Yuval; Henson, Alon B.; Gersten, Sasha; Kłos, Jacek; Żuchowski, Piotr S.; Narevicius, Julia; Narevicius, Edvardas

    2014-04-01

    Quantum phenomena in the translational motion of reactants, which are usually negligible at room temperature, can dominate reaction dynamics at low temperatures. In such cold conditions, even the weak centrifugal force is enough to create a potential barrier that keeps reactants separated. However, reactions may still proceed through tunnelling because, at low temperatures, wave-like properties become important. At certain de Broglie wavelengths, the colliding particles can become trapped in long-lived metastable scattering states, leading to sharp increases in the total reaction rate. Here, we show that these metastable states are responsible for a dramatic, order-of-magnitude-strong, quantum kinetic isotope effect by measuring the absolute Penning ionization reaction rates between hydrogen isotopologues and metastable helium down to 0.01 K. We demonstrate that measurements of a single isotope are insufficient to constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to remove ambiguity among possible potential energy surfaces.

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

    PubMed

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

    2017-02-09

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

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

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

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

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

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

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

    NASA Astrophysics Data System (ADS)

    Hamel, Mark D.

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

  8. The Impact of Nuclear Reaction Rate Uncertainties on the Evolution of Core-collapse Supernova Progenitors

    NASA Astrophysics Data System (ADS)

    Fields, C. E.; Timmes, F. X.; Farmer, R.; Petermann, I.; Wolf, William M.; Couch, S. M.

    2018-02-01

    We explore properties of core-collapse supernova progenitors with respect to the composite uncertainties in the thermonuclear reaction rates by coupling the probability density functions of the reaction rates provided by the STARLIB reaction rate library with MESA stellar models. We evolve 1000 models of 15{M}ȯ from the pre-main sequence to core O-depletion at solar and subsolar metallicities for a total of 2000 Monte Carlo stellar models. For each stellar model, we independently and simultaneously sample 665 thermonuclear reaction rates and use them in a MESA in situ reaction network that follows 127 isotopes from 1H to 64Zn. With this framework we survey the core mass, burning lifetime, composition, and structural properties at five different evolutionary epochs. At each epoch we measure the probability distribution function of the variations of each property and calculate Spearman rank-order correlation coefficients for each sampled reaction rate to identify which reaction rate has the largest impact on the variations on each property. We find that uncertainties in the reaction rates of {}14{{N}}{({{p}},γ )}15{{O}}, triple-α, {}12{{C}}{(α ,γ )}16{{O}}, 12C(12C,p)23Na, 12C(16O, p)27Al, 16O(16O,n)31S, 16O(16O, p)31P, and 16O(16O,α)28Si dominate the variations of the properties surveyed. We find that variations induced by uncertainties in nuclear reaction rates grow with each passing phase of evolution, and at core H-, He-depletion they are of comparable magnitude to the variations induced by choices of mass resolution and network resolution. However, at core C-, Ne-, and O-depletion, the reaction rate uncertainties can dominate the variation, causing uncertainty in various properties of the stellar model in the evolution toward iron core-collapse.

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

    ERIC Educational Resources Information Center

    Olbris, Donald J.; Herzfeld, Judith

    2002-01-01

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

  10. 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

  11. Absolute and relative educational inequalities in depression in Europe.

    PubMed

    Dudal, Pieter; Bracke, Piet

    2016-09-01

    To investigate (1) the size of absolute and relative educational inequalities in depression, (2) their variation between European countries, and (3) their relationship with underlying prevalence rates. Analyses are based on the European Social Survey, rounds three and six (N = 57,419). Depression is measured using the shortened Centre of Epidemiologic Studies Depression Scale. Education is coded by use of the International Standard Classification of Education. Country-specific logistic regressions are applied. Results point to an elevated risk of depressive symptoms among the lower educated. The cross-national patterns differ between absolute and relative measurements. For men, large relative inequalities are found for countries including Denmark and Sweden, but are accompanied by small absolute inequalities. For women, large relative and absolute inequalities are found in Belgium, Bulgaria, and Hungary. Results point to an empirical association between inequalities and the underlying prevalence rates. However, the strength of the association is only moderate. This research stresses the importance of including both measurements for comparative research and suggests the inclusion of the level of population health in research into inequalities in health.

  12. Laser Flash Photolysis Studies of Radical-Radical Reaction Kinetics: The O((sup 3)P(sub J)) + BrO Reaction

    NASA Technical Reports Server (NTRS)

    Thorn, R. P.; Cronkhite, J. M.; Nicovich, J. M.; Wine, P. H.

    1997-01-01

    A novel dual laser flash photolysis-long path absorption-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reaction 0((sup 3)P(sub j)) + Br yields(k1) BrO((sup 2)P(sub J)) + O2 as a function of temperature (231-328 K) and pressure (25-150 Torr) in N2 buffer gas. The experimental approach preserves the principal advantages of the flash photolysis method, i.e., complete absence of surface reactions and a wide range of accessible pressures, but also employs techniques which are characteristic of the discharge flow method, namely chemical titration as a means for deducing the absolute concentration of a radical reactant and use of multiple detection axes. We find that k1 is independent of pressure, and that the temperature dependence of k1 is adequately described by the Arrhenius expression k1(T) = 1.91 x 10(exp -11)(230/J) cu cm/ molecule.s; the absolute accuracy of measured values for k1 is estimated to vary from +/- 20 percent at at T approximately 230 K to +/- 30 percent at T approximately 330 K. Our results demonstrate that the O((sup 3)P(sub j)) + BrO rate coefficient is significantly faster than previously 'guesstimated,' and suggest that the catalytic cycle with the O((sup 3)P(sub j)) + BrO reaction as its rate-limiting step is the dominant stratospheric BrO(x), odd-oxygen destruction cycle at altitudes above 24 km.

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

    PubMed

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

    1985-02-01

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

  14. Universality and chaoticity in ultracold K+KRb chemical reactions

    DOE PAGES

    Croft, J. F. E.; Makrides, C.; Li, M.; ...

    2017-07-19

    A fundamental question in the study of chemical reactions is how reactions proceed at a collision energy close to absolute zero. This question is no longer hypothetical: quantum degenerate gases of atoms and molecules can now be created at temperatures lower than a few tens of nanokelvin. Here we consider the benchmark ultracold reaction between, the most-celebrated ultracold molecule, KRb and K. We map out an accurate ab initio ground-state potential energy surface of the K 2Rb complex in full dimensionality and report numerically-exact quantum-mechanical reaction dynamics. The distribution of rotationally resolved rates is shown to be Poissonian. An analysismore » of the hyperspherical adiabatic potential curves explains this statistical character revealing a chaotic distribution for the short-range collision complex that plays a key role in governing the reaction outcome.« less

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

    NASA Astrophysics Data System (ADS)

    Bondarev, B. V.

    1986-04-01

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

  16. The Influence of Particle Charge on Heterogeneous Reaction Rate Coefficients

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

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

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

    PubMed

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

    2012-07-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011), 10.1063/1.3611400] various calculations of the rate coefficient for the Mu + H2 → MuH + H reaction were presented and compared to experiment. The widely used standard quasiclassical trajectory (QCT) method was shown to overestimate the rate coefficients by several orders of magnitude over the temperature range 200-1000 K. This was attributed to a major failure of that method to describe the correct threshold for the reaction owing to the large difference in zero-point energies (ZPE) of the reactant H2 and product MuH (˜0.32 eV). In this Communication we show that by performing standard QCT calculations for the reverse reaction and then applying detailed balance, the resulting rate coefficient is in very good agreement with the other computational results that respect the ZPE, (as well as with the experiment) but which are more demanding computationally.

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

    DOE PAGES

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

    2016-09-14

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

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

    PubMed Central

    2017-01-01

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

  1. Establishing Ion Ratio Thresholds Based on Absolute Peak Area for Absolute Protein Quantification using Protein Cleavage Isotope Dilution Mass Spectrometry

    PubMed Central

    Loziuk, Philip L.; Sederoff, Ronald R.; Chiang, Vincent L.; Muddiman, David C.

    2014-01-01

    Quantitative mass spectrometry has become central to the field of proteomics and metabolomics. Selected reaction monitoring is a widely used method for the absolute quantification of proteins and metabolites. This method renders high specificity using several product ions measured simultaneously. With growing interest in quantification of molecular species in complex biological samples, confident identification and quantitation has been of particular concern. A method to confirm purity or contamination of product ion spectra has become necessary for achieving accurate and precise quantification. Ion abundance ratio assessments were introduced to alleviate some of these issues. Ion abundance ratios are based on the consistent relative abundance (RA) of specific product ions with respect to the total abundance of all product ions. To date, no standardized method of implementing ion abundance ratios has been established. Thresholds by which product ion contamination is confirmed vary widely and are often arbitrary. This study sought to establish criteria by which the relative abundance of product ions can be evaluated in an absolute quantification experiment. These findings suggest that evaluation of the absolute ion abundance for any given transition is necessary in order to effectively implement RA thresholds. Overall, the variation of the RA value was observed to be relatively constant beyond an absolute threshold ion abundance. Finally, these RA values were observed to fluctuate significantly over a 3 year period, suggesting that these values should be assessed as close as possible to the time at which data is collected for quantification. PMID:25154770

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

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

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

    1999-11-01

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

  3. Teaching Absolute Value Meaningfully

    ERIC Educational Resources Information Center

    Wade, Angela

    2012-01-01

    What is the meaning of absolute value? And why do teachers teach students how to solve absolute value equations? Absolute value is a concept introduced in first-year algebra and then reinforced in later courses. Various authors have suggested instructional methods for teaching absolute value to high school students (Wei 2005; Stallings-Roberts…

  4. Neutron activation analysis of certified samples by the absolute method

    NASA Astrophysics Data System (ADS)

    Kadem, F.; Belouadah, N.; Idiri, Z.

    2015-07-01

    The nuclear reactions analysis technique is mainly based on the relative method or the use of activation cross sections. In order to validate nuclear data for the calculated cross section evaluated from systematic studies, we used the neutron activation analysis technique (NAA) to determine the various constituent concentrations of certified samples for animal blood, milk and hay. In this analysis, the absolute method is used. The neutron activation technique involves irradiating the sample and subsequently performing a measurement of the activity of the sample. The fundamental equation of the activation connects several physical parameters including the cross section that is essential for the quantitative determination of the different elements composing the sample without resorting to the use of standard sample. Called the absolute method, it allows a measurement as accurate as the relative method. The results obtained by the absolute method showed that the values are as precise as the relative method requiring the use of standard sample for each element to be quantified.

  5. Cytogenetic and molecular aspects of absolute teratozoospermia: comparison between polymorphic and monomorphic forms.

    PubMed

    Brahem, Sonia; Elghezal, Hatem; Ghédir, Houda; Landolsi, Hanène; Amara, Abdelbacett; Ibala, Samira; Gribaa, Moez; Saad, Ali; Mehdi, Meriem

    2011-12-01

    To compare the results of cytogenetic and molecular analysis between absolute polymorphic and monomorphic teratozoospermia. The semen samples from patients with polymorphic teratozoospermia (n = 20), globozoospermia (n = 8), or macrocephalic sperm head syndrome (n = 12), and healthy fertile men (n = 20) were analyzed according to the World Health Organization criteria. The constitutional blood karyotype of the patients was performed on cultured lymphocytes, according to standard techniques. Microdeletion analysis of the Y chromosomes used a sequence tagged site-polymerase chain reaction technique. Triple-color fluorescent in situ hybridization for chromosomes X, Y, and 18 were used to analyze the meiotic segregation. DNA fragmentation was detected using the terminal desoxynucleotidyl transferase-mediated deoxyuridine triphosphate biotin nick-end labeling assay. Whatever the type of teratozoospermia, a normal karyotype and an absence of Y chromosome microdeletion were shown for all patients. A significant increase in the sperm aneuploidy rate and DNA fragmentation were shown, regardless of the type of teratozoospermia. Spermatozoa of the patients with globozoospermia carry an abnormal chromosomal constitution and DNA damage rate with the same frequency as that found in the sperm of patients with absolute polymorphic teratozoospermia. However, a greater sperm aneuploidy rate and DNA fragmentation were found in patients whose teratozoospermia was mainly characterized by increased rates of spermatozoa with macrocephalic head and multiple flagella. Our data have demonstrated that DNA fragmentation and sperm aneuploidy are critical tests in teratozoospermic men, because the results could negatively affect the intracytoplasmic sperm injection outcomes and might play an important role in the counseling of couples considering intracytoplasmic sperm injection. Copyright © 2011 Elsevier Inc. All rights reserved.

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

    PubMed

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

    2011-01-01

    A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transport over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics. Copyright © 2010 The Author(s). Journal compilation © 2010 National Ground Water Association.

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

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

    Gong, R; Lu, C; Luo, Jian

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

  8. Study of the H + O + M reaction forming OH{sup *}: Kinetics of OH{sup *} chemiluminescence in hydrogen combustion systems

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

    Kathrotia, T.; Riedel, U.; Fikri, M.

    The temporal variation of OH{sup *} (A{sup 2}{sigma}{sup +}) chemiluminescence in hydrogen oxidation chemistry has been studied in a shock tube behind reflected shock waves at temperatures of 1400-3300 K and at a pressure of 1 bar. The aim of the present work is to obtain a validated reaction scheme to describe OH{sup *} formation in the H{sub 2}/O{sub 2} system. Temporal OH{sup *} emission profiles and ignition delay times for lean and stoichiometric H{sub 2}/O{sub 2} mixtures diluted in 97-98% argon were obtained from the shock-tube experiments. Based on a literature review for the hydrogen combustion system, the keymore » reaction considered was H + O + M = OH{sup *} + M. The temperature dependence of the measured peak OH{sup *} emission from the shock tube and the peak OH{sup *} concentration from a homogeneous closed reactor model are compared. Based on these results a reaction rate coefficient of k{sub 1} = (1.5 {+-} 0.4) x 10{sup 13} exp(-25 kJ mol{sup -1}/RT) cm{sup 6} mol{sup -2} s{sup -1} was found for the forward reaction which is slightly higher than the rate coefficient suggested by Hidaka et al. (1982). The comparison of measured and simulated absolute concentrations shows good agreement. Additionally, a one-dimensional laminar premixed low-pressure flame calculation was performed for where absolute OH{sup *} concentration measurements have been reported by Smith et al. (2005). The absolute peak OH{sup *} concentration is fairly well reproduced if the above mentioned rate coefficient is used in the simulation. (author)« less

  9. Accurate Quantification of Cardiovascular Biomarkers in Serum Using Protein Standard Absolute Quantification (PSAQ™) and Selected Reaction Monitoring*

    PubMed Central

    Huillet, Céline; Adrait, Annie; Lebert, Dorothée; Picard, Guillaume; Trauchessec, Mathieu; Louwagie, Mathilde; Dupuis, Alain; Hittinger, Luc; Ghaleh, Bijan; Le Corvoisier, Philippe; Jaquinod, Michel; Garin, Jérôme; Bruley, Christophe; Brun, Virginie

    2012-01-01

    Development of new biomarkers needs to be significantly accelerated to improve diagnostic, prognostic, and toxicity monitoring as well as therapeutic follow-up. Biomarker evaluation is the main bottleneck in this development process. Selected Reaction Monitoring (SRM) combined with stable isotope dilution has emerged as a promising option to speed this step, particularly because of its multiplexing capacities. However, analytical variabilities because of upstream sample handling or incomplete trypsin digestion still need to be resolved. In 2007, we developed the PSAQ™ method (Protein Standard Absolute Quantification), which uses full-length isotope-labeled protein standards to quantify target proteins. In the present study we used clinically validated cardiovascular biomarkers (LDH-B, CKMB, myoglobin, and troponin I) to demonstrate that the combination of PSAQ and SRM (PSAQ-SRM) allows highly accurate biomarker quantification in serum samples. A multiplex PSAQ-SRM assay was used to quantify these biomarkers in clinical samples from myocardial infarction patients. Good correlation between PSAQ-SRM and ELISA assay results was found and demonstrated the consistency between these analytical approaches. Thus, PSAQ-SRM has the capacity to improve both accuracy and reproducibility in protein analysis. This will be a major contribution to efficient biomarker development strategies. PMID:22080464

  10. 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

  11. 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.

  12. Absolute instabilities of travelling wave solutions in a Keller-Segel model

    NASA Astrophysics Data System (ADS)

    Davis, P. N.; van Heijster, P.; Marangell, R.

    2017-11-01

    We investigate the spectral stability of travelling wave solutions in a Keller-Segel model of bacterial chemotaxis with a logarithmic chemosensitivity function and a constant, sublinear, and linear consumption rate. Linearising around the travelling wave solutions, we locate the essential and absolute spectrum of the associated linear operators and find that all travelling wave solutions have parts of the essential spectrum in the right half plane. However, we show that in the case of constant or sublinear consumption there exists a range of parameters such that the absolute spectrum is contained in the open left half plane and the essential spectrum can thus be weighted into the open left half plane. For the constant and sublinear consumption rate models we also determine critical parameter values for which the absolute spectrum crosses into the right half plane, indicating the onset of an absolute instability of the travelling wave solution. We observe that this crossing always occurs off of the real axis.

  13. 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.

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

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

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

    Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H 2/O 2-mechanism chain branching reaction H + O 2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the givenmore » summary statistics, using Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto-ignition computations to

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

    DOE PAGES

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

    2016-10-15

    Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H 2/O 2-mechanism chain branching reaction H + O 2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the givenmore » summary statistics, using Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto-ignition computations to

  16. 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.

  17. Determining the 13C(α, n)16O absolute cross section through the concurrent application of ANC and THM and astrophysical consequences for the s-process in AGB-LMSs.

    NASA Astrophysics Data System (ADS)

    Trippella, Oscar; La Cognata, Marco

    2018-01-01

    The 13C(α, n)16O reaction is considered to be the most important neutron source for the s-process main component in low-mass asymptotic giant branch stars. No direct experimental data exist at very low energies and measurements performed through direct techniques show inconsistent results, mostly in their absolute values. In this context, we reversed the usual normalization procedure combining two indirect approaches, the asymptotic normalization coefficient and the Trojan Horse Method, to unambiguously determine the absolute value of the 13C(α, n)16O astrophysical S(E)-factor in the most relevant energy-region for astrophysics. Adopting the new reaction rate for the n-source in the NEWTON s-process nucleosynthesis code, astrophysical calculations show only limited variations, less than 1%, for those nuclei whose production is considered to be totally due to slow neutron captures.

  18. Comprehensive Panel of Real-Time TaqMan™ Polymerase Chain Reaction Assays for Detection and Absolute Quantification of Filoviruses, Arenaviruses, and New World Hantaviruses

    PubMed Central

    Trombley, Adrienne R.; Wachter, Leslie; Garrison, Jeffrey; Buckley-Beason, Valerie A.; Jahrling, Jordan; Hensley, Lisa E.; Schoepp, Randal J.; Norwood, David A.; Goba, Augustine; Fair, Joseph N.; Kulesh, David A.

    2010-01-01

    Viral hemorrhagic fever is caused by a diverse group of single-stranded, negative-sense or positive-sense RNA viruses belonging to the families Filoviridae (Ebola and Marburg), Arenaviridae (Lassa, Junin, Machupo, Sabia, and Guanarito), and Bunyaviridae (hantavirus). Disease characteristics in these families mark each with the potential to be used as a biological threat agent. Because other diseases have similar clinical symptoms, specific laboratory diagnostic tests are necessary to provide the differential diagnosis during outbreaks and for instituting acceptable quarantine procedures. We designed 48 TaqMan™-based polymerase chain reaction (PCR) assays for specific and absolute quantitative detection of multiple hemorrhagic fever viruses. Forty-six assays were determined to be virus-specific, and two were designated as pan assays for Marburg virus. The limit of detection for the assays ranged from 10 to 0.001 plaque-forming units (PFU)/PCR. Although these real-time hemorrhagic fever virus assays are qualitative (presence of target), they are also quantitative (measure a single DNA/RNA target sequence in an unknown sample and express the final results as an absolute value (e.g., viral load, PFUs, or copies/mL) on the basis of concentration of standard samples and can be used in viral load, vaccine, and antiviral drug studies. PMID:20439981

  19. Easy Absolute Values? Absolutely

    ERIC Educational Resources Information Center

    Taylor, Sharon E.; Mittag, Kathleen Cage

    2015-01-01

    The authors teach a problem-solving course for preservice middle-grades education majors that includes concepts dealing with absolute-value computations, equations, and inequalities. Many of these students like mathematics and plan to teach it, so they are adept at symbolic manipulations. Getting them to think differently about a concept that they…

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

    PubMed

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

    2017-12-21

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

  1. Experimental study of the reactions of limonene with OH and OD radicals: kinetics and products.

    PubMed

    Braure, Tristan; Bedjanian, Yuri; Romanias, Manolis N; Morin, Julien; Riffault, Véronique; Tomas, Alexandre; Coddeville, Patrice

    2014-10-09

    The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 → products (1), OD + C10H16 → products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K.

  2. Absolute measurements of the triplet-triplet annihilation rate and the charge-carrier recombination layer thickness in working polymer light-emitting diodes based on polyspirobifluorene

    NASA Astrophysics Data System (ADS)

    Rothe, C.; Al Attar, H. A.; Monkman, A. P.

    2005-10-01

    The triplet exciton densities in electroluminescent devices prepared from two polyspirobifluorene derivatives have been investigated by means of time-resolved transient triplet absorption as a function of optical and electrical excitation power at 20 K. Because of the low mobility of the triplet excitons at this temperature, the triplet generation profile within the active polymer layer is preserved throughout the triplet lifetime and as a consequence the absolute triplet-triplet annihilation efficiency is not homogeneously distributed but depends on position within the active layer. This then gives a method to measure the charge-carrier recombination layer after electrical excitation relative to the light penetration depth, which is identical to the triplet generation layer after optical excitation. With the latter being obtained from ellipsometry, an absolute value of 5 nm is found for the exciton formation layer in polyspirobifluorene devices. This layer increases to 11 nm if the balance between the electron and the hole mobility is improved by chemically modifying the polymer backbone. Also, and consistent with previous work, triplet diffusion is dispersive at low temperature. As a consequence of this, the triplet-triplet annihilation rate is not a constant in the classical sense but depends on the triplet excitation dose. At 20 K and for typical excitation doses, absolute values of the latter rate are of the order of 10-14cm3s-1 .

  3. Enhancement of autonomic and psychomotor arousal by exposures to blue wavelength light: importance of both absolute and relative contents of melanopic component.

    PubMed

    Yuda, Emi; Ogasawara, Hiroki; Yoshida, Yutaka; Hayano, Junichiro

    2017-01-31

    Blue light containing rich melanopsin-stimulating (melanopic) component has been reported to enhance arousal level, but it is unclear whether the determinant of the effects is the absolute or relative content of melanopic component. We compared the autonomic and psychomotor arousal effects of melanopic-enriched blue light of organic light-emitting diode (OLED) with those of OLED lights with lesser absolute amount of melanopic component (green light) and with greater absolute but lesser relative content (white light). Using a ceiling light consisting of 120 panels (55 × 55 mm square) of OLED modules with adjustable color and brightness, we examined the effects of blue, green, and white lights (melanopic photon flux densities, 0.23, 0.14, and 0.38 μmol/m 2 /s and its relative content ratios, 72, 17, and 14%, respectively) on heart rate variability (HRV) during exposures and on the performance of psychomotor vigilance test (PVT) after exposures in ten healthy subjects with normal color vision. For each of the three colors, five consecutive 10-min sessions of light exposures were performed in the supine position, interleaved by four 10-min intervals during which 5-min PVT was performed under usual fluorescent light in sitting position. Low-frequency (LF, 0.04-0.15 Hz) and high-frequency (HF, 0.15-0.40 Hz) power and LF-to-HF ratio (LF/HF) of HRV during light exposures and reaction time (RT) and minor lapse (RT >500 ms) of PVT were analyzed. Heart rate was higher and the HF power reflecting autonomic resting was lower during exposures to the blue light than the green and white lights, while LF/HF did not differ significantly. Also, the number of minor lapse and the variation of reaction time reflecting decreased vigilance were lower after exposures to the blue light than the green light. The effects of blue OLED light for maintaining autonomic and psychomotor arousal levels depend on both absolute and relative contents of melanopic component in the light.

  4. Absolutely relative or relatively absolute: violations of value invariance in human decision making.

    PubMed

    Teodorescu, Andrei R; Moran, Rani; Usher, Marius

    2016-02-01

    Making decisions based on relative rather than absolute information processing is tied to choice optimality via the accumulation of evidence differences and to canonical neural processing via accumulation of evidence ratios. These theoretical frameworks predict invariance of decision latencies to absolute intensities that maintain differences and ratios, respectively. While information about the absolute values of the choice alternatives is not necessary for choosing the best alternative, it may nevertheless hold valuable information about the context of the decision. To test the sensitivity of human decision making to absolute values, we manipulated the intensities of brightness stimuli pairs while preserving either their differences or their ratios. Although asked to choose the brighter alternative relative to the other, participants responded faster to higher absolute values. Thus, our results provide empirical evidence for human sensitivity to task irrelevant absolute values indicating a hard-wired mechanism that precedes executive control. Computational investigations of several modelling architectures reveal two alternative accounts for this phenomenon, which combine absolute and relative processing. One account involves accumulation of differences with activation dependent processing noise and the other emerges from accumulation of absolute values subject to the temporal dynamics of lateral inhibition. The potential adaptive role of such choice mechanisms is discussed.

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

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L.

    1986-01-01

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

  6. Reversible Hydrogen Transfer Reactions in Thiyl Radicals From Cysteine and Related Molecules: Absolute Kinetics and Equilibrium Constants Determined by Pulse Radiolysis

    PubMed Central

    Koppenol, Willem H.

    2013-01-01

    The mercapto group of cysteine (Cys) is a predominant target for oxidative modification, where one-electron oxidation leads to the formation of Cys thiyl radicals, CysS•. These Cys thiyl radicals enter 1,2- and 1,3-hydrogen transfer reactions, for which rate constants are reported in this paper. The products of these 1,2- and 1,3-hydrogen transfer reactions are carbon-centered radicals at position C3 (α-mercaptoalkyl radicals) and C2 (•Cα radicals) of Cys, respectively. Both processes can be monitored separately in Cys analogues such as cysteamine (CyaSH) and penicillamine (PenSH). At acidic pH, thiyl radicals from CyaSH permit only the 1,2-hydrogen transfer according to equilibrium 12, +H3NCH2CH2S• ⇌ +H3NCH2 •CH–SH, where rate constants for forward and reverse reaction are k12 ≈ 105 s−1 and k−12 ≈ 1.5 × 105s−1, respectively. In contrast, only the 1,3-hydrogen transfer is possible for thiyl radicals from PenSH according to equilibrium 14, (+H3N/CO2H)Cα–C(CH3)2–S• ⇌ (+H3N/CO2H)•Cα–C(CH3)2–SH, where rate constants for the forward and the reverse reaction are k14 = 8 × 104 s−1 and k−14 = 1.4 × 106 s−1. The •Cα radicals from PenSH and Cys have the additional opportunity for β-elimination of HS•/S•−, which proceeds with k39 ≈ (3 ± 1) × 104 s−1 from •Cα radicals from PenSH and k−34 ≈ 5 × 103 s−1 from •Cα radicals from Cys. The rate constants quantified for the 1,2- and 1,3-hydrogen transfer reactions can be used as a basis to calculate similar processes for Cys thiyl radicals in proteins, where hydrogen transfer reactions, followed by the addition of oxygen, may lead to the irreversible modification of target proteins. PMID:22483034

  7. A high-performance liquid chromatography-electronic circular dichroism online method for assessing the absolute enantiomeric excess and conversion ratio of asymmetric reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Xiang; Wang, Mingchao; Li, Li; Yin, Dali

    2017-03-01

    Asymmetric reactions often need to be evaluated during the synthesis of chiral compounds. However, traditional evaluation methods require the isolation of the individual enantiomer, which is tedious and time-consuming. Thus, it is desirable to develop simple, practical online detection methods. We developed a method based on high-performance liquid chromatography-electronic circular dichroism (HPLC-ECD) that simultaneously analyzes the material conversion ratio and absolute optical purity of each enantiomer. In particular, only a reverse-phase C18 column instead of a chiral column is required in our method because the ECD measurement provides a g-factor that describes the ratio of each enantiomer in the mixtures. We used our method to analyze the asymmetric hydrosilylation of β-enamino esters, and we discussed the advantage, feasibility, and effectiveness of this new methodology.

  8. Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions

    PubMed Central

    Aquilanti, Vincenzo; Coutinho, Nayara Dantas

    2017-01-01

    This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d < 0, to those where d > 0, corresponding to the Pareto–Tsallis statistical weights: these generalize the Boltzmann–Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d < 0, formally corresponding to Fermion-like or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super-Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub-Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti-Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the

  9. Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions.

    PubMed

    Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique

    2017-04-28

    This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d  < 0, to those where d  > 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d  = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d  > 0 or for a negative binomial distribution if d  < 0, formally corresponding to Fermion-like or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super -Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub -Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti -Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the

  10. Reaction Rate of Small Diffusing Molecules on a Cylindrical Membrane

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Calculating the True and Observed Rates of Complex Heterogeneous Catalytic Reactions

    NASA Astrophysics Data System (ADS)

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

    2018-06-01

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

  17. THE ABSOLUTE RATE OF LGRB FORMATION

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

    Graham, J. F.; Schady, P.

    2016-06-01

    We estimate the long-duration gamma-ray burst (LGRB) progenitor rate using our recent work on the effects of environmental metallically on LGRB formation in concert with supernovae (SNe) statistics via an approach patterned loosely off the Drake equation. Beginning with the cosmic star formation history, we consider the expected number of broad-line Type Ic events (the SNe type associated with LGRBs) that are in low-metallicity host environments adjusted by the contribution of high-metallicity host environments at a much reduced rate. We then compare this estimate to the observed LGRB rate corrected for instrumental selection effects to provide a combined estimate ofmore » the efficiency fraction of these progenitors to produce LGRBs and the fraction of which are beamed in our direction. From this we estimate that an aligned LGRB occurs for approximately every 4000 ± 2000 low-metallically broad-lined SNe Ic. Therefore, if one assumes a semi-nominal beaming factor of 100, then only about one such supernova out of 40 produce an LGRB. Finally, we propose an off-axis LGRB search strategy of targeting only broad-line Type Ic events that occur in low-metallicity hosts for radio observation.« less

  18. The Absolute Rate of LGRB Formation

    NASA Astrophysics Data System (ADS)

    Graham, J. F.; Schady, P.

    2016-06-01

    We estimate the long-duration gamma-ray burst (LGRB) progenitor rate using our recent work on the effects of environmental metallically on LGRB formation in concert with supernovae (SNe) statistics via an approach patterned loosely off the Drake equation. Beginning with the cosmic star formation history, we consider the expected number of broad-line Type Ic events (the SNe type associated with LGRBs) that are in low-metallicity host environments adjusted by the contribution of high-metallicity host environments at a much reduced rate. We then compare this estimate to the observed LGRB rate corrected for instrumental selection effects to provide a combined estimate of the efficiency fraction of these progenitors to produce LGRBs and the fraction of which are beamed in our direction. From this we estimate that an aligned LGRB occurs for approximately every 4000 ± 2000 low-metallically broad-lined SNe Ic. Therefore, if one assumes a semi-nominal beaming factor of 100, then only about one such supernova out of 40 produce an LGRB. Finally, we propose an off-axis LGRB search strategy of targeting only broad-line Type Ic events that occur in low-metallicity hosts for radio observation.

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

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

  20. Absolute photon-flux measurements in the vacuum ultraviolet

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Haddad, G. N.

    1974-01-01

    Absolute photon-flux measurements in the vacuum ultraviolet have extended to short wavelengths by use of rare-gas ionization chambers. The technique involves the measurement of the ion current as a function of the gas pressure in the ion chamber. The true value of the ion current, and hence the absolute photon flux, is obtained by extrapolating the ion current to zero gas pressure. Examples are given at 162 and 266 A. The short-wavelength limit is determined only by the sensitivity of the current-measuring apparatus and by present knowledge of the photoionization processes that occur in the rate gases.

  1. 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.

  2. Hyperplex-MRM: a hybrid multiple reaction monitoring method using mTRAQ/iTRAQ labeling for multiplex absolute quantification of human colorectal cancer biomarker.

    PubMed

    Yin, Hong-Rui; Zhang, Lei; Xie, Li-Qi; Huang, Li-Yong; Xu, Ye; Cai, San-Jun; Yang, Peng-Yuan; Lu, Hao-Jie

    2013-09-06

    Novel biomarker verification assays are urgently required to improve the efficiency of biomarker development. Benefitting from lower development costs, multiple reaction monitoring (MRM) has been used for biomarker verification as an alternative to immunoassay. However, in general MRM analysis, only one sample can be quantified in a single experiment, which restricts its application. Here, a Hyperplex-MRM quantification approach, which combined mTRAQ for absolute quantification and iTRAQ for relative quantification, was developed to increase the throughput of biomarker verification. In this strategy, equal amounts of internal standard peptides were labeled with mTRAQ reagents Δ0 and Δ8, respectively, as double references, while 4-plex iTRAQ reagents were used to label four different samples as an alternative to mTRAQ Δ4. From the MRM trace and MS/MS spectrum, total amounts and relative ratios of target proteins/peptides of four samples could be acquired simultaneously. Accordingly, absolute amounts of target proteins/peptides in four different samples could be achieved in a single run. In addition, double references were used to increase the reliability of the quantification results. Using this approach, three biomarker candidates, ademosylhomocysteinase (AHCY), cathepsin D (CTSD), and lysozyme C (LYZ), were successfully quantified in colorectal cancer (CRC) tissue specimens of different stages with high accuracy, sensitivity, and reproducibility. To summarize, we demonstrated a promising quantification method for high-throughput verification of biomarker candidates.

  3. Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

    PubMed

    Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

    2009-06-08

    Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

  4. Directly Relating Gas-Phase Cluster Measurements to Solution-Phase Hydrolysis, the Absolute Standard Hydrogen Electrode Potential, and the Absolute Proton Solvation Energy

    PubMed Central

    Donald, William A.; Leib, Ryan D.; O’Brien, Jeremy T.; Williams, Evan R.

    2009-01-01

    Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M-(H2O)242+(g)+e−(g)→M(H2O)24+(g) and 2) M(H2O)242+(g)+e−(g)→MOH(H2O)23+(g)+H(g) and the hydrogen atom affinities of MOH(H2O)23+(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e−(g) (standard deviation of 0.02 V) and a real proton solvation free energy of −265 kcal mol−1 are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution. PMID:19440999

  5. Absolute biological needs.

    PubMed

    McLeod, Stephen

    2014-07-01

    Absolute needs (as against instrumental needs) are independent of the ends, goals and purposes of personal agents. Against the view that the only needs are instrumental needs, David Wiggins and Garrett Thomson have defended absolute needs on the grounds that the verb 'need' has instrumental and absolute senses. While remaining neutral about it, this article does not adopt that approach. Instead, it suggests that there are absolute biological needs. The absolute nature of these needs is defended by appeal to: their objectivity (as against mind-dependence); the universality of the phenomenon of needing across the plant and animal kingdoms; the impossibility that biological needs depend wholly upon the exercise of the abilities characteristic of personal agency; the contention that the possession of biological needs is prior to the possession of the abilities characteristic of personal agency. Finally, three philosophical usages of 'normative' are distinguished. On two of these, to describe a phenomenon or claim as 'normative' is to describe it as value-dependent. A description of a phenomenon or claim as 'normative' in the third sense does not entail such value-dependency, though it leaves open the possibility that value depends upon the phenomenon or upon the truth of the claim. It is argued that while survival needs (or claims about them) may well be normative in this third sense, they are normative in neither of the first two. Thus, the idea of absolute need is not inherently normative in either of the first two senses. © 2013 John Wiley & Sons Ltd.

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

    PubMed Central

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

    2011-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

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

    PubMed

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

    2017-04-06

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

  9. Kinetic studies of the reaction of the hydroxymethyl radical with NO and NO sub 2

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

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

    1989-06-29

    The absolute rate constant for the reaction CD{sub 2}OH + NO has been measured from 230 to 373 K in a discharge-flow system. The decay of the CD{sub 2}OH radical was monitored in excess NO by collision-free sampling mass spectrometry. At 298 K, k{sub 1} = (2.2 {plus minus} 0.4) {times} 10{sup {minus}12} cm{sup 3}s{sup {minus}1} (2{sigma}) independent of pressure from 0.5 to 1.5 Torr. For the 230-298 K interval, an activation energy of 1.2 kcal/mol is obtained, but k{sub 1} does not appear to change within experimental error on going from 298 to 373 K. The absolute rate constantmore » at 298 K has also been measured for the reaction CH{sub 2}OH + NO{sub 2} by the same technique. The result is k{sub 2} = (8.3 {plus minus} 4.1) {times} 10{sup {minus}12} cm{sup 3} s{sup {minus}1} (2{sigma}). Qualitative detection was made of D{sub 2}CO and H{sub 2}CO as products of these reactions, but no evidence was obtained for the expected accompanying products HNO and HNO{sub 2} nor for the CD{sub 2}OHNO and CH{sub 2}OHNO{sub 2} adducts. It is suggested, partially by analogy with the CH{sub 2}OH + O{sub 2} reaction, that the reaction mechanism in both cases involves initial formation of a vibrationally excited complex that, depending on reaction conditions, can dissociate back to reactants or, after isomerization, dissociate to products. Collisional stabilization of the addition complex may be feasible, but they have no evidence for this under the low-pressure condition of their experiments. The rate constants for reaction of CH{sub 2}OH with O{sub 2}, NO, and NO{sub 2} are briefly compared.« less

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

    PubMed

    da Silva, Gabriel; Bozzelli, Joseph W

    2012-12-14

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

  11. 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.

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

    NASA Technical Reports Server (NTRS)

    Masarik, J.; Reedy, R. C.

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Meisel, Zach

    2018-06-01

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

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

    PubMed

    Nguyen, Thanh Lam; Stanton, John F

    2013-04-04

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

  15. 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).

  16. Scanning mass spectrometer for quantitative reaction studies on catalytically active microstructures.

    PubMed

    Roos, M; Kielbassa, S; Schirling, C; Häring, T; Bansmann, J; Behm, R J

    2007-08-01

    We describe an apparatus for spatially resolving scanning mass spectrometry which is able to measure the gas composition above catalytically active microstructures or arrays of these microstructures with a lateral resolution of better than 100 mum under reaction conditions and which allows us to quantitatively determine reaction rates on individual microstructures. Measurements of the three-dimensional gas composition at different vertical distances and separations between active structures allow the evaluation of gas phase mass transport effects. The system is based on a piezoelectrically driven positioning substage for controlled lateral and vertical positioning of the sample under a rigidly mounted capillary probe connecting to a mass spectrometer. Measurements can be performed at pressures in the range of <10(-2)-10 mbars and temperatures between room temperature and 450 degrees C. The performance of the setup is demonstrated using the CO oxidation reaction on Pt microstructures on Si with sizes between 100 and 300 mum and distances in the same order of magnitude, evaluating CO(2) formation and CO consumption above the microstructures. The rapidly decaying lateral resolution with increasing distance between sample and probe underlines the effects of (lateral) gas transport in the room between sample and probe. The reaction rates and apparent activation energy obtained from such measurements agree with previous data on extended surfaces, demonstrating the feasibility of determining absolute reaction rates on individual microstructures.

  17. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1968-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

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

  20. Absolute Sea-level Changes Derived from Integrated Geodetic Datasets (1955-2016) in the Caribbean Sea

    NASA Astrophysics Data System (ADS)

    Yang, L.; Wang, G.; Liu, H.

    2017-12-01

    Rising sea level has important direct impacts on coastal and island regions such as the Caribbean where the influence of sea-level rise is becoming more apparent. The Caribbean Sea is a semi-enclosed sea adjacent to the landmasses of South and Central America to the south and west, and the Greater Antilles and the Lesser Antilles separate it from the Atlantic Ocean to the north and east. The work focus on studying the relative and absolute sea-level changes by integrating tide gauge, GPS, and satellite altimetry datasets (1955-2016) within the Caribbean Sea. Further, the two main components of absolute sea-level change, ocean mass and steric sea-level changes, are respectively studied using GRACE, temperature, and salinity datasets (1955-2016). According to the analysis conducted, the sea-level change rates have considerable temporal and spatial variations, and estimates may be subject to the techniques used and observation periods. The average absolute sea-level rise rate is 1.8±0.3 mm/year for the period from 1955 to 2015 according to the integrated tide gauge and GPS observations; the average absolute sea-level rise rate is 3.5±0.6 mm/year for the period from 1993 to 2016 according to the satellite altimetry observations. This study shows that the absolute sea-level change budget in the Caribbean Sea is closed in the periods from 1955 to 2016, in which ocean mass change dominates the absolute sea-level rise. The absolute sea-level change budget is also closed in the periods from 2004 to 2016, in which steric sea-level rise dominates the absolute sea-level rise.

  1. Quantum Reactive Scattering of Ultracold K+KRb Reaction: Universality and Chaotic Dynamics

    NASA Astrophysics Data System (ADS)

    Croft, J. F. E.; Makrides, C.; Li, M.; Petrov, A.; Kendrick, B. K.; Balakrishnan, N.; Kotochigova, S.

    2017-04-01

    A fundamental question in the study of chemical reactions is how reactions proceed at a collision energy close to absolute zero. This question is no longer hypothetical: quantum degenerate gases of atoms and molecules can now be created at temperatures lower than a few tens of nanoKelvin. In this talk, we discuss the benchmark ultracold reaction between, the most-celebrated ultracold molecule, KRb and K. We report numerically exact quantum-mechanical calculations of the K+KRb reaction on an accurate ab initio ground state potential energy surface of the K2Rb system and compare our results with available experimental data and predictions of universal models. The role of non-additive three-body contributions to the interaction potential is examined and is found to be small for the total reaction rates. However, the rotationally resolved rate coefficients are shown to be sensitive to the short-range interaction potential and follow a Poissonian distribution. This work was supported in part by NSF Grants PHY-1505557 (N.B.), PHY-1619788 (S.K.), ARO MURI Grant No. W911NF-12-1-0476 (N.B. & S.K.), and DOE LDRD Grant No. 20170221ER (B.K.).

  2. 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.

  3. Jasminum flexile flower absolute from India--a detailed comparison with three other jasmine absolutes.

    PubMed

    Braun, Norbert A; Kohlenberg, Birgit; Sim, Sherina; Meier, Manfred; Hammerschmidt, Franz-Josef

    2009-09-01

    Jasminum flexile flower absolute from the south of India and the corresponding vacuum headspace (VHS) sample of the absolute were analyzed using GC and GC-MS. Three other commercially available Indian jasmine absolutes from the species: J. sambac, J. officinale subsp. grandiflorum, and J. auriculatum and the respective VHS samples were used for comparison purposes. One hundred and twenty-one compounds were characterized in J. flexile flower absolute, with methyl linolate, benzyl salicylate, benzyl benzoate, (2E,6E)-farnesol, and benzyl acetate as the main constituents. A detailed olfactory evaluation was also performed.

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

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

  5. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K [Pleasanton, CA; Snyderman, Neal J [Berkeley, CA; Rowland, Mark S [Alamo, CA

    2012-05-15

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  6. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K [Pleasanton, CA; Snyderman, Neal J [Berkeley, CA; Rowland, Mark S [Alamo, CA

    2010-07-13

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

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

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

    Peters, Catherine A

    2013-02-28

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

  8. Absolute rate expressions for hydrogen atom abstraction from molybdenum hydrides by carbon-centered radicals

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

    Franz, J.A.; Linehan, J.C.; Birnbaum, J.C.

    1999-10-27

    A new family of basis rate expressions for hydrogen atom abstraction by primary, secondary, and tertiary alkyl radicals in dodecane and benzyl radical in benzene from the molybdenum hydride Cp*Mo-(CO){sub 3}H and for reactions of a primary alkyl radical with CpMo(CO){sub 3}H in dodecane are reported (Cp* = {eta}{sup 5}-pentamethylcyclopentadienyl, Cp = {eta}{sup 5}-cyclopentadienyl). Rate expressions for reaction of primary, secondary, and tertiary radical clocks with Cp*Mo(CO){sub 3}H were as follows: for hex-5-enyl, log(k/M{sup {minus}1} s{sup {minus}1}) = (9.27 {+-} 0.13) {minus} (1.36 {+-} 0.22)/{theta}, {theta} = 2.303RT kcal/mol; for hept-6-en-2-yl, log(k/M{sup {minus}1} s{sup {minus}1}) = (9.12 {+-} 0.42) {minus}more » (1.91 {+-} 0.74)/{theta}; and for 2-methylhept-6-en-2-yl, log(k/M{sup {minus}1} s{sup {minus}1}) = (9.36 {+-} 0.18) {minus} (3.19 {+-} 0.30)/{theta} (errors are 2{sigma}). Hydrogen atom abstraction from CpMo(CO){sub 3}H by hex-5-enyl is described by log(k/M{sup {minus}1} s{sup {minus}1}) = (9.53 {+-} 0.34) {minus} (1.24 {+-} 0.62)/{theta}. Relative rate constants for 1{degree}:2{degree}:3{degree} alkyl radicals were found to be 26:7:1 at 298 K. Benzyl radical was found to react 1.4 times faster than tertiary alkyl radical. The much higher selectivities for CP*Mo(CO){sub 3}H than those observed for main group hydrides (Bu{sub 3}SnH, PhSeH, PhSH) with alkyl radicals, together with the very fast benzyl hydrogen-transfer rate, suggest the relative unimportance of simple enthalpic effects and the dominance of steric effects for the early transition-state hydrogen transfers. Hydrogen abstraction from Cp*Mo(CO){sub 3}H by benzyl radicals is described by log(k/M{sup {minus}1} s{sup {minus}1}) = (8.89 {+-} 0.22) {minus} (2.31 {+-} 0.33)/{theta}.« less

  9. Effect of the absolute statistic on gene-sampling gene-set analysis methods.

    PubMed

    Nam, Dougu

    2017-06-01

    Gene-set enrichment analysis and its modified versions have commonly been used for identifying altered functions or pathways in disease from microarray data. In particular, the simple gene-sampling gene-set analysis methods have been heavily used for datasets with only a few sample replicates. The biggest problem with this approach is the highly inflated false-positive rate. In this paper, the effect of absolute gene statistic on gene-sampling gene-set analysis methods is systematically investigated. Thus far, the absolute gene statistic has merely been regarded as a supplementary method for capturing the bidirectional changes in each gene set. Here, it is shown that incorporating the absolute gene statistic in gene-sampling gene-set analysis substantially reduces the false-positive rate and improves the overall discriminatory ability. Its effect was investigated by power, false-positive rate, and receiver operating curve for a number of simulated and real datasets. The performances of gene-set analysis methods in one-tailed (genome-wide association study) and two-tailed (gene expression data) tests were also compared and discussed.

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

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

    Liu, Yuanyuan; Liu, Chongxuan; Zhang, Changyong

    2015-08-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

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

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

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

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

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

    DOE PAGES

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

    2017-11-10

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

  16. Optical factors determined by the T-matrix method in turbidity measurement of absolute coagulation rate constants.

    PubMed

    Xu, Shenghua; Liu, Jie; Sun, Zhiwei

    2006-12-01

    Turbidity measurement for the absolute coagulation rate constants of suspensions has been extensively adopted because of its simplicity and easy implementation. A key factor in deriving the rate constant from experimental data is how to theoretically evaluate the so-called optical factor involved in calculating the extinction cross section of doublets formed during aggregation. In a previous paper, we have shown that compared with other theoretical approaches, the T-matrix method provides a robust solution to this problem and is effective in extending the applicability range of the turbidity methodology, as well as increasing measurement accuracy. This paper will provide a more comprehensive discussion of the physical insight for using the T-matrix method in turbidity measurement and associated technical details. In particular, the importance of ensuring the correct value for the refractive indices for colloidal particles and the surrounding medium used in the calculation is addressed, because the indices generally vary with the wavelength of the incident light. The comparison of calculated results with experiments shows that the T-matrix method can correctly calculate optical factors even for large particles, whereas other existing theories cannot. In addition, the data of the optical factor calculated by the T-matrix method for a range of particle radii and incident light wavelengths are listed.

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

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

    Meisel, Zach

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

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

    DOE PAGES

    Meisel, Zach

    2018-06-21

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

  19. 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.

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

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

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

    2014-11-21

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

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

    PubMed

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

    2012-07-05

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

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

    NASA Astrophysics Data System (ADS)

    Manogaran, Lavaneesvari; Sek, Siok Kun

    2017-04-01

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

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

    USGS Publications Warehouse

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

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

  4. Modeling microbial reaction rates in a submarine hydrothermal vent chimney wall

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Schweigert, Igor

    2014-03-01

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

  6. 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.

  7. 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.

  8. 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.

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

    DOEpatents

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

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    PubMed

    Grima, R

    2010-07-21

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

  12. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

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

    NASA Astrophysics Data System (ADS)

    Bertulani, C. A.

    2018-01-01

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

  14. Rate constant for the reaction NH2 + NO from 216 to 480 K

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Brobst, W. D.; Nava, D. F.; Borkowski, R. P.; Michael, J. V.

    1982-01-01

    The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

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

    PubMed

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

    2018-07-01

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

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

    PubMed

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

    2010-12-17

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

  17. Thermodynamic criteria for estimating the kinetic parameters of catalytic reactions

    NASA Astrophysics Data System (ADS)

    Mitrichev, I. I.; Zhensa, A. V.; Kol'tsova, E. M.

    2017-01-01

    Kinetic parameters are estimated using two criteria in addition to the traditional criterion that considers the consistency between experimental and modeled conversion data: thermodynamic consistency and the consistency with entropy production (i.e., the absolute rate of the change in entropy due to exchange with the environment is consistent with the rate of entropy production in the steady state). A special procedure is developed and executed on a computer to achieve the thermodynamic consistency of a set of kinetic parameters with respect to both the standard entropy of a reaction and the standard enthalpy of a reaction. A problem of multi-criterion optimization, reduced to a single-criterion problem by summing weighted values of the three criteria listed above, is solved. Using the reaction of NO reduction with CO on a platinum catalyst as an example, it is shown that the set of parameters proposed by D.B. Mantri and P. Aghalayam gives much worse agreement with experimental values than the set obtained on the basis of three criteria: the sum of the squares of deviations for conversion, the thermodynamic consistency, and the consistency with entropy production.

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

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

    PubMed

    Woon, D E; Herbst, E

    1997-03-01

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

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

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

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

    2016-04-14

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

  1. 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.

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

    PubMed Central

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

    2013-01-01

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

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

    DTIC Science & Technology

    2003-06-12

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

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

  5. Estimating the absolute wealth of households.

    PubMed

    Hruschka, Daniel J; Gerkey, Drew; Hadley, Craig

    2015-07-01

    To estimate the absolute wealth of households using data from demographic and health surveys. We developed a new metric, the absolute wealth estimate, based on the rank of each surveyed household according to its material assets and the assumed shape of the distribution of wealth among surveyed households. Using data from 156 demographic and health surveys in 66 countries, we calculated absolute wealth estimates for households. We validated the method by comparing the proportion of households defined as poor using our estimates with published World Bank poverty headcounts. We also compared the accuracy of absolute versus relative wealth estimates for the prediction of anthropometric measures. The median absolute wealth estimates of 1,403,186 households were 2056 international dollars per capita (interquartile range: 723-6103). The proportion of poor households based on absolute wealth estimates were strongly correlated with World Bank estimates of populations living on less than 2.00 United States dollars per capita per day (R(2)  = 0.84). Absolute wealth estimates were better predictors of anthropometric measures than relative wealth indexes. Absolute wealth estimates provide new opportunities for comparative research to assess the effects of economic resources on health and human capital, as well as the long-term health consequences of economic change and inequality.

  6. Transcriptional dynamics with time-dependent reaction rates

    NASA Astrophysics Data System (ADS)

    Nandi, Shubhendu; Ghosh, Anandamohan

    2015-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2018-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  9. Quantifying risk: the role of absolute and relative measures in interpreting risk of adverse reactions from product labels of antipsychotic medications.

    PubMed

    Citrome, Leslie

    2009-09-01

    Pharmaceutical product labeling as approved by regulatory agencies include statements of adverse event risk. Product labels include descriptive statements such as whether events are uncommon or rare, as well as percentage occurrence for more common events. In addition tables are provided with the frequencies of the latter events for both product and placebo as observed in clinical trials. Competing products are not mentioned in a specific drug's product labeling but indirect comparisons can be made using the corresponding label information for the alternate product. Two types of tools are easily used for this purpose: absolute measures such as number needed to harm (NNH), and relative measures such as relative risk increase (RRI). The calculations for both of these types of quantitative measures are presented using as examples the oral first-line second-generation antipsychotic medications. Among three sample outcomes selected a priori, akathisia, weight gain, and discontinuation from a clinical trial because of an adverse reaction, there appears to be differences among the different antipsychotics versus placebo. Aripiprazole was associated with the highest risk for akathisia, particularly when used as adjunctive treatment of major depressive disorder (NNH 5, 95% CI 4-7; RRI 525%, 95% CI 267%-964%). Although insufficient information was available in product labeling to calculate the CI, olanzapine was associated with the highest risk for weight gain of at least 7% from baseline (NNH 6, RRI 640% for adults; NNH 4, RRI 314% for adolescents), and quetiapine for the indication of bipolar depression was associated with the highest risk of discontinuation from a clinical trial because of an adverse reaction (NNH 8, RRI 265% for 600 mg/d; NNH 15, RRI 137% for 300 mg/d). In conclusion, with certain limitations, it is possible for the clinician to extract information from medication product labeling regarding the frequency with which certain adverse reactions can be

  10. Flame Chemiluminescence Rate Constants for Quantitative Microgravity Combustion Diagnostics

    NASA Technical Reports Server (NTRS)

    Luque, Jorge; Smith, Gregory P.; Jeffries, Jay B.; Crosley, David R.; Weiland, Karen (Technical Monitor)

    2001-01-01

    Absolute excited state concentrations of OH(A), CH(A), and C2(d) were determined in three low pressure premixed methane-air flames. Two dimensional images of chemiluminescence from these states were recorded by a filtered CCD camera, processed by Abel inversion, and calibrated against Rayleigh scattering, Using a previously validated 1-D flame model with known chemistry and excited state quenching rate constants, rate constants are extracted for the reactions CH + O2 (goes to) OH(A) + CO and C2H + O (goes to) CH(A) + CO at flame temperatures. Variations of flame emission intensities with stoichiometry agree well with model predictions.

  11. 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.

  12. Prospective Teachers' Reactions to "Right-or-Wrong" Tasks: The Case of Derivatives of Absolute Value Functions

    ERIC Educational Resources Information Center

    Tsamir, Pessia; Rasslan, Shaker; Dreyfus, Tommy

    2006-01-01

    This paper illustrates the role of a "Thinking-about-Derivatives" task in identifying learners' derivative conceptions and for promoting their critical thinking about derivatives of absolute value functions. The task included three parts: "Define" the derivative of a function f(x) at x = x[subscript 0], "Solve-if-Possible" the derivative of f(x) =…

  13. 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.

  14. Estimating the absolute wealth of households

    PubMed Central

    Gerkey, Drew; Hadley, Craig

    2015-01-01

    Abstract Objective To estimate the absolute wealth of households using data from demographic and health surveys. Methods We developed a new metric, the absolute wealth estimate, based on the rank of each surveyed household according to its material assets and the assumed shape of the distribution of wealth among surveyed households. Using data from 156 demographic and health surveys in 66 countries, we calculated absolute wealth estimates for households. We validated the method by comparing the proportion of households defined as poor using our estimates with published World Bank poverty headcounts. We also compared the accuracy of absolute versus relative wealth estimates for the prediction of anthropometric measures. Findings The median absolute wealth estimates of 1 403 186 households were 2056 international dollars per capita (interquartile range: 723–6103). The proportion of poor households based on absolute wealth estimates were strongly correlated with World Bank estimates of populations living on less than 2.00 United States dollars per capita per day (R2 = 0.84). Absolute wealth estimates were better predictors of anthropometric measures than relative wealth indexes. Conclusion Absolute wealth estimates provide new opportunities for comparative research to assess the effects of economic resources on health and human capital, as well as the long-term health consequences of economic change and inequality. PMID:26170506

  15. 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.

  16. Absolute calibration of neutron detectors on the C-2U advanced beam-driven FRC.

    PubMed

    Magee, R M; Clary, R; Korepanov, S; Jauregui, F; Allfrey, I; Garate, E; Valentine, T; Smirnov, A

    2016-11-01

    In the C-2U fusion energy experiment, high power neutral beam injection creates a large fast ion population that sustains a field-reversed configuration (FRC) plasma. The diagnosis of the fast ion pressure in these high-performance plasmas is therefore critical, and the measurement of the flux of neutrons from the deuterium-deuterium (D-D) fusion reaction is well suited to the task. Here we describe the absolute, in situ calibration of scintillation neutron detectors via two independent methods: firing deuterium beams into a high density gas target and calibration with a 2 × 10 7 n/s AmBe source. The practical issues of each method are discussed and the resulting calibration factors are shown to be in good agreement. Finally, the calibration factor is applied to C-2U experimental data where the measured neutron rate is found to exceed the classical expectation.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

    Naine, Tarun Bharath; Gundawar, Manoj Kumar

    2017-09-01

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

  20. Implementation of steady state approximation for modelling of reaction kinetic of UV catalysed hydrogen peroxide oxidation of starch

    NASA Astrophysics Data System (ADS)

    Kumoro, Andri Cahyo; Retnowati, Diah Susetyo; Ratnawati, Budiyati, Catarina Sri

    2015-12-01

    With regard to its low viscosity, high stability, clarity, film forming and binding properties, oxidised starch has been widely used in various applications specifically in the food, paper, textile, laundry finishing and binding materials industries. A number of methods have been used to produce oxidised starch through reactions with various oxidizing agents, such as hydrogen peroxide, air oxygen, ozone, bromine, chromic acid, permanganate, nitrogen dioxide and hypochlorite. Unfortunately, most of previous works reported in the literatures were focused on the study of reaction mechanism and physicochemical properties characterization of the oxidised starches produced without investigation of the reaction kinetics of the oxidation process. This work aimed to develop a simple kinetic model for UV catalysed hydrogen peroxide oxidation of starch through implementation of steady state approximation for the radical reaction rates. The model was then verified using experimental data available in the literature. The model verification revealed that the proposed model shows its good agreement with the experimental data as indicated by an average absolute relative error of only 2.45%. The model also confirmed that carboxyl groups are oxidised further by hydroxyl radical. The carbonyl production rate was found to follow first order reaction with respect to carbonyl concentration. Similarly, carboxyl production rate also followed first order reaction with respect to carbonyl concentration. The apparent reaction rate constant for carbonyl formation and oxidation were 6.24 × 104 s-1 and 1.01 × 104 M-1.s-1, respectively. While apparent reaction rate constant for carboxyl oxidation was 4.86 × 104 M-1.s-1.

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

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

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-12-09

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

  2. Determination of Absolute Configuration of Secondary Alcohols Using Thin-Layer Chromatography

    PubMed Central

    Wagner, Alexander J.; Rychnovsky, Scott D.

    2013-01-01

    A new implementation of the Competing Enantioselective Conversion (CEC) method was developed to qualitatively determine the absolute configuration of enantioenriched secondary alcohols using thin-layer chromatography. The entire process for the method requires approximately 60 min and utilizes micromole quantities of the secondary alcohol being tested. A number of synthetically relevant secondary alcohols are presented. Additionally, 1H NMR spectroscopy was conducted on all samples to provide evidence of reaction conversion that supports the qualitative method presented herein. PMID:23593963

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

    NASA Astrophysics Data System (ADS)

    Holmen, B. A.; Stevens, T.

    2009-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

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

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

    PubMed

    Beniwal, Vijay; Manna, Arpan; Kumar, Anil

    2016-07-04

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

  6. 20 CFR 404.1205 - Absolute coverage groups.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 20 Employees' Benefits 2 2011-04-01 2011-04-01 false Absolute coverage groups. 404.1205 Section... Covered § 404.1205 Absolute coverage groups. (a) General. An absolute coverage group is a permanent... are not under a retirement system. An absolute coverage group may include positions which were...

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

    NASA Astrophysics Data System (ADS)

    Cannon, William R.; Baker, Scott E.

    2017-10-01

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

  8. Measurement of absolute gamma emission probabilities

    NASA Astrophysics Data System (ADS)

    Sumithrarachchi, Chandana S.; Rengan, Krish; Griffin, Henry C.

    2003-06-01

    The energies and emission probabilities (intensities) of gamma-rays emitted in radioactive decays of particular nuclides are the most important characteristics by which to quantify mixtures of radionuclides. Often, quantification is limited by uncertainties in measured intensities. A technique was developed to reduce these uncertainties. The method involves obtaining a pure sample of a nuclide using radiochemical techniques, and using appropriate fractions for beta and gamma measurements. The beta emission rates were measured using a liquid scintillation counter, and the gamma emission rates were measured with a high-purity germanium detector. Results were combined to obtain absolute gamma emission probabilities. All sources of uncertainties greater than 0.1% were examined. The method was tested with 38Cl and 88Rb.

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

    PubMed

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

    2016-03-03

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

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

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

    DOE PAGES

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

    2017-09-01

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

  12. Indirectly estimated absolute lung cancer mortality rates by smoking status and histological type based on a systematic review

    PubMed Central

    2013-01-01

    Background National smoking-specific lung cancer mortality rates are unavailable, and studies presenting estimates are limited, particularly by histology. This hinders interpretation. We attempted to rectify this by deriving estimates indirectly, combining data from national rates and epidemiological studies. Methods We estimated study-specific absolute mortality rates and variances by histology and smoking habit (never/ever/current/former) based on relative risk estimates derived from studies published in the 20th century, coupled with WHO mortality data for age 70–74 for the relevant country and period. Studies with populations grossly unrepresentative nationally were excluded. 70–74 was chosen based on analyses of large cohort studies presenting rates by smoking and age. Variations by sex, period and region were assessed by meta-analysis and meta-regression. Results 148 studies provided estimates (Europe 59, America 54, China 22, other Asia 13), 54 providing estimates by histology (squamous cell carcinoma, adenocarcinoma). For all smoking habits and lung cancer types, mortality rates were higher in males, the excess less evident for never smokers. Never smoker rates were clearly highest in China, and showed some increasing time trend, particularly for adenocarcinoma. Ever smoker rates were higher in parts of Europe and America than in China, with the time trend very clear, especially for adenocarcinoma. Variations by time trend and continent were clear for current smokers (rates being higher in Europe and America than Asia), but less clear for former smokers. Models involving continent and trend explained much variability, but non-linearity was sometimes seen (with rates lower in 1991–99 than 1981–90), and there was regional variation within continent (with rates in Europe often high in UK and low in Scandinavia, and higher in North than South America). Conclusions The indirect method may be questioned, because of variations in definition of smoking and

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

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher E.; Walch, Stephen P.

    2002-01-01

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

  14. [Adverse drug reaction reporting in emergency medicine].

    PubMed

    Milojevic, Kolia; Chassagnol, Isabelle; Brion, Nathalie; Cléro, Joël; Degrèze, Nathalie; Lambert, Yves

    2004-01-01

    A regional survey was performed between June and September 2002, to evaluate knowledge and attitudes of emergency physicians regarding adverse drug reaction (ADR) reporting in a French district. 100 questionnaires completed by physicians working in emergency departments and/or mobile intensive care units were analysed. The frequency of ADRs encountered by emergency practitioners was estimated at > or = 0.73 per year and per physician. The ADR notification rate in emergency medicine was estimated at < or = 6%. A minority of physicians were responsible for the majority of ADR reporting. Sixty-four percent of emergency physicians underestimated the conditions required for ADR notification: 28% thought that certain causality was an absolute necessary condition for notification, while 37% considered that notification was required only for ADRs that were both severe and unexpected. Interventions focused on advertising ADR reporting procedures could help to improve the notification rate in emergency medicine.

  15. 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.

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

    PubMed

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

    2018-05-04

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

  17. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Pellet

    NASA Astrophysics Data System (ADS)

    Li, Fei; Tangstad, Merete

    2018-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Li, Fei; Tangstad, Merete

    2018-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Funaki, Yasuro

    2015-04-01

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

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

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

    Cook, D.

    1976-06-11

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

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

    PubMed

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

    2009-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Engdahl, N. B.

    2016-12-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Schwarz, Karsten; Rieger, Heiko

    2013-03-01

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

  5. Absolute calibration of neutron detectors on the C-2U advanced beam-driven FRC

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

    Magee, R. M., E-mail: rmagee@trialphaenergy.com; Clary, R.; Korepanov, S.

    2016-11-15

    In the C-2U fusion energy experiment, high power neutral beam injection creates a large fast ion population that sustains a field-reversed configuration (FRC) plasma. The diagnosis of the fast ion pressure in these high-performance plasmas is therefore critical, and the measurement of the flux of neutrons from the deuterium-deuterium (D-D) fusion reaction is well suited to the task. Here we describe the absolute, in situ calibration of scintillation neutron detectors via two independent methods: firing deuterium beams into a high density gas target and calibration with a 2 × 10{sup 7} n/s AmBe source. The practical issues of each methodmore » are discussed and the resulting calibration factors are shown to be in good agreement. Finally, the calibration factor is applied to C-2U experimental data where the measured neutron rate is found to exceed the classical expectation.« less

  6. Fingerprints of flower absolutes using supercritical fluid chromatography hyphenated with high resolution mass spectrometry.

    PubMed

    Santerre, Cyrille; Vallet, Nadine; Touboul, David

    2018-06-02

    Supercritical fluid chromatography hyphenated with high resolution mass spectrometry (SFC-HRMS) was developed for fingerprint analysis of different flower absolutes commonly used in cosmetics field, especially in perfumes. Supercritical fluid chromatography-atmospheric pressure photoionization-high resolution mass spectrometry (SFC-APPI-HRMS) technique was employed to identify the components of the fingerprint. The samples were separated with a porous graphitic carbon (PGC) Hypercarb™ column (100 mm × 2.1 mm, 3 μm) by gradient elution using supercritical CO 2 and ethanol (0.0-20.0 min (2-30% B), 20.0-25.0 min (30% B), 25.0-26.0 min (30-2% B) and 26.0-30.0 min (2% B)) as mobile phase at a flow rate of 1.5 mL/min. In order to compare the SFC fingerprints between five different flower absolutes: Jasminum grandiflorum absolutes, Jasminum sambac absolutes, Narcissus jonquilla absolutes, Narcissus poeticus absolutes, Lavandula angustifolia absolutes from different suppliers and batches, the chemometric procedure including principal component analysis (PCA) was applied to classify the samples according to their genus and their species. Consistent results were obtained to show that samples could be successfully discriminated. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. 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.

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

    PubMed Central

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

    2011-01-01

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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1995-02-01

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

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

    PubMed

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

    2015-07-01

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

  12. Absolute plate motions relative to deep mantle plumes

    NASA Astrophysics Data System (ADS)

    Wang, Shimin; Yu, Hongzheng; Zhang, Qiong; Zhao, Yonghong

    2018-05-01

    Advances in whole waveform seismic tomography have revealed the presence of broad mantle plumes rooted at the base of the Earth's mantle beneath major hotspots. Hotspot tracks associated with these deep mantle plumes provide ideal constraints for inverting absolute plate motions as well as testing the fixed hotspot hypothesis. In this paper, 27 observed hotspot trends associated with 24 deep mantle plumes are used together with the MORVEL model for relative plate motions to determine an absolute plate motion model, in terms of a maximum likelihood optimization for angular data fitting, combined with an outlier data detection procedure based on statistical tests. The obtained T25M model fits 25 observed trends of globally distributed hotspot tracks to the statistically required level, while the other two hotspot trend data (Comores on Somalia and Iceland on Eurasia) are identified as outliers, which are significantly incompatible with other data. For most hotspots with rate data available, T25M predicts plate velocities significantly lower than the observed rates of hotspot volcanic migration, which cannot be fully explained by biased errors in observed rate data. Instead, the apparent hotspot motions derived by subtracting the observed hotspot migration velocities from the T25M plate velocities exhibit a combined pattern of being opposite to plate velocities and moving towards mid-ocean ridges. The newly estimated net rotation of the lithosphere is statistically compatible with three recent estimates, but differs significantly from 30 of 33 prior estimates.

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

    PubMed

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

    2012-11-01

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

  14. Forecasting Error Calculation with Mean Absolute Deviation and Mean Absolute Percentage Error

    NASA Astrophysics Data System (ADS)

    Khair, Ummul; Fahmi, Hasanul; Hakim, Sarudin Al; Rahim, Robbi

    2017-12-01

    Prediction using a forecasting method is one of the most important things for an organization, the selection of appropriate forecasting methods is also important but the percentage error of a method is more important in order for decision makers to adopt the right culture, the use of the Mean Absolute Deviation and Mean Absolute Percentage Error to calculate the percentage of mistakes in the least square method resulted in a percentage of 9.77% and it was decided that the least square method be worked for time series and trend data.

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

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

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

    PubMed

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

    2015-10-01

    In this study, we aimed to investigate whether progesterone-induced acrosome reaction (AR) rate could be an indicator for fertilisation rate in vitro. Twenty-six couples with unexplained infertility and undergoing in vitro fertilisation (IVF) treatment were involved. On the oocytes retrieval day after routine IVF, residual sperm samples were collected to receive progesterone induction (progesterone group) or not (control group). AR rate was calculated and fertilisation rate was recorded. The correlation between progesterone-induced AR and fertilisation rate and between sperm normal morphology and 3PN (tripronuclear) were analysed using the Spearman correlation analysis. The AR rate of progesterone group was statistically higher than that of the control group (15.6 ± 5.88% versus 9.66 ± 5.771%, P < 0.05), but not significantly correlated with fertilisation rate (r = -0.053, P > 0.01) or rate of high-quality embryo development (r = -0.055, P > 0.01). Normal sperm morphology also showed no significant correlation with the amount of 3PN zygotes (r = 0.029, P > 0.01), rate of 3PN zygotes production (r = 0.20, P > 0.01), rate of 3PN embryo development (r = -0.406, P > 0.01), fertilisation rate (r = -0.148, P > 0.01) or progesterone-induced AR rate (r = 0.214, P > 0.01). Progesterone can induce AR in vitro significantly; however, the progesterone-induced AR may not be used to indicate fertilisation rate. © 2014 Blackwell Verlag GmbH.

  20. 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.

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

    PubMed Central

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

    2015-01-01

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

  2. 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.

  3. Concurrent Application of ANC and THM to assess the 13C(α, n)16O Absolute Cross Section at Astrophysical Energies and Possible Consequences for Neutron Production in Low-mass AGB Stars

    NASA Astrophysics Data System (ADS)

    Trippella, O.; La Cognata, M.

    2017-03-01

    The {}13{{C}}{(α ,n)}16{{O}} reaction is considered to be the main neutron source responsible for the production of heavy nuclides (from {Sr} to {Bi}) through slow n-capture nucleosynthesis (s-process) at low temperatures during the asymptotic giant branch phase of low-mass stars (≲ 3{--}4 {M}⊙ , or LMSs). In recent years, several direct and indirect measurements have been carried out to determine the cross section at the energies of astrophysical interest (around 190+/- 40 {keV}). However, they yield inconsistent results that cause a highly uncertain reaction rate and affect the neutron release in LMSs. In this work we have combined two indirect approaches, the asymptotic normalization coefficient and the Trojan horse method, to unambiguously determine the absolute value of the {}13{{C}}{(α ,n)}16{{O}} astrophysical factor. With these, we have determined a very accurate reaction rate to be introduced into astrophysical models of s-process nucleosynthesis in LMSs. Calculations using this recommended rate have shown limited variations in the production of those neutron-rich nuclei (with 86≤slant A≤slant 209) that receive contribution only by slow neutron captures.

  4. 20 CFR 404.1205 - Absolute coverage groups.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 20 Employees' Benefits 2 2014-04-01 2014-04-01 false Absolute coverage groups. 404.1205 Section... INSURANCE (1950- ) Coverage of Employees of State and Local Governments What Groups of Employees May Be Covered § 404.1205 Absolute coverage groups. (a) General. An absolute coverage group is a permanent...

  5. 20 CFR 404.1205 - Absolute coverage groups.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 20 Employees' Benefits 2 2013-04-01 2013-04-01 false Absolute coverage groups. 404.1205 Section... INSURANCE (1950- ) Coverage of Employees of State and Local Governments What Groups of Employees May Be Covered § 404.1205 Absolute coverage groups. (a) General. An absolute coverage group is a permanent...

  6. 20 CFR 404.1205 - Absolute coverage groups.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 20 Employees' Benefits 2 2012-04-01 2012-04-01 false Absolute coverage groups. 404.1205 Section... INSURANCE (1950- ) Coverage of Employees of State and Local Governments What Groups of Employees May Be Covered § 404.1205 Absolute coverage groups. (a) General. An absolute coverage group is a permanent...

  7. Droplet Digital Enzyme-Linked Oligonucleotide Hybridization Assay for Absolute RNA Quantification.

    PubMed

    Guan, Weihua; Chen, Liben; Rane, Tushar D; Wang, Tza-Huei

    2015-09-03

    We present a continuous-flow droplet-based digital Enzyme-Linked Oligonucleotide Hybridization Assay (droplet digital ELOHA) for sensitive detection and absolute quantification of RNA molecules. Droplet digital ELOHA incorporates direct hybridization and single enzyme reaction via the formation of single probe-RNA-probe (enzyme) complex on magnetic beads. It enables RNA detection without reverse transcription and PCR amplification processes. The magnetic beads are subsequently encapsulated into a large number of picoliter-sized droplets with enzyme substrates in a continuous-flow device. This device is capable of generating droplets at high-throughput. It also integrates in-line enzymatic incubation and detection of fluorescent products. Our droplet digital ELOHA is able to accurately quantify (differentiate 40% difference) as few as ~600 RNA molecules in a 1 mL sample (equivalent to 1 aM or lower) without molecular replication. The absolute quantification ability of droplet digital ELOHA is demonstrated with the analysis of clinical Neisseria gonorrhoeae 16S rRNA to show its potential value in real complex samples.

  8. Droplet Digital Enzyme-Linked Oligonucleotide Hybridization Assay for Absolute RNA Quantification

    PubMed Central

    Guan, Weihua; Chen, Liben; Rane, Tushar D.; Wang, Tza-Huei

    2015-01-01

    We present a continuous-flow droplet-based digital Enzyme-Linked Oligonucleotide Hybridization Assay (droplet digital ELOHA) for sensitive detection and absolute quantification of RNA molecules. Droplet digital ELOHA incorporates direct hybridization and single enzyme reaction via the formation of single probe-RNA-probe (enzyme) complex on magnetic beads. It enables RNA detection without reverse transcription and PCR amplification processes. The magnetic beads are subsequently encapsulated into a large number of picoliter-sized droplets with enzyme substrates in a continuous-flow device. This device is capable of generating droplets at high-throughput. It also integrates in-line enzymatic incubation and detection of fluorescent products. Our droplet digital ELOHA is able to accurately quantify (differentiate 40% difference) as few as ~600 RNA molecules in a 1 mL sample (equivalent to 1 aM or lower) without molecular replication. The absolute quantification ability of droplet digital ELOHA is demonstrated with the analysis of clinical Neisseria gonorrhoeae 16S rRNA to show its potential value in real complex samples. PMID:26333806

  9. Droplet Digital Enzyme-Linked Oligonucleotide Hybridization Assay for Absolute RNA Quantification

    NASA Astrophysics Data System (ADS)

    Guan, Weihua; Chen, Liben; Rane, Tushar D.; Wang, Tza-Huei

    2015-09-01

    We present a continuous-flow droplet-based digital Enzyme-Linked Oligonucleotide Hybridization Assay (droplet digital ELOHA) for sensitive detection and absolute quantification of RNA molecules. Droplet digital ELOHA incorporates direct hybridization and single enzyme reaction via the formation of single probe-RNA-probe (enzyme) complex on magnetic beads. It enables RNA detection without reverse transcription and PCR amplification processes. The magnetic beads are subsequently encapsulated into a large number of picoliter-sized droplets with enzyme substrates in a continuous-flow device. This device is capable of generating droplets at high-throughput. It also integrates in-line enzymatic incubation and detection of fluorescent products. Our droplet digital ELOHA is able to accurately quantify (differentiate 40% difference) as few as ~600 RNA molecules in a 1 mL sample (equivalent to 1 aM or lower) without molecular replication. The absolute quantification ability of droplet digital ELOHA is demonstrated with the analysis of clinical Neisseria gonorrhoeae 16S rRNA to show its potential value in real complex samples.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2018-02-01

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

  12. 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.

  13. [Prognostic value of absolute monocyte count in chronic lymphocytic leukaemia].

    PubMed

    Szerafin, László; Jakó, János; Riskó, Ferenc

    2015-04-01

    The low peripheral absolute lymphocyte and high monocyte count have been reported to correlate with poor clinical outcome in various lymphomas and other cancers. However, a few data known about the prognostic value of absolute monocyte count in chronic lymphocytic leukaemia. The aim of the authors was to investigate the impact of absolute monocyte count measured at the time of diagnosis in patients with chronic lymphocytic leukaemia on the time to treatment and overal survival. Between January 1, 2005 and December 31, 2012, 223 patients with newly-diagnosed chronic lymphocytic leukaemia were included. The rate of patients needing treatment, time to treatment, overal survival and causes of mortality based on Rai stages, CD38, ZAP-70 positivity and absolute monocyte count were analyzed. Therapy was necessary in 21.1%, 57.4%, 88.9%, 88.9% and 100% of patients in Rai stage 0, I, II, III an IV, respectively; in 61.9% and 60.8% of patients exhibiting CD38 and ZAP-70 positivity, respectively; and in 76.9%, 21.2% and 66.2% of patients if the absolute monocyte count was <0.25 G/l, between 0.25-0.75 G/l and >0.75 G/l, respectively. The median time to treatment and the median overal survival were 19.5, 65, and 35.5 months; and 41.5, 65, and 49.5 months according to the three groups of monocyte counts. The relative risk of beginning the therapy was 1.62 (p<0.01) in patients with absolute monocyte count <0.25 G/l or >0.75 G/l, as compared to those with 0.25-0.75 G/l, and the risk of overal survival was 2.41 (p<0.01) in patients with absolute monocyte count lower than 0.25 G/l as compared to those with higher than 0.25 G/l. The relative risks remained significant in Rai 0 patients, too. The leading causes of mortality were infections (41.7%) and the chronic lymphocytic leukaemia (58.3%) in patients with low monocyte count, while tumours (25.9-35.3%) and other events (48.1 and 11.8%) occurred in patients with medium or high monocyte counts. Patients with low and high monocyte

  14. Centrifugal step emulsification applied for absolute quantification of nucleic acids by digital droplet RPA.

    PubMed

    Schuler, Friedrich; Schwemmer, Frank; Trotter, Martin; Wadle, Simon; Zengerle, Roland; von Stetten, Felix; Paust, Nils

    2015-07-07

    Aqueous microdroplets provide miniaturized reaction compartments for numerous chemical, biochemical or pharmaceutical applications. We introduce centrifugal step emulsification for the fast and easy production of monodisperse droplets. Homogenous droplets with pre-selectable diameters in a range from 120 μm to 170 μm were generated with coefficients of variation of 2-4% and zero run-in time or dead volume. The droplet diameter depends on the nozzle geometry (depth, width, and step size) and interfacial tensions only. Droplet size is demonstrated to be independent of the dispersed phase flow rate between 0.01 and 1 μl s(-1), proving the robustness of the centrifugal approach. Centrifugal step emulsification can easily be combined with existing centrifugal microfluidic unit operations, is compatible to scalable manufacturing technologies such as thermoforming or injection moulding and enables fast emulsification (>500 droplets per second and nozzle) with minimal handling effort (2-3 pipetting steps). The centrifugal microfluidic droplet generation was used to perform the first digital droplet recombinase polymerase amplification (ddRPA). It was used for absolute quantification of Listeria monocytogenes DNA concentration standards with a total analysis time below 30 min. Compared to digital droplet polymerase chain reaction (ddPCR), with processing times of about 2 hours, the overall processing time of digital analysis was reduced by more than a factor of 4.

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

    NASA Astrophysics Data System (ADS)

    Ji, Y.; Shen, C.

    2014-03-01

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

  16. Theoretical considerations concerning the effect of relativistic velocities on the rate of biological processes.

    PubMed

    Heneine, I F

    1997-06-01

    Theoretical considerations were advanced on the reaction rate of biological systems in a rocket accelerated at fractional levels of the velocity of light. The values of mass increase in reacting molecules and length contraction of space under these relativistic velocities attained by the hypothetical rocket were inserted in equations of the absolute reaction rate theory. The equations employed were for the frequency of collisions, and for the internal kinetic energy of molecular reactions. Results of both sets of equations indicated that reduction of reaction rates were correlated to the mass increase. This would imply a general slowing of all chemical, biochemical and biological processes taking place. A human would suffer a related decrease in metabolic rate. Contrary to what is generally accepted, the biological aging of the space traveler under velocities bearable by humans, namely under 0.50c, would follow a pace very similar to that of an observer remaining in the resting frame of reference. With increased increments of the velocity, the space traveler would display a more intense lowering of the metabolic rate, with signs and symptoms comparable to body core hypothermia. Metabolic rates at insufficient levels to maintain the vital functions would be attained at 0.70c and higher, leading swiftly to coma and death. The presence of an endocrine dysfunction such as hypothyroidism or obesity in the space traveler would aggravate the signs and symptoms. Space travel at efficient velocities would be unbearable for a warm-blooded animal.

  17. Method of differential-phase/absolute-amplitude QAM

    DOEpatents

    Dimsdle, Jeffrey William [Overland Park, KS

    2007-07-03

    A method of quadrature amplitude modulation involving encoding phase differentially and amplitude absolutely, allowing for a high data rate and spectral efficiency in data transmission and other communication applications, and allowing for amplitude scaling to facilitate data recovery; amplitude scale tracking to track-out rapid and severe scale variations and facilitate successful demodulation and data retrieval; 2.sup.N power carrier recovery; incoherent demodulation where coherent carrier recovery is not possible or practical due to signal degradation; coherent demodulation; multipath equalization to equalize frequency dependent multipath; and demodulation filtering.

  18. Method of differential-phase/absolute-amplitude QAM

    DOEpatents

    Dimsdle, Jeffrey William [Overland Park, KS

    2008-10-21

    A method of quadrature amplitude modulation involving encoding phase differentially and amplitude absolutely, allowing for a high data rate and spectral efficiency in data transmission and other communication applications, and allowing for amplitude scaling to facilitate data recovery; amplitude scale tracking to track-out rapid and severe scale variations and facilitate successful demodulation and data retrieval; 2.sup.N power carrier recovery; incoherent demodulation where coherent carrier recovery is not possible or practical due to signal degradation; coherent demodulation; multipath equalization to equalize frequency dependent multipath; and demodulation filtering.

  19. Method of differential-phase/absolute-amplitude QAM

    DOEpatents

    Dimsdle, Jeffrey William [Overland Park, KS

    2009-09-01

    A method of quadrature amplitude modulation involving encoding phase differentially and amplitude absolutely, allowing for a high data rate and spectral efficiency in data transmission and other communication applications, and allowing for amplitude scaling to facilitate data recovery; amplitude scale tracking to track-out rapid and severe scale variations and facilitate successful demodulation and data retrieval; 2.sup.N power carrier recovery; incoherent demodulation where coherent carrier recovery is not possible or practical due to signal degradation; coherent demodulation; multipath equalization to equalize frequency dependent multipath; and demodulation filtering.

  20. Method of differential-phase/absolute-amplitude QAM

    DOEpatents

    Dimsdle, Jeffrey William [Overland Park, KS

    2007-07-17

    A method of quadrature amplitude modulation involving encoding phase differentially and amplitude absolutely, allowing for a high data rate and spectral efficiency in data transmission and other communication applications, and allowing for amplitude scaling to facilitate data recovery; amplitude scale tracking to track-out rapid and severe scale variations and facilitate successful demodulation and data retrieval; 2.sup.N power carrier recovery; incoherent demodulation where coherent carrier recovery is not possible or practical due to signal degradation; coherent demodulation; multipath equalization to equalize frequency dependent multipath; and demodulation filtering.

  1. Method of differential-phase/absolute-amplitude QAM

    DOEpatents

    Dimsdle, Jeffrey William

    2007-10-02

    A method of quadrature amplitude modulation involving encoding phase differentially and amplitude absolutely, allowing for a high data rate and spectral efficiency in data transmission and other communication applications, and allowing for amplitude scaling to facilitate data recovery; amplitude scale tracking to track-out rapid and severe scale variations and facilitate successful demodulation and data retrieval; 2.sup.N power carrier recovery; incoherent demodulation where coherent carrier recovery is not possible or practical due to signal degradation; coherent demodulation; multipath equalization to equalize frequency dependent multipath; and demodulation filtering.

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

    PubMed

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

    2015-12-03

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

  3. The absolute threshold of cone vision

    PubMed Central

    Koeing, Darran; Hofer, Heidi

    2013-01-01

    We report measurements of the absolute threshold of cone vision, which has been previously underestimated due to sub-optimal conditions or overly strict subjective response criteria. We avoided these limitations by using optimized stimuli and experimental conditions while having subjects respond within a rating scale framework. Small (1′ fwhm), brief (34 msec), monochromatic (550 nm) stimuli were foveally presented at multiple intensities in dark-adapted retina for 5 subjects. For comparison, 4 subjects underwent similar testing with rod-optimized stimuli. Cone absolute threshold, that is, the minimum light energy for which subjects were just able to detect a visual stimulus with any response criterion, was 203 ± 38 photons at the cornea, ∼0.47 log units lower than previously reported. Two-alternative forced-choice measurements in a subset of subjects yielded consistent results. Cone thresholds were less responsive to criterion changes than rod thresholds, suggesting a limit to the stimulus information recoverable from the cone mosaic in addition to the limit imposed by Poisson noise. Results were consistent with expectations for detection in the face of stimulus uncertainty. We discuss implications of these findings for modeling the first stages of human cone vision and interpreting psychophysical data acquired with adaptive optics at the spatial scale of the receptor mosaic. PMID:21270115

  4. Absolute photoionization cross section of the ethyl radical in the range 8-11.5 eV: synchrotron and vacuum ultraviolet laser measurements.

    PubMed

    Gans, Bérenger; Garcia, Gustavo A; Boyé-Péronne, Séverine; Loison, Jean-Christophe; Douin, Stéphane; Gaie-Levrel, François; Gauyacq, Dolores

    2011-06-02

    The absolute photoionization cross section of C(2)H(5) has been measured at 10.54 eV using vacuum ultraviolet (VUV) laser photoionization. The C(2)H(5) radical was produced in situ using the rapid C(2)H(6) + F → C(2)H(5) + HF reaction. Its absolute photoionization cross section has been determined in two different ways: first using the C(2)H(5) + NO(2) → C(2)H(5)O + NO reaction in a fast flow reactor, and the known absolute photoionization cross section of NO. In a second experiment, it has been measured relative to the known absolute photoionization cross section of CH(3) as a reference by using the CH(4) + F → CH(3) + HF and C(2)H(6) + F → C(2)H(5) + HF reactions successively. Both methods gave similar results, the second one being more precise and yielding the value: σ(C(2)H(5))(ion) = (5.6 ± 1.4) Mb at 10.54 eV. This value is used to calibrate on an absolute scale the photoionization curve of C(2)H(5) produced in a pyrolytic source from the C(2)H(5)NO(2) precursor, and ionized by the VUV beam of the DESIRS beamline at SOLEIL synchrotron facility. In this latter experiment, a recently developed ion imaging technique is used to discriminate the direct photoionization process from dissociative ionization contributions to the C(2)H(5)(+) signal. The imaging technique applied on the photoelectron signal also allows a slow photoelectron spectrum with a 40 meV resolution to be extracted, indicating that photoionization around the adiabatic ionization threshold involves a complex vibrational overlap between the neutral and cationic ground states, as was previously observed in the literature. Comparison with earlier photoionization studies, in particular with the photoionization yield recorded by Ruscic et al. is also discussed. © 2011 American Chemical Society

  5. Variance computations for functional of absolute risk estimates.

    PubMed

    Pfeiffer, R M; Petracci, E

    2011-07-01

    We present a simple influence function based approach to compute the variances of estimates of absolute risk and functions of absolute risk. We apply this approach to criteria that assess the impact of changes in the risk factor distribution on absolute risk for an individual and at the population level. As an illustration we use an absolute risk prediction model for breast cancer that includes modifiable risk factors in addition to standard breast cancer risk factors. Influence function based variance estimates for absolute risk and the criteria are compared to bootstrap variance estimates.

  6. Variance computations for functional of absolute risk estimates

    PubMed Central

    Pfeiffer, R.M.; Petracci, E.

    2011-01-01

    We present a simple influence function based approach to compute the variances of estimates of absolute risk and functions of absolute risk. We apply this approach to criteria that assess the impact of changes in the risk factor distribution on absolute risk for an individual and at the population level. As an illustration we use an absolute risk prediction model for breast cancer that includes modifiable risk factors in addition to standard breast cancer risk factors. Influence function based variance estimates for absolute risk and the criteria are compared to bootstrap variance estimates. PMID:21643476

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  8. 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…

  9. 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.

  10. 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.

  11. Manual choice reaction times in the rate-domain

    PubMed Central

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

    2014-01-01

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

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

    PubMed

    Yang, Mino

    2007-06-07

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

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

    PubMed

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

    2017-07-06

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

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

    NASA Astrophysics Data System (ADS)

    Shizgal, Bernie D.; Chikhaoui, Aziz

    2006-06-01

    The present paper considers a detailed analysis of the nonequilibrium effects for a model reactive system with the Chapman-Eskog (CE) solution of the Boltzmann equation as well as an explicit time dependent solution. The elastic cross sections employed are a hard sphere cross section and the Maxwell molecule cross section. Reactive cross sections which model reactions with and without activation energy are used. A detailed comparison is carried out with these solutions of the Boltzmann equation and the approximation introduced by Cukrowski and coworkers [J. Chem. Phys. 97 (1992) 9086; Chem. Phys. 89 (1992) 159; Physica A 188 (1992) 344; Chem. Phys. Lett. A 297 (1998) 402; Physica A 275 (2000) 134; Chem. Phys. Lett. 341 (2001) 585; Acta Phys. Polonica B 334 (2003) 3607.] based on the temperature of the reactive particles. We show that the Cukrowski approximation has limited applicability for the large class of reactive systems studied in this paper. The explicit time dependent solutions of the Boltzmann equation demonstrate that the CE approach is valid only for very slow reactions for which the corrections to the equilibrium rate coefficient are very small.

  15. Direct and inverse reactions of LiH+ with He(1S) from quantum calculations: mechanisms and rates.

    PubMed

    Tacconi, M; Bovino, S; Gianturco, F A

    2012-01-14

    The gas-phase reaction of LiH(+) (X(2)Σ) with He((1)S) atoms, yielding Li(+)He with a small endothermicity for the rotovibrational ground state of the reagents, is analysed using the quantum reactive approach that employs the Negative Imaginary Potential (NIP) scheme discussed earlier in the literature. The dependence of low-T rates on the initial vibrational state of LiH(+) is analysed and the role of low-energy Feshbach resonances is also discussed. The inverse destruction reaction of LiHe(+), a markedly exothermic process, is also investigated and the rates are computed in the same range of temperatures. The possible roles of these reactions in early universe astrophysical networks, in He droplets environments or in cold traps are briefly discussed.

  16. Absolute Summ

    NASA Astrophysics Data System (ADS)

    Phillips, Alfred, Jr.

    Summ means the entirety of the multiverse. It seems clear, from the inflation theories of A. Guth and others, that the creation of many universes is plausible. We argue that Absolute cosmological ideas, not unlike those of I. Newton, may be consistent with dynamic multiverse creations. As suggested in W. Heisenberg's uncertainty principle, and with the Anthropic Principle defended by S. Hawking, et al., human consciousness, buttressed by findings of neuroscience, may have to be considered in our models. Predictability, as A. Einstein realized with Invariants and General Relativity, may be required for new ideas to be part of physics. We present here a two postulate model geared to an Absolute Summ. The seedbed of this work is part of Akhnaton's philosophy (see S. Freud, Moses and Monotheism). Most important, however, is that the structure of human consciousness, manifest in Kenya's Rift Valley 200,000 years ago as Homo sapiens, who were the culmination of the six million year co-creation process of Hominins and Nature in Africa, allows us to do the physics that we do. .

  17. Reaction Event Counting Statistics of Biopolymer Reaction Systems with Dynamic Heterogeneity.

    PubMed

    Lim, Yu Rim; Park, Seong Jun; Park, Bo Jung; Cao, Jianshu; Silbey, Robert J; Sung, Jaeyoung

    2012-04-10

    We investigate the reaction event counting statistics (RECS) of an elementary biopolymer reaction in which the rate coefficient is dependent on states of the biopolymer and the surrounding environment and discover a universal kinetic phase transition in the RECS of the reaction system with dynamic heterogeneity. From an exact analysis for a general model of elementary biopolymer reactions, we find that the variance in the number of reaction events is dependent on the square of the mean number of the reaction events when the size of measurement time is small on the relaxation time scale of rate coefficient fluctuations, which does not conform to renewal statistics. On the other hand, when the size of the measurement time interval is much greater than the relaxation time of rate coefficient fluctuations, the variance becomes linearly proportional to the mean reaction number in accordance with renewal statistics. Gillespie's stochastic simulation method is generalized for the reaction system with a rate coefficient fluctuation. The simulation results confirm the correctness of the analytic results for the time dependent mean and variance of the reaction event number distribution. On the basis of the obtained results, we propose a method of quantitative analysis for the reaction event counting statistics of reaction systems with rate coefficient fluctuations, which enables one to extract information about the magnitude and the relaxation times of the fluctuating reaction rate coefficient, without a bias that can be introduced by assuming a particular kinetic model of conformational dynamics and the conformation dependent reactivity. An exact relationship is established between a higher moment of the reaction event number distribution and the multitime correlation of the reaction rate for the reaction system with a nonequilibrium initial state distribution as well as for the system with the equilibrium initial state distribution.

  18. Self-digitization microfluidic chip for absolute quantification of mRNA in single cells.

    PubMed

    Thompson, Alison M; Gansen, Alexander; Paguirigan, Amy L; Kreutz, Jason E; Radich, Jerald P; Chiu, Daniel T

    2014-12-16

    Quantification of mRNA in single cells provides direct insight into how intercellular heterogeneity plays a role in disease progression and outcomes. Quantitative polymerase chain reaction (qPCR), the current gold standard for evaluating gene expression, is insufficient for providing absolute measurement of single-cell mRNA transcript abundance. Challenges include difficulties in handling small sample volumes and the high variability in measurements. Microfluidic digital PCR provides far better sensitivity for minute quantities of genetic material, but the typical format of this assay does not allow for counting of the absolute number of mRNA transcripts samples taken from single cells. Furthermore, a large fraction of the sample is often lost during sample handling in microfluidic digital PCR. Here, we report the absolute quantification of single-cell mRNA transcripts by digital, one-step reverse transcription PCR in a simple microfluidic array device called the self-digitization (SD) chip. By performing the reverse transcription step in digitized volumes, we find that the assay exhibits a linear signal across a wide range of total RNA concentrations and agrees well with standard curve qPCR. The SD chip is found to digitize a high percentage (86.7%) of the sample for single-cell experiments. Moreover, quantification of transferrin receptor mRNA in single cells agrees well with single-molecule fluorescence in situ hybridization experiments. The SD platform for absolute quantification of single-cell mRNA can be optimized for other genes and may be useful as an independent control method for the validation of mRNA quantification techniques.

  19. The effects of finite-rate reactions at the gas/surface interface in support of thermal protection system design

    NASA Astrophysics Data System (ADS)

    Beerman, Adam Farrell

    2011-12-01

    Gas-surface modeling is dependent on material type and atmospheric reentry conditions. Lower molecular collisions at the low pressure trajectories make it more likely for occurrences of nonequilibrium, or finite-rate, reactions. Equilibrium is often assumed at the surface of a material as it is a subset of nonequilibrium and is easier to compute, though it can lead to overly conservative predictions. A case where a low density material experiences a low pressure trajectory and designed for equilibrium is the Stardust Return Capsule (SRC) with the Phenolic Impregnated Carbon Ablator (PICA) as its heatshield. Post-flight analysis of the recession on the SRC found that the prediction from the equilibrium model can be more than 50% larger than the measured recession. The Modified Park Model was chosen as the finite-rate model as it contains simple four reactions (oxidation, sublimation, and nitridation) and has been previously used to study individual points of the SRC trajectory. The Modified Park Model cannot model equilibrium so a model BFIAT was developed that allows finite-rate reactions to be applied to the surface for a certain length of time. Finite-rate sublimation was determined to be reaction of importance in the Park Model for SRC-like conditions. The predicted recession on the SRC heatshield experienced a reduction in its overprediction; the finite-rate predictions fall with the measurement error of the recession at three points on the heatshield. The recession reduction was driven by a significant reduction in char formation. There was little change in the pyrolysis gas rate. The finite-rate model was also applied to simulations of various arc-jet tests that covered a range of heating conditions on the surface of the PICA material. Comparison to this experimental data further showed the role of finite-rate reactions and sublimation in the Park Model and conditions that favor the nonequilibrium assumption (heating over 1000 W/cm2). For the emerging PICA

  20. Measurement of the 2H(7Be, 6Li)3He reaction rate and its contribution to the primordial lithium abundance

    NASA Astrophysics Data System (ADS)

    Li, Er-Tao; Li, Zhi-Hong; Yan, Sheng-Quan; Su, Jun; Guo, Bing; Li, Yun-Ju; Wang, You-Bao; Lian, Gang; Zeng, Sheng; Chen, Si-Zhe; Ma, Shao-Bo; Li, Xiang-Qing; He, Cao; Sun, Hui-Bin; Liu, Wei-Ping

    2018-04-01

    In the standard Big Bang nucleosynthesis (SBBN) model, the lithium puzzle has attracted intense interest over the past few decades, but still has not been solved. Conventionally, the approach is to include more reactions flowing into or out of lithium, and study the potential effects of those reactions which were not previously considered. 7Be(d, 3He)6Li is a reaction that not only produces 6Li but also destroys 7Be, which decays to 7Li, thereby affecting 7Li indirectly. Therefore, this reaction could alleviate the lithium discrepancy if its reaction rate is sufficiently high. However, there is not much information available about the 7Be(d, 3He)6Li reaction rate. In this work, the angular distributions of the 7Be(d, 3He)6Li reaction are measured at the center of mass energies E cm = 4.0 MeV and 6.7 MeV with secondary 7Be beams for the first time. The excitation function of the 7Be(d, 3He)6Li reaction is first calculated with the computer code TALYS and then normalized to the experimental data, then its reaction rate is deduced. A SBBN network calculation is performed to investigate its influence on the 6Li and 7Li abundances. The results show that the 7Be(d, 3He)6Li reaction has a minimal effect on 6Li and 7Li because of its small reaction rate. Therefore, the 7Be(d, 3He)6Li reaction is ruled out by this experiment as a means of alleviating the lithium discrepancy. Supported by National Natural Science Foundation of China (11375269, 11505117, 11490560, 11475264, 11321064), Natural Science Foundation of Guangdong Province (2015A030310012), 973 program of China (2013CB834406) and National key Research and Development Province (2016YFA0400502)

  1. Absolute optical metrology : nanometers to kilometers

    NASA Technical Reports Server (NTRS)

    Dubovitsky, Serge; Lay, O. P.; Peters, R. D.; Liebe, C. C.

    2005-01-01

    We provide and overview of the developments in the field of high-accuracy absolute optical metrology with emphasis on space-based applications. Specific work on the Modulation Sideband Technology for Absolute Ranging (MSTAR) sensor is described along with novel applications of the sensor.

  2. 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

  3. 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.

  4. A rare gas optics-free absolute photon flux and energy analyzer to provide absolute photoionization rates of inflowing interstellar neutrals

    NASA Technical Reports Server (NTRS)

    Judge, Darrell L.

    1994-01-01

    A prototype spectrometer has been developed for space applications requiring long term absolute EUV photon flux measurements. The energy spectrum of the incoming photons is transformed directly into an electron energy spectrum by taking advantage of the photoelectric effect in one of several rare gases at low pressures. Using an electron energy spectrometer, followed by an electron multiplier detector, pulses due to individual electrons are counted. The overall efficiency of this process can be made essentially independent of gain drifts in the signal path, and the secular degradation of optical components which is often a problem in other techniques is avoided. A very important feature of this approach is its freedom from the problem of overlapping spectral orders that plagues grating EUV spectrometers. An instrument with these features has not been flown before, but is essential to further advances in our understanding of solar EUV flux dynamics, and the coupled dynamics of terrestrial and planetary atmospheres. The detailed characteristics of this optics-free spectrometer are presented in the publications section.

  5. 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.

    1986-01-01

    A computationally-viable model describing the interaction between fluid-mechanical turbulence and finite-rate combustion reactions, principally in high-speed flows was developed. Chemical kinetic mechanisms, complete and global, were developed describing the finite rate reaction of fuels of interest to NASA. These fuels included principally hydrogen and silane, although a limited amount of work involved hydrocarbon fuels as well.

  6. Gender equality and women's absolute status: a test of the feminist models of rape.

    PubMed

    Martin, Kimberly; Vieraitis, Lynne M; Britto, Sarah

    2006-04-01

    Feminist theory predicts both a positive and negative relationship between gender equality and rape rates. Although liberal and radical feminist theory predicts that gender equality should ameliorate rape victimization, radical feminist theorists have argued that gender equality may increase rape in the form of male backlash. Alternatively, Marxist criminologists focus on women's absolute socioeconomic status rather than gender equality as a predictor of rape rates, whereas socialist feminists combine both radical and Marxist perspectives. This study uses factor analysis to overcome multicollinearity limitations of past studies while exploring the relationship between women's absolute and relative socioeconomic status on rape rates in major U.S. cities using 2000 census data. The findings indicate support for both the Marxist and radical feminist explanations of rape but no support for the ameliorative hypothesis. These findings support a more inclusive socialist feminist theory that takes both Marxist and radical feminist hypotheses into account.

  7. Entrenched geographical and socioeconomic disparities in child mortality: trends in absolute and relative inequalities in Cambodia.

    PubMed

    Jimenez-Soto, Eliana; Durham, Jo; Hodge, Andrew

    2014-01-01

    Cambodia has made considerable improvements in mortality rates for children under the age of five and neonates. These improvements may, however, mask considerable disparities between subnational populations. In this paper, we examine the extent of the country's child mortality inequalities. Mortality rates for children under-five and neonates were directly estimated using the 2000, 2005 and 2010 waves of the Cambodian Demographic Health Survey. Disparities were measured on both absolute and relative scales using rate differences and ratios, and where applicable, slope and relative indices of inequality by levels of rural/urban location, regions and household wealth. Since 2000, considerable reductions in under-five and to a lesser extent in neonatal mortality rates have been observed. This mortality decline has, however, been accompanied by an increase in relative inequality in both rates of child mortality for geography-related stratifying markers. For absolute inequality amongst regions, most trends are increasing, particularly for neonatal mortality, but are not statistically significant. The only exception to this general pattern is the statistically significant positive trend in absolute inequality for under-five mortality in the Coastal region. For wealth, some evidence for increases in both relative and absolute inequality for neonates is observed. Despite considerable gains in reducing under-five and neonatal mortality at a national level, entrenched and increased geographical and wealth-based inequality in mortality, at least on a relative scale, remain. As expected, national progress seems to be associated with the period of political and macroeconomic stability that started in the early 2000s. However, issues of quality of care and potential non-inclusive economic growth might explain remaining disparities, particularly across wealth and geography markers. A focus on further addressing key supply and demand side barriers to accessing maternal and child

  8. Atmospheric reactions of methylcyclohexanes with Cl atoms and OH radicals: determination of rate coefficients and degradation products.

    PubMed

    Ballesteros, Bernabé; Ceacero-Vega, Antonio A; Jiménez, Elena; Albaladejo, José

    2015-04-01

    As the result of biogenic and anthropogenic activities, large quantities of chemical compounds are emitted into the troposphere. Alkanes, in general, and cycloalkanes are an important chemical class of hydrocarbons found in diesel, jet and gasoline, vehicle exhaust emissions, and ambient air in urban areas. In general, the primary atmospheric fate of organic compounds in the gas phase is the reaction with hydroxyl radicals (OH). The oxidation by Cl atoms has gained importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments, and in the Arctic troposphere. The aim of this paper is to study of the atmospheric reactivity of methylcylohexanes with Cl atoms and OH radicals under atmospheric conditions (in air at room temperature and pressure). Relative kinetic techniques have been used to determine the rate coefficients for the reaction of Cl atoms and OH radicals with methylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,4-dimethylcyclohexane, and 1,3,5-trimethylcyclohexane at 298 ± 2 K and 720 ± 5 Torr of air by Fourier transform infrared) spectroscopy and gas chromatography-mass spectrometry (GC-MS) in two atmospheric simulation chambers. The products formed in the reaction under atmospheric conditions were investigated using a 200-L Teflon bag and employing the technique of solid-phase microextraction coupled to a GC-MS. The rate coefficients obtained for the reaction of Cl atoms with the studied compounds are the following ones (in units of 10(-10) cm(3) molecule(-1) s(-1)): (3.11 ± 0.16), (2.89 ± 0.16), (2.89 ± 0.26), and (2.61 ± 0.42), respectively. For the reactions with OH radicals the determined rate coefficients are (in units of 10(-11) cm(3) molecule(-1) s(-1)): (1.18 ± 0.12), (1.49 ± 0.16), (1.41 ± 0.15), and (1.77 ± 0.23), respectively. The reported error is twice the standard deviation. A detailed

  9. A global algorithm for estimating Absolute Salinity

    NASA Astrophysics Data System (ADS)

    McDougall, T. J.; Jackett, D. R.; Millero, F. J.; Pawlowicz, R.; Barker, P. M.

    2012-12-01

    The International Thermodynamic Equation of Seawater - 2010 has defined the thermodynamic properties of seawater in terms of a new salinity variable, Absolute Salinity, which takes into account the spatial variation of the composition of seawater. Absolute Salinity more accurately reflects the effects of the dissolved material in seawater on the thermodynamic properties (particularly density) than does Practical Salinity. When a seawater sample has standard composition (i.e. the ratios of the constituents of sea salt are the same as those of surface water of the North Atlantic), Practical Salinity can be used to accurately evaluate the thermodynamic properties of seawater. When seawater is not of standard composition, Practical Salinity alone is not sufficient and the Absolute Salinity Anomaly needs to be estimated; this anomaly is as large as 0.025 g kg-1 in the northernmost North Pacific. Here we provide an algorithm for estimating Absolute Salinity Anomaly for any location (x, y, p) in the world ocean. To develop this algorithm, we used the Absolute Salinity Anomaly that is found by comparing the density calculated from Practical Salinity to the density measured in the laboratory. These estimates of Absolute Salinity Anomaly however are limited to the number of available observations (namely 811). In order to provide a practical method that can be used at any location in the world ocean, we take advantage of approximate relationships between Absolute Salinity Anomaly and silicate concentrations (which are available globally).

  10. Benchmark experiments at ASTRA facility on definition of space distribution of {sup 235}U fission reaction rate

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

    Bobrov, A. A.; Boyarinov, V. F.; Glushkov, A. E.

    2012-07-01

    Results of critical experiments performed at five ASTRA facility configurations modeling the high-temperature helium-cooled graphite-moderated reactors are presented. Results of experiments on definition of space distribution of {sup 235}U fission reaction rate performed at four from these five configurations are presented more detail. Analysis of available information showed that all experiments on criticality at these five configurations are acceptable for use them as critical benchmark experiments. All experiments on definition of space distribution of {sup 235}U fission reaction rate are acceptable for use them as physical benchmark experiments. (authors)

  11. Zero absolute vorticity: insight from experiments in rotating laminar plane Couette flow.

    PubMed

    Suryadi, Alexandre; Segalini, Antonio; Alfredsson, P Henrik

    2014-03-01

    For pressure-driven turbulent channel flows undergoing spanwise system rotation, it has been observed that the absolute vorticity, i.e., the sum of the averaged spanwise flow vorticity and system rotation, tends to zero in the central region of the channel. This observation has so far eluded a convincing theoretical explanation, despite experimental and numerical evidence reported in the literature. Here we show experimentally that three-dimensional laminar structures in plane Couette flow, which appear under anticyclonic system rotation, give the same effect, namely, that the absolute vorticity tends to zero if the rotation rate is high enough. It is shown that this is equivalent to a local Richardson number of approximately zero, which would indicate a stable condition. We also offer an explanation based on Kelvin's circulation theorem to demonstrate that the absolute vorticity should remain constant and approximately equal to zero in the central region of the channel when going from the nonrotating fully turbulent state to any state with sufficiently high rotation.

  12. Nuclear Data and Reaction Rate Databases in Nuclear Astrophysics

    NASA Astrophysics Data System (ADS)

    Lippuner, Jonas

    2018-06-01

    Astrophysical simulations and models require a large variety of micro-physics data, such as equation of state tables, atomic opacities, properties of nuclei, and nuclear reaction rates. Some of the required data is experimentally accessible, but the extreme conditions present in many astrophysical scenarios cannot be reproduced in the laboratory and thus theoretical models are needed to supplement the empirical data. Collecting data from various sources and making them available as a database in a unified format is a formidable task. I will provide an overview of the data requirements in astrophysics with an emphasis on nuclear astrophysics. I will then discuss some of the existing databases, the science they enable, and their limitations. Finally, I will offer some thoughts on how to design a useful database.

  13. Absolute instability of the Gaussian wake profile

    NASA Technical Reports Server (NTRS)

    Hultgren, Lennart S.; Aggarwal, Arun K.

    1987-01-01

    Linear parallel-flow stability theory has been used to investigate the effect of viscosity on the local absolute instability of a family of wake profiles with a Gaussian velocity distribution. The type of local instability, i.e., convective or absolute, is determined by the location of a branch-point singularity with zero group velocity of the complex dispersion relation for the instability waves. The effects of viscosity were found to be weak for values of the wake Reynolds number, based on the center-line velocity defect and the wake half-width, larger than about 400. Absolute instability occurs only for sufficiently large values of the center-line wake defect. The critical value of this parameter increases with decreasing wake Reynolds number, thereby indicating a shrinking region of absolute instability with decreasing wake Reynolds number. If backflow is not allowed, absolute instability does not occur for wake Reynolds numbers smaller than about 38.

  14. Kinetics of the creatine kinase reaction in neonatal rabbit heart: An empirical analysis of the rate equation

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

    McAuliffe, J.J.; Perry, S.B.; Brooks, E.E.

    1991-03-12

    Here the authors define the kinetics of the creatine kinase (CK) reaction in an intact mammalian heart containing the full rnage of CK isoenzymes. Previously derived kinetic constants were refit for the reaction occurring at 37C. Steady-state metabolite concentrations from {sup 31}P NMR and standard biochemical techniques were determined. {sup 31}P magnetization transfer data were obtained to determine unidirectional creatine kinase fluxes in hearts with differing total creatine contents and differing mitochondrial CK activities during KCl arrest and isovolumic work for both the forward reaction (MgATP synthesis) and reverse reaction (phosphocreatine synthesis). The NMR kinetic data and substrate concentrations datamore » were used in conjunction with a kinetic model based on MM-CK in solution to determine the applicability of the solution-based kinetic models to the CK kinetics of the intact heart. The results indicated that no single set of rate equation constants could describe both the KCl-arrested and working hearts. Analysis of the results indicated that the CK reaction is rate limited in the direction of ATP synthesis, the size of the guanidino substrate pool drives the measured CK flux in the intact heart, and during isovolumic work, the CK reaction operates under saturating conditions; that is, the substrate concentrations are at least 2-fold greater than the K{sub m} or K{sub im} for each substrate. However, during KCl arrest the reaction does not operate under saturating conditions and the CK reaction velocity is strongly influenced by the guanidino substrate pool size.« less

  15. α -unbound levels in 34Ar from 36Ar(p ,t )34Ar reaction measurements and implications for the astrophysical 30S(α ,p )33Cl reaction rate

    NASA Astrophysics Data System (ADS)

    Long, A. M.; Adachi, T.; Beard, M.; Berg, G. P. A.; Couder, M.; deBoer, R. J.; Dozono, M.; Görres, J.; Fujita, H.; Fujita, Y.; Hatanaka, K.; Ishikawa, D.; Kubo, T.; Matsubara, H.; Namiki, Y.; O'Brien, S.; Ohkuma, Y.; Okamura, H.; Ong, H. J.; Patel, D.; Sakemi, Y.; Shimbara, Y.; Suzuki, S.; Talwar, R.; Tamii, A.; Volya, A.; Wakasa, T.; Watanabe, R.; Wiescher, M.; Yamada, R.; Zenihiro, J.

    2018-05-01

    The 30S(α ,p )33Cl reaction has been identified in several type-1 x-ray burst (XRB) sensitivity studies as a significant reaction within the α p process, possibly influencing not only the abundances of burst ashes but also the bolometric shape of double-peaked light curves coming from certain XRB systems. Given the dearth of experimental data on the 30S(α ,p ) 33Cl reaction at burst temperatures, we have performed high energy-resolution forward-angle 36Ar(p ,t )34Ar measurements in order to identify levels in 34Ar that could appear as resonances in the 30S(α ,p )33Cl reaction. Energies of levels identified in this work, along with model-based assumptions for spin assignments and spectroscopic factors, were then used to determine a rate for the 30S(α ,p )33Cl reaction based on a narrow-resonance formalism. The rates determined in this work are then compared with two standard Hauser-Feshbach model predictions over a range of XRB temperatures.

  16. 49 CFR 236.709 - Block, absolute.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 4 2010-10-01 2010-10-01 false Block, absolute. 236.709 Section 236.709 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... Block, absolute. A block in which no train is permitted to enter while it is occupied by another train. ...

  17. 49 CFR 236.709 - Block, absolute.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 4 2011-10-01 2011-10-01 false Block, absolute. 236.709 Section 236.709 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... Block, absolute. A block in which no train is permitted to enter while it is occupied by another train. ...

  18. Absolute quantification of microbial taxon abundances.

    PubMed

    Props, Ruben; Kerckhof, Frederiek-Maarten; Rubbens, Peter; De Vrieze, Jo; Hernandez Sanabria, Emma; Waegeman, Willem; Monsieurs, Pieter; Hammes, Frederik; Boon, Nico

    2017-02-01

    High-throughput amplicon sequencing has become a well-established approach for microbial community profiling. Correlating shifts in the relative abundances of bacterial taxa with environmental gradients is the goal of many microbiome surveys. As the abundances generated by this technology are semi-quantitative by definition, the observed dynamics may not accurately reflect those of the actual taxon densities. We combined the sequencing approach (16S rRNA gene) with robust single-cell enumeration technologies (flow cytometry) to quantify the absolute taxon abundances. A detailed longitudinal analysis of the absolute abundances resulted in distinct abundance profiles that were less ambiguous and expressed in units that can be directly compared across studies. We further provide evidence that the enrichment of taxa (increase in relative abundance) does not necessarily relate to the outgrowth of taxa (increase in absolute abundance). Our results highlight that both relative and absolute abundances should be considered for a comprehensive biological interpretation of microbiome surveys.

  19. (CH3)3COOH (tert-butyl hydroperoxide): OH reaction rate coefficients between 206 and 375 K and the OH photolysis quantum yield at 248 nm.

    PubMed

    Baasandorj, Munkhbayar; Papanastasiou, Dimitrios K; Talukdar, Ranajit K; Hasson, Alam S; Burkholder, James B

    2010-10-14

    Rate coefficients, k, for the gas-phase reaction of the OH radical with (CH(3))(3)COOH (tert-butyl hydroperoxide) were measured as a function of temperature (206-375 K) and pressure (25-200 Torr (He, N(2))). Rate coefficients were measured under pseudo-first-order conditions using pulsed laser photolysis to produce OH and laser induced fluorescence (PLP-LIF) to measure the OH temporal profile. Two independent methods were used to determine the gas-phase infrared cross sections of (CH(3))(3)COOH, absolute pressure and chemical titration, that were used to determine the (CH(3))(3)COOH concentration in the LIF reactor. The temperature dependence of the rate coefficients is described, within the measurement precision, by the Arrhenius expression k(1)(T) = (7.0 ± 1.0) × 10(-13) exp[(485 ± 20)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (3.58 ± 0.54) × 10(-12) cm(3) molecule(-1) s(-1). The uncertainties are 2σ (95% confidence level) and include estimated systematic errors. UV absorption cross sections of (CH(3))(3)COOH were determined at 185, 214, 228, and 254 nm and over the wavelength range 210-300 nm. The OH quantum yield following the 248 nm pulsed laser photolysis of (CH(3))(3)COOH was measured relative to the OH quantum yields of H(2)O(2) and HNO(3) using PLP-LIF and found to be near unity.

  20. Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)

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

    B. J. Mincher; S. K. Cole; W. J. Cooper

    2007-02-01

    Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance ofmore » the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.« less

  1. Reaction rates of α-tocopheroxyl radicals confined in micelles and in human plasma lipoproteins.

    PubMed

    Vanzani, Paola; Rigo, Adelio; Zennaro, Lucio; Di Paolo, Maria Luisa; Scarpa, Marina; Rossetto, Monica

    2014-08-01

    α-Tocopherol, the main component of vitamin E, traps highly reactive radicals which otherwise might react with lipids present in plasmatic lipoproteins or in cell membranes. The α-tocopheroxyl radicals generated by this process have also a pro-oxidant action which is contrasted by their reaction with ascorbate or by bimolecular self-reaction (dismutation). The kinetics of this bimolecular self-reaction were explored in solution such as ethanol, and in heterogeneous systems such as deoxycholic acid micelles and in human plasma. According to ESR measurements, the kinetic rate constant (2k(d)) of the bimolecular self-reaction of α-tocopheroxyl radicals in micelles and in human plasma was calculated to be of the order of 10(5) M(-1) s(-1) at 37 °C. This value was obtained considering that the reactive radicals are confined into the micellar pseudophase and is one to two orders of magnitude higher than the value we found in homogeneous phase. The physiological significance of this high value is discussed considering the competition between bimolecular self-reaction and the α-tocopheroxyl radical recycling by ascorbate. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Absolute cross-sections for DNA strand breaks and crosslinks induced by low energy electrons

    PubMed Central

    Chen, Wenzhuang; Chen, Shiliang; Dong, Yanfang; Cloutier, Pierre; Sanche, Léon

    2016-01-01

    Absolute cross sections (CSs) for the interaction of low energy electrons with condensed macromolecules are essential parameters to accurately model ionizing radiation induced reactions. To determine CSs for various conformational DNA damage induced by 2–20 eV electrons, we investigated the influence of the attenuation length (AL) and penetration factor (f) using a mathematical model. Solid films of super-coiled plasmid DNA with thicknesses of 10, 15 and 20 nm were irradiated with 4.6, 5.6, 9.6 and 14.6 eV electrons. DNA conformational changes were quantified by gel electrophoresis, and the respective yields were extrapolated from exposure–response curves. The absolute CS, AL and f values were generated by applying the model developed by Rezaee et al. The values of AL were found to lie between 11 and 16 nm with the maximum at 14.6 eV. The absolute CSs for the loss of the supercoiled (LS) configuration and production of crosslinks (CL), single strand breaks (SSB) and double strand breaks (DSB) induced by 4.6, 5.6, 9.6 and 14.6 eV electrons are obtained. The CSs for SSB are smaller, but similar to those for LS, indicating that SSB are the main conformational damage. The CSs for DSB and CL are about one order of magnitude smaller than those of LS and SSB. The value of f is found to be independent of electron energy, which allows extending the absolute CSs for these types of damage within the range 2–20 eV, from previous measurements of effective CSs. When comparison is possible, the absolute CSs are found to be in good agreement with those obtained from previous similar studies with double-stranded DNA. The high values of the absolute CSs of 4.6 and 9.6 eV provide quantitative evidence for the high efficiency of low energy electrons to induce DNA damage via the formation of transient anions. PMID:27878170

  3. Absolute cross-sections for DNA strand breaks and crosslinks induced by low energy electrons.

    PubMed

    Chen, Wenzhuang; Chen, Shiliang; Dong, Yanfang; Cloutier, Pierre; Zheng, Yi; Sanche, Léon

    2016-12-07

    Absolute cross sections (CSs) for the interaction of low energy electrons with condensed macromolecules are essential parameters to accurately model ionizing radiation induced reactions. To determine CSs for various conformational DNA damage induced by 2-20 eV electrons, we investigated the influence of the attenuation length (AL) and penetration factor (f) using a mathematical model. Solid films of supercoiled plasmid DNA with thicknesses of 10, 15 and 20 nm were irradiated with 4.6, 5.6, 9.6 and 14.6 eV electrons. DNA conformational changes were quantified by gel electrophoresis, and the respective yields were extrapolated from exposure-response curves. The absolute CS, AL and f values were generated by applying the model developed by Rezaee et al. The values of AL were found to lie between 11 and 16 nm with the maximum at 14.6 eV. The absolute CSs for the loss of the supercoiled (LS) configuration and production of crosslinks (CL), single strand breaks (SSB) and double strand breaks (DSB) induced by 4.6, 5.6, 9.6 and 14.6 eV electrons are obtained. The CSs for SSB are smaller, but similar to those for LS, indicating that SSB are the main conformational damage. The CSs for DSB and CL are about one order of magnitude smaller than those of LS and SSB. The value of f is found to be independent of electron energy, which allows extending the absolute CSs for these types of damage within the range 2-20 eV, from previous measurements of effective CSs. When comparison is possible, the absolute CSs are found to be in good agreement with those obtained from previous similar studies with double-stranded DNA. The high values of the absolute CSs of 4.6 and 9.6 eV provide quantitative evidence for the high efficiency of low energy electrons to induce DNA damage via the formation of transient anions.

  4. Fractional order absolute vibration suppression (AVS) controllers

    NASA Astrophysics Data System (ADS)

    Halevi, Yoram

    2017-04-01

    Absolute vibration suppression (AVS) is a control method for flexible structures. The first step is an accurate, infinite dimension, transfer function (TF), from actuation to measurement. This leads to the collocated, rate feedback AVS controller that in some cases completely eliminates the vibration. In case of the 1D wave equation, the TF consists of pure time delays and low order rational terms, and the AVS controller is rational. In all other cases, the TF and consequently the controller are fractional order in both the delays and the "rational parts". The paper considers stability, performance and actual implementation in such cases.

  5. 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.

  6. Absolute Quantification of Selected Proteins in the Human Osteoarthritic Secretome

    PubMed Central

    Peffers, Mandy J.; Beynon, Robert J.; Clegg, Peter D.

    2013-01-01

    Osteoarthritis (OA) is characterized by a loss of extracellular matrix which is driven by catabolic cytokines. Proteomic analysis of the OA cartilage secretome enables the global study of secreted proteins. These are an important class of molecules with roles in numerous pathological mechanisms. Although cartilage studies have identified profiles of secreted proteins, quantitative proteomics techniques have been implemented that would enable further biological questions to be addressed. To overcome this limitation, we used the secretome from human OA cartilage explants stimulated with IL-1β and compared proteins released into the media using a label-free LC-MS/MS-based strategy. We employed QconCAT technology to quantify specific proteins using selected reaction monitoring. A total of 252 proteins were identified, nine were differentially expressed by IL-1 β stimulation. Selected protein candidates were quantified in absolute amounts using QconCAT. These findings confirmed a significant reduction in TIMP-1 in the secretome following IL-1β stimulation. Label-free and QconCAT analysis produced equivocal results indicating no effect of cytokine stimulation on aggrecan, cartilage oligomeric matrix protein, fibromodulin, matrix metalloproteinases 1 and 3 or plasminogen release. This study enabled comparative protein profiling and absolute quantification of proteins involved in molecular pathways pertinent to understanding the pathogenesis of OA. PMID:24132152

  7. Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Zero Point Energy Conservation in Mu + H2 → MuH + H.

    PubMed

    Pérez de Tudela, Ricardo; Aoiz, F J; Suleimanov, Yury V; Manolopoulos, David E

    2012-02-16

    A fundamental issue in the field of reaction dynamics is the inclusion of the quantum mechanical (QM) effects such as zero point energy (ZPE) and tunneling in molecular dynamics simulations, and in particular in the calculation of chemical reaction rates. In this work we study the chemical reaction between a muonium atom and a hydrogen molecule. The recently developed ring polymer molecular dynamics (RPMD) technique is used, and the results are compared with those of other methods. For this reaction, the thermal rate coefficients calculated with RPMD are found to be in excellent agreement with the results of an accurate QM calculation. The very minor discrepancies are within the convergence error even at very low temperatures. This exceptionally good agreement can be attributed to the dominant role of ZPE in the reaction, which is accounted for extremely well by RPMD. Tunneling only plays a minor role in the reaction.

  8. Secondary Electron Emission From Solar Cell Coverslides And Its Effect On Absolute Vehicle Charging

    NASA Astrophysics Data System (ADS)

    Ferguson, Dale C.

    2011-10-01

    It has often been stated that earthed conductive solar cell coverslides are the best way to prevent electrostatic discharges on space solar arrays in GEO. While it is true that such coverslides will prevent differential charging on the solar arrays, it will be shown through NASCAP- 2k simulations that the secondary electron emission of such coverslides is very important for absolute vehicle charging. In particular, carbon nanotube coatings, due to the extremely low secondary electron emission from carbon, may exacerbate absolute vehicle charging. However, if they are earthed, because of their conductivity they may minimize differential charging and the possibility of arcing elsewhere on the spacecraft. Such results may also be true for insulative coverslides if spacecraft thermal blankets are made of materials with high secondary electron emission. Finally, photoemission from coverslides is investigated, with regard to anti-reflection coatings. Surfaces which reflect UV can have low photoemission, while those that absorb may have higher photoemission rates. Thus, anti-reflection coatings may lead to higher absolute spacecraft charging rates. NASCAP-2k simulations will be used to investigate these dependences for realistic spacecraft.

  9. Low absolute neutrophil counts in African infants.

    PubMed

    Kourtis, Athena P; Bramson, Brian; van der Horst, Charles; Kazembe, Peter; Ahmed, Yusuf; Chasela, Charles; Hosseinipour, Mina; Knight, Rodney; Lugalia, Lebah; Tegha, Gerald; Joaki, George; Jafali, Robert; Jamieson, Denise J

    2005-07-01

    Infants of African origin have a lower normal range of absolute neutrophil counts than white infants; this fact, however, remains under appreciated by clinical researchers in the United States. During the initial stages of a clinical trial in Malawi, the authors noted an unexpectedly high number of infants with absolute neutrophil counts that would be classifiable as neutropenic using the National Institutes of Health's Division of AIDS toxicity tables. The authors argue that the relevant Division of AIDS table does not take into account the available evidence of low absolute neutrophil counts in African infants and that a systematic collection of data from many African settings might help establish the absolute neutrophil count cutpoints to be used for defining neutropenia in African populations.

  10. Absolute colorimetric characterization of a DSLR camera

    NASA Astrophysics Data System (ADS)

    Guarnera, Giuseppe Claudio; Bianco, Simone; Schettini, Raimondo

    2014-03-01

    A simple but effective technique for absolute colorimetric camera characterization is proposed. It offers a large dynamic range requiring just a single, off-the-shelf target and a commonly available controllable light source for the characterization. The characterization task is broken down in two modules, respectively devoted to absolute luminance estimation and to colorimetric characterization matrix estimation. The characterized camera can be effectively used as a tele-colorimeter, giving an absolute estimation of the XYZ data in cd=m2. The user is only required to vary the f - number of the camera lens or the exposure time t, to better exploit the sensor dynamic range. The estimated absolute tristimulus values closely match the values measured by a professional spectro-radiometer.

  11. Reaction rates and kinetic isotope effects of H{sub 2} + OH → H{sub 2}O + H

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

    Meisner, Jan; Kästner, Johannes, E-mail: kaestner@theochem.uni-stuttgart.de

    2016-05-07

    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{sup −20} to 4 ⋅ 10{sup −17} cm{sup 3} s{sup −1}, demonstrating thatmore » 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.« less

  12. Upper limits to the reaction rate coefficients of C(n)(-) and C(n)H(-) (n = 2, 4, 6) with molecular hydrogen.

    PubMed

    Endres, Eric S; Lakhmanskaya, Olga; Hauser, Daniel; Huber, Stefan E; Best, Thorsten; Kumar, Sunil S; Probst, Michael; Wester, Roland

    2014-08-21

    In the interstellar medium (ISM) ion–molecule reactions play a key role in forming complex molecules. Since 2006, after the radioastronomical discovery of the first of by now six interstellar anions, interest has grown in understanding the formation and destruction pathways of negative ions in the ISM. Experiments have focused on reactions and photodetachment of the identified negatively charged ions. Hints were found that the reactions of CnH(–) with H2 may proceed with a low (<10(–13) cm(3) s(–1)), but finite rate [Eichelberger, B.; et al. Astrophys. J. 2007, 667, 1283]. Because of the high abundance of molecular hydrogen in the ISM, a precise knowledge of the reaction rate is needed for a better understanding of the low-temperature chemistry in the ISM. A suitable tool to analyze rare reactions is the 22-pole radiofrequency ion trap. Here, we report on reaction rates for Cn(–) and CnH(–) (n = 2, 4, 6) with buffer gas temperatures of H2 at 12 and 300 K. Our experiments show the absence of these reactions with an upper limit to the rate coefficients between 4 × 10(–16) and 5 × 10(–15) cm(3) s(–1), except for the case of C2(–), which does react with a finite rate with H2 at low temperatures. For the cases of C2H(–) and C4H(–), the experimental results were confirmed with quantum chemical calculations. In addition, the possible influence of a residual reactivity on the abundance of C4H(–) and C6H(–) in the ISM were estimated on the basis of a gas-phase chemical model based on the KIDA database. We found that the simulated ion abundances are already unaffected if reaction rate coefficients with H2 were below 10(–14) cm(3) s(–1).

  13. Automated Discovery of New Chemical Reactions and Accurate Calculation of Their Rates

    DTIC Science & Technology

    2015-06-02

    formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones . Phys. Chem. Chem. Phys. 2013, 15, 16841-16852. [39...dioxolan-3-ol – our second case study - we confirmed that fragmentation of the cyclic peroxide leads to two possible pairs of acid and aldehyde products...Rate Prediction via Group Additivity, Part 2: H-Abstraction from Alkenes, Alkynes, Alcohols, Aldehydes , and Acids by H Atoms. J. Phys. Chem. A 2001, 105

  14. Cryogenic, Absolute, High Pressure Sensor

    NASA Technical Reports Server (NTRS)

    Chapman, John J. (Inventor); Shams. Qamar A. (Inventor); Powers, William T. (Inventor)

    2001-01-01

    A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

  15. The chemistry of bromine in the stratosphere: Influence of a new rate constant for the reaction BrO + HO2

    NASA Technical Reports Server (NTRS)

    Pirre, Michel; Marceau, Francois J.; Lebras, Georges; Maguin, Francoise; Poulet, Gille; Ramaroson, Radiela

    1994-01-01

    The impact of new laboratory data for the reaction BrO + HO2 yields HOBr + O2 in the depletion of global stratospheric ozone has been estimated using a one-dimensional photochemical model taking into account the heterogeneous reaction on sulphate aerosols which converts N2O5 into HNO3. Assuring an aerosol loading 2 times as large as the 'background' and a reaction probability of 0.1 for the above heterogeneous reaction, the 6 fold increase in the measured rate constant for the reaction of BrO with HO2 increases the computed depletion of global ozone produced by 20 ppt of total bromine from 2.01 percent to 2.36 percent. The use of the higher rate constant increases the HOBr mixing ratio and makes the bromine partitioning and the ozone depletion very sensitive to the branching ratio of the potential channel forming HBr in the BrO + HO2 reaction.

  16. Absolute Income, Relative Income, and Happiness

    ERIC Educational Resources Information Center

    Ball, Richard; Chernova, Kateryna

    2008-01-01

    This paper uses data from the World Values Survey to investigate how an individual's self-reported happiness is related to (i) the level of her income in absolute terms, and (ii) the level of her income relative to other people in her country. The main findings are that (i) both absolute and relative income are positively and significantly…

  17. The effect of learning models and emotional intelligence toward students learning outcomes on reaction rate

    NASA Astrophysics Data System (ADS)

    Sutiani, Ani; Silitonga, Mei Y.

    2017-08-01

    This research focused on the effect of learning models and emotional intelligence in students' chemistry learning outcomes on reaction rate teaching topic. In order to achieve the objectives of the research, with 2x2 factorial research design was used. There were two factors tested, namely: the learning models (factor A), and emotional intelligence (factor B) factors. Then, two learning models were used; problem-based learning/PBL (A1), and project-based learning/PjBL (A2). While, the emotional intelligence was divided into higher and lower types. The number of population was six classes containing 243 grade X students of SMAN 10 Medan, Indonesia. There were 15 students of each class were chosen as the sample of the research by applying purposive sampling technique. The data were analyzed by applying two-ways analysis of variance (2X2) at the level of significant α = 0.05. Based on hypothesis testing, there was the interaction between learning models and emotional intelligence in students' chemistry learning outcomes. Then, the finding of the research showed that students' learning outcomes in reaction rate taught by using PBL with higher emotional intelligence is higher than those who were taught by using PjBL. There was no significant effect between students with lower emotional intelligence taught by using both PBL and PjBL in reaction rate topic. Based on the finding, the students with lower emotional intelligence were quite hard to get in touch with other students in group discussion.

  18. Universal Cosmic Absolute and Modern Science

    NASA Astrophysics Data System (ADS)

    Kostro, Ludwik

    The official Sciences, especially all natural sciences, respect in their researches the principle of methodic naturalism i.e. they consider all phenomena as entirely natural and therefore in their scientific explanations they do never adduce or cite supernatural entities and forces. The purpose of this paper is to show that Modern Science has its own self-existent, self-acting, and self-sufficient Natural All-in Being or Omni-Being i.e. the entire Nature as a Whole that justifies the scientific methodic naturalism. Since this Natural All-in Being is one and only It should be considered as the own scientifically justified Natural Absolute of Science and should be called, in my opinion, the Universal Cosmic Absolute of Modern Science. It will be also shown that the Universal Cosmic Absolute is ontologically enormously stratified and is in its ultimate i.e. in its most fundamental stratum trans-reistic and trans-personal. It means that in its basic stratum. It is neither a Thing or a Person although It contains in Itself all things and persons with all other sentient and conscious individuals as well, On the turn of the 20th century the Science has begun to look for a theory of everything, for a final theory, for a master theory. In my opinion the natural Universal Cosmic Absolute will constitute in such a theory the radical all penetrating Ultimate Basic Reality and will substitute step by step the traditional supernatural personal Absolute.

  19. 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.

  20. Theory and simulation of the time-dependent rate coefficients of diffusion-influenced reactions.

    PubMed Central

    Zhou, H X; Szabo, A

    1996-01-01

    A general formalism is developed for calculating the time-dependent rate coefficient k(t) of an irreversible diffusion-influenced reaction. This formalism allows one to treat most factors that affect k(t), including rotational Brownian motion and conformational gating of reactant molecules and orientation constraint for product formation. At long times k(t) is shown to have the asymptotic expansion k(infinity)[1 + k(infinity) (pie Dt)-1/2 /4 pie D + ...], where D is the relative translational diffusion constant. An approximate analytical method for calculating k(t) is presented. This is based on the approximation that the probability density of the reactant pair in the reactive region keeps the equilibrium distribution but with a decreasing amplitude. The rate coefficient then is determined by the Green function in the absence of chemical reaction. Within the framework of this approximation, two general relations are obtained. The first relation allows the rate coefficient for an arbitrary amplitude of the reactivity to be found if the rate coefficient for one amplitude of the reactivity is known. The second relation allows the rate coefficient in the presence of conformational gating to be found from that in the absence of conformational gating. The ratio k(t)/k(0) is shown to be the survival probability of the reactant pair at time t starting from an initial distribution that is localized in the reactive region. This relation forms the basis of the calculation of k(t) through Brownian dynamics simulations. Two simulation procedures involving the propagation of nonreactive trajectories initiated only from the reactive region are described and illustrated on a model system. Both analytical and simulation results demonstrate the accuracy of the equilibrium-distribution approximation method. PMID:8913584

  1. Jasminum sambac flower absolutes from India and China--geographic variations.

    PubMed

    Braun, Norbert A; Sim, Sherina

    2012-05-01

    Seven Jasminum sambac flower absolutes from different locations in the southern Indian state of Tamil Nadu were analyzed using GC and GC-MS. Focus was placed on 41 key ingredients to investigate geographic variations in this species. These seven absolutes were compared with an Indian bud absolute and commercially available J. sambac flower absolutes from India and China. All absolutes showed broad variations for the 10 main ingredients between 8% and 96%. In addition, the odor of Indian and Chinese J. sambac flower absolutes were assessed.

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

    PubMed

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

    2012-11-13

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

  3. Advancing Absolute Calibration for JWST and Other Applications

    NASA Astrophysics Data System (ADS)

    Rieke, George; Bohlin, Ralph; Boyajian, Tabetha; Carey, Sean; Casagrande, Luca; Deustua, Susana; Gordon, Karl; Kraemer, Kathleen; Marengo, Massimo; Schlawin, Everett; Su, Kate; Sloan, Greg; Volk, Kevin

    2017-10-01

    We propose to exploit the unique optical stability of the Spitzer telescope, along with that of IRAC, to (1) transfer the accurate absolute calibration obtained with MSX on very bright stars directly to two reference stars within the dynamic range of the JWST imagers (and of other modern instrumentation); (2) establish a second accurate absolute calibration based on the absolutely calibrated spectrum of the sun, transferred onto the astronomical system via alpha Cen A; and (3) provide accurate infrared measurements for the 11 (of 15) highest priority stars with no such data but with accurate interferometrically measured diameters, allowing us to optimize determinations of effective temperatures using the infrared flux method and thus to extend the accurate absolute calibration spectrally. This program is integral to plans for an accurate absolute calibration of JWST and will also provide a valuable Spitzer legacy.

  4. Absolute radiometric calibration of advanced remote sensing systems

    NASA Technical Reports Server (NTRS)

    Slater, P. N.

    1982-01-01

    The distinction between the uses of relative and absolute spectroradiometric calibration of remote sensing systems is discussed. The advantages of detector-based absolute calibration are described, and the categories of relative and absolute system calibrations are listed. The limitations and problems associated with three common methods used for the absolute calibration of remote sensing systems are addressed. Two methods are proposed for the in-flight absolute calibration of advanced multispectral linear array systems. One makes use of a sun-illuminated panel in front of the sensor, the radiance of which is monitored by a spectrally flat pyroelectric radiometer. The other uses a large, uniform, high-radiance reference ground surface. The ground and atmospheric measurements required as input to a radiative transfer program to predict the radiance level at the entrance pupil of the orbital sensor are discussed, and the ground instrumentation is described.

  5. Determination of the rate coefficient for the N2/+/ + O reaction in the ionosphere

    NASA Technical Reports Server (NTRS)

    Torr, D. G.; Torr, M. R.; Orsini, N.; Hanson, W. B.; Hoffman, J. H.; Walker, J. C. G.

    1977-01-01

    Using approximately 400 simultaneous measurements of ion and neutral densities and temperatures, and the spectrum of the solar flux measured by the Atmosphere Explorer C satellite, we have determined the rate constant k1 for the reaction between N2(+) and O in the ionosphere for ion temperatures between 600 and 700 K. We find that k1 = 1.1 x 10 to the minus 10th power cu cm per sec, with a standard deviation of + or - 15%. If we use the temperature dependence for this reaction determined in the laboratory then at 300 K we find excellent agreement with the recommended laboratory value.

  6. A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Shaw, Jacob T.; Lidster, Richard T.; Cryer, Danny R.; Ramirez, Noelia; Whiting, Fiona C.; Boustead, Graham A.; Whalley, Lisa K.; Ingham, Trevor; Rickard, Andrew R.; Dunmore, Rachel E.; Heard, Dwayne E.; Lewis, Ally C.; Carpenter, Lucy J.; Hamilton, Jacqui F.; Dillon, Terry J.

    2018-03-01

    Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k = 5.7 (±0.3) × 10-11 cm3 molecule-1 s-1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T = 323 (±10) K.

  7. The Temperature Optima and Temperature Sensitivity of Soil Respiration Explained By Macromolecular Rate Theory (MMRT).

    NASA Astrophysics Data System (ADS)

    Schipper, L. A.; O'Neill, T.; Arcus, V. L.

    2014-12-01

    One of the most fundamental factors controlling all biological and chemical processes is changing temperature. Temperature dependence was originally described by the Arrhenius function in the 19th century. This function provides an excellent description of chemical reaction rates. However, the Arrhenius function does not predict the temperature optimum of biological rates that is clearly evident in laboratory and field measurements. Previously, the temperature optimum of biological processes has been ascribed to denaturation of enzymes but the observed temperature optima in soil are often rather modest, occurring at about 40-50°C and generally less than recognised temperatures for protein unfolding. We have modified the Arrhenius function incorporating a temperature-dependent activation energy derived directly from first principles from thermodynamics of macromolecules. MacroMolecular Rate Theory (MMRT) accounts for large changes in the flexibility of enzymes during catalysis that result in changes in heat capacity (ΔC‡p) of the enzyme during the reaction. MMRT predicts an initially Arrhenius-like response followed by a temperature optimum without the need for enzyme denaturation (Hobbs et al., 2013. ACS Chemical Biology. 8: 2388-2393). Denaturation, of course, occurs at much higher temperatures. We have shown that MMRT fits biogeochemical data collected from laboratory and field studies with important implications for changes in absolute temperature sensitivity as temperature rises (Schipper et al., 2014. Global Change Biology). As the temperature optimum is approached the absolute temperature sensitivity of biological processes decreases to zero. Consequently, the absolute temperature-sensitivity of soil biological processes depends on both the change in ecosystem temperature and the temperature optimum of the biological process. MMRT also very clearly explains why Q10 values decline with increasing temperature more quickly than would be predicted from the

  8. Selected specific rates of reactions of transients from water in aqueous solution. Hydrated electron, supplemental data. [Reactions with transients from water, with inorganic solutes, and with solutes

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

    Ross, A.B.

    1975-06-01

    A compilation of rates of reactions of hydrated electrons with other transients and with organic and inorganic solutes in aqueous solution appeared in NSRDS-NBS 43, and covered the literature up to early 1971. This supplement includes additional rates which have been published through July 1973.

  9. The protoelectric potential map (PPM): an absolute two-dimensional chemical potential scale for a global understanding of chemistry.

    PubMed

    Radtke, Valentin; Himmel, Daniel; Pütz, Katharina; Goll, Sascha K; Krossing, Ingo

    2014-04-07

    We introduce the protoelectric potential map (PPM) as a novel, two-dimensional plot of the absolute reduction potential (peabs scale) combined with the absolute protochemical potential (Brønsted acidity: pHabs scale). The validity of this thermodynamically derived PPM is solvent-independent due to the scale zero points, which were chosen as the ideal electron gas and the ideal proton gas at standard conditions. To tie a chemical environment to these reference states, the standard Gibbs energies for the transfer of the gaseous electrons/protons to the medium are needed as anchor points. Thereby, the thermodynamics of any redox, acid-base or combined system in any medium can be related to any other, resulting in a predictability of reactions even over different media or phase boundaries. Instruction is given on how to construct the PPM from the anchor points derived and tabulated with this work. Since efforts to establish "absolute" reduction potential scales and also "absolute" pH scales already exist, a short review in this field is given and brought into relation to the PPM. Some comments on the electrochemical validation and realization conclude this concept article. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Radar prediction of absolute rain fade distributions for earth-satellite paths and general methods for extrapolation of fade statistics to other locations

    NASA Technical Reports Server (NTRS)

    Goldhirsh, J.

    1982-01-01

    The first absolute rain fade distribution method described establishes absolute fade statistics at a given site by means of a sampled radar data base. The second method extrapolates absolute fade statistics from one location to another, given simultaneously measured fade and rain rate statistics at the former. Both methods employ similar conditional fade statistic concepts and long term rain rate distributions. Probability deviations in the 2-19% range, with an 11% average, were obtained upon comparison of measured and predicted levels at given attenuations. The extrapolation of fade distributions to other locations at 28 GHz showed very good agreement with measured data at three sites located in the continental temperate region.

  11. 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. Copyright © 2014 Elsevier Inc. All rights reserved.

  12. Application of an Artificial Neural Network to the Prediction of OH Radical Reaction Rate Constants for Evaluating Global Warming Potential.

    PubMed

    Allison, Thomas C

    2016-03-03

    Rate constants for reactions of chemical compounds with hydroxyl radical are a key quantity used in evaluating the global warming potential of a substance. Experimental determination of these rate constants is essential, but it can also be difficult and time-consuming to produce. High-level quantum chemistry predictions of the rate constant can suffer from the same issues. Therefore, it is valuable to devise estimation schemes that can give reasonable results on a variety of chemical compounds. In this article, the construction and training of an artificial neural network (ANN) for the prediction of rate constants at 298 K for reactions of hydroxyl radical with a diverse set of molecules is described. Input to the ANN consists of counts of the chemical bonds and bends present in the target molecule. The ANN is trained using 792 (•)OH reaction rate constants taken from the NIST Chemical Kinetics Database. The mean unsigned percent error (MUPE) for the training set is 12%, and the MUPE of the testing set is 51%. It is shown that the present methodology yields rate constants of reasonable accuracy for a diverse set of inputs. The results are compared to high-quality literature values and to another estimation scheme. This ANN methodology is expected to be of use in a wide range of applications for which (•)OH reaction rate constants are required. The model uses only information that can be gathered from a 2D representation of the molecule, making the present approach particularly appealing, especially for screening applications.

  13. Greater absolute risk for all subtypes of breast cancer in the US than Malaysia.

    PubMed

    Horne, Hisani N; Beena Devi, C R; Sung, Hyuna; Tang, Tieng Swee; Rosenberg, Philip S; Hewitt, Stephen M; Sherman, Mark E; Anderson, William F; Yang, Xiaohong R

    2015-01-01

    Hormone receptor (HR) negative breast cancers are relatively more common in low-risk than high-risk countries and/or populations. However, the absolute variations between these different populations are not well established given the limited number of cancer registries with incidence rate data by breast cancer subtype. We, therefore, used two unique population-based resources with molecular data to compare incidence rates for the 'intrinsic' breast cancer subtypes between a low-risk Asian population in Malaysia and high-risk non-Hispanic white population in the National Cancer Institute's surveillance, epidemiology, and end results 18 registries database (SEER 18). The intrinsic breast cancer subtypes were recapitulated with the joint expression of the HRs (estrogen receptor and progesterone receptor) and human epidermal growth factor receptor-2 (HER2). Invasive breast cancer incidence rates overall were fivefold greater in SEER 18 than in Malaysia. The majority of breast cancers were HR-positive in SEER 18 and HR-negative in Malaysia. Notwithstanding the greater relative distribution for HR-negative cancers in Malaysia, there was a greater absolute risk for all subtypes in SEER 18; incidence rates were nearly 7-fold higher for HR-positive and 2-fold higher for HR-negative cancers in SEER 18. Despite the well-established relative breast cancer differences between low-risk and high-risk countries and/or populations, there was a greater absolute risk for HR-positive and HR-negative subtypes in the US than Malaysia. Additional analytical studies are sorely needed to determine the factors responsible for the elevated risk of all subtypes of breast cancer in high-risk countries like the United States.

  14. Absolutely nondestructive discrimination of Huoshan Dendrobium nobile species with miniature near-infrared (NIR) spectrometer engine.

    PubMed

    Hu, Tian; Yang, Hai-Long; Tang, Qing; Zhang, Hui; Nie, Lei; Li, Lian; Wang, Jin-Feng; Liu, Dong-Ming; Jiang, Wei; Wang, Fei; Zang, Heng-Chang

    2014-10-01

    As one very precious traditional Chinese medicine (TCM), Huoshan Dendrobium has not only high price, but also significant pharmaceutical efficacy. However, different species of Huoshan Dendrobium exhibit considerable difference in pharmaceutical efficacy, so rapid and absolutely non-destructive discrimination of Huoshan Dendrobium nobile according to different species is crucial to quality control and pharmaceutical effect. In this study, as one type of miniature near-infrared (NIR) spectrometer, MicroNIR 1700 was used for absolutely nondestructive determination of NIR spectra of 90 batches of Dendrobium from five species of differ- ent commodity grades. The samples were intact and not smashed. Soft independent modeling of class analogy (SIMCA) pattern recognition based on principal component analysis (PCA) was used to classify and recognize different species of Dendrobium samples. The results indicated that the SIMCA qualitative models established with pretreatment method of standard normal variate transformation (SNV) in the spectra range selected by Qs method had 100% recognition rates and 100% rejection rates. This study demonstrated that a rapid and absolutely non-destructive analytical technique based on MicroNIR 1700 spectrometer was developed for successful discrimination of five different species of Huoshan Dendrobium with acceptable accuracy.

  15. Absolute photoionization cross sections of two cyclic ketones: cyclopentanone and cyclohexanone.

    PubMed

    Price, Chelsea; Fathi, Yasmin; Meloni, Giovanni

    2017-05-01

    Absolute photoionization cross sections for cyclopentanone and cyclohexanone, as well as partial ionization cross sections for the dissociative ionized fragments, are presented in this investigation. Experiments are performed via a multiplexed photoionization mass spectrometer utilizing vacuum ultraviolet (VUV) synchrotron radiation supplied by the Advanced Light Source of Lawrence Berkeley National Laboratory. These results allow the quantification of these species that is relevant to investigate the kinetics and combustion reactions of potential biofuels. The CBS-QB3 calculated values for the adiabatic ionization energies agree well with the experimental values, and the identification of possible dissociative fragments is discussed for both systems. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  16. 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

  17. A Study of Interactions between Mixing and Chemical Reaction Using the Rate-Controlled Constrained-Equilibrium Method

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    The rate-controlled constrained-equilibrium (RCCE) method is employed to study the interactions between mixing and chemical reaction. Considering that mixing can influence the RCCE state, the key objective is to assess the accuracy and numerical performance of the method in simulations involving both reaction and mixing. The RCCE formulation includes rate equations for constraint potentials, density and temperature, which allows taking account of mixing alongside chemical reaction without splitting. The RCCE is a dimension reduction method for chemical kinetics based on thermodynamics laws. It describes the time evolution of reacting systems using a series of constrained-equilibrium states determined by RCCE constraints. The full chemical composition at each state is obtained by maximizing the entropy subject to the instantaneous values of the constraints. The RCCE is applied to a spatially homogeneous constant pressure partially stirred reactor (PaSR) involving methane combustion in oxygen. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The chemical kinetics, comprised of 29 species and 133 reaction steps, is represented by 12 RCCE constraints. The RCCE predictions are compared with those obtained by direct integration of the same kinetics, termed detailed kinetics model (DKM). The RCCE shows accurate prediction of combustion in PaSR with different mixing intensities. The method also demonstrates reduced numerical stiffness and overall computational cost compared to DKM.

  18. 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.

  19. CO + OH --> CO2 + H: The relative reaction rate of five CO isotopologues with OH and OD

    NASA Astrophysics Data System (ADS)

    Feilberg, K. L.; Nielsen, C. J.; Griffith, D. W.; Johnson, M. S.

    2003-04-01

    The reaction of carbon monoxide with the hydroxyl radical (CO + OH) plays a central role in tropospheric chemistry. While the analysis of stable isotope enrichment has been used to refine models of the sources and sinks of atmospheric CO and CO_2, less is known about the mechanism behind the enrichment [T. Röckmann et al., 1998]. We have previously reported the relative reaction rate of five CO isotopologues with OH radicals [K. L. Feilberg et al. 2002]; the present work is an expansion of the previous work in which the relative reaction rate with OD as well as with OH is measured using an improved technique. The hydroxyl radical was generated by the UV photolysis of ozone in the presence of hydrogen gas. The concentrations of the carbon monoxide isotopologues as a function of photolysis time is determined using a global fit of the rovibrationally resolved FTIR spectrum of the gas mixture in a stainless steel smog chamber. The observed inverse kinetic isotope effect is best understood in terms of the effect of isotopic substitution on the relative rate of unimolecular dissociation of the HOCO intermediate to reform reagents versus dissociate to products. In addition, we present the results of a quantum dressed classical mechanics calculation for the reaction CO + OD rightarrow CO_2 + D analogous to a previously published calculation for the reaction CO + OD rightarrow CO_2 + H [K. L. Feilberg et al. 2001]. References T. Röckmann, C. A. M. Brenninkmeijer, G. Saueressig, P. Bergamaschi, J. N. Crowley, H. Fischer and P. J. Crutzen, Science, 1998, 281, 544. K. L. Feilberg, C. J. Nielsen, D. W. T. Griffith and M. S. Johnson, Physical Chemistry Chemical Physics 4, 4687-4693, 2002. K. L. Feilberg, G. D. Billing and M. S. Johnson, Journal of Physical Chemistry A, 105(50), 11171, 2001.

  20. Plasticity of Performance Curves Can Buffer Reaction Rates from Body Temperature Variation in Active Endotherms.

    PubMed

    Seebacher, Frank; Little, Alexander G

    2017-01-01

    Endotherms regulate their core body temperature by adjusting metabolic heat production and insulation. Endothermic body temperatures are therefore relatively stable compared to external temperatures. The thermal sensitivity of biochemical reaction rates is thought to have co-evolved with body temperature regulation so that optimal reaction rates occur at the regulated body temperature. However, recent data show that core body temperatures even of non-torpid endotherms fluctuate considerably. Additionally, peripheral temperatures can be considerably lower and more variable than core body temperatures. Here we discuss whether published data support the hypothesis that thermal performance curves of physiological reaction rates are plastic so that performance is maintained despite variable body temperatures within active (non-torpid) endotherms, and we explore mechanisms that confer plasticity. There is evidence that thermal performance curves in tissues that experience thermal fluctuations can be plastic, although this question remains relatively unexplored for endotherms. Mechanisms that alter thermal responses locally at the tissue level include transient potential receptor ion channels (TRPV and TRPM) and the AMP-activated protein kinase (AMPK) both of which can influence metabolism and energy expenditure. Additionally, the thermal sensitivity of processes that cause post-transcriptional RNA degradation can promote the relative expression of cold-responsive genes. Endotherms can respond to environmental fluctuations similarly to ectotherms, and thermal plasticity complements core body temperature regulation to increase whole-organism performance. Thermal plasticity is ancestral to endothermic thermoregulation, but it has not lost its selective advantage so that modern endotherms are a physiological composite of ancestral ectothermic and derived endothermic traits.

  1. Plasticity of Performance Curves Can Buffer Reaction Rates from Body Temperature Variation in Active Endotherms

    PubMed Central

    Seebacher, Frank; Little, Alexander G.

    2017-01-01

    Endotherms regulate their core body temperature by adjusting metabolic heat production and insulation. Endothermic body temperatures are therefore relatively stable compared to external temperatures. The thermal sensitivity of biochemical reaction rates is thought to have co-evolved with body temperature regulation so that optimal reaction rates occur at the regulated body temperature. However, recent data show that core body temperatures even of non-torpid endotherms fluctuate considerably. Additionally, peripheral temperatures can be considerably lower and more variable than core body temperatures. Here we discuss whether published data support the hypothesis that thermal performance curves of physiological reaction rates are plastic so that performance is maintained despite variable body temperatures within active (non-torpid) endotherms, and we explore mechanisms that confer plasticity. There is evidence that thermal performance curves in tissues that experience thermal fluctuations can be plastic, although this question remains relatively unexplored for endotherms. Mechanisms that alter thermal responses locally at the tissue level include transient potential receptor ion channels (TRPV and TRPM) and the AMP-activated protein kinase (AMPK) both of which can influence metabolism and energy expenditure. Additionally, the thermal sensitivity of processes that cause post-transcriptional RNA degradation can promote the relative expression of cold-responsive genes. Endotherms can respond to environmental fluctuations similarly to ectotherms, and thermal plasticity complements core body temperature regulation to increase whole-organism performance. Thermal plasticity is ancestral to endothermic thermoregulation, but it has not lost its selective advantage so that modern endotherms are a physiological composite of ancestral ectothermic and derived endothermic traits. PMID:28824463

  2. Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions

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

    Ross, F; Ross, A B

    1977-01-01

    Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.

  3. Experimental and theoretical study of the gas phase reaction of ethynyl radical with methane (HCC+CH 4)

    NASA Astrophysics Data System (ADS)

    Ceursters, Benny; Thi Nguyen, Hue Minh; Peeters, Jozef; Tho Nguyen, Minh

    2000-10-01

    Absolute rate coefficients of the reaction of ethynyl radical with methane were measured for the first time at higher temperatures by a pulsed laser photolysis/chemiluminescence (PLP/CL) technique. Ethynyl radicals (HCC) radicals were generated pulsewise upon excimer laser photodissociation of acetylene at 193 nm and pseudo-first-order exponential decays of thermalized HCC were monitored in real-time by the CH( A2Δ → X2Π ) chemiluminescence produced by their reaction with O 2. The rate coefficients k(HCC+CH 4), over 295⩽T ( K)<800 , exhibit strong non-Arrhenius behaviour, being k(T)=1.39×10 -18T 2.34±0.40exp[(380±180) K/T] cm3 molecule-1 s-1. Calculations at the CCSD(T)/aug-cc-pvTZ level reveal that the direct H-abstraction yielding HCCH+CH 3 has the lowest energy barrier of about 10 kJ mol -1.

  4. Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D : reflected shock tube and theoretical studies.

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

    Sivaramakrishnan, R.; Su, M.-C.; Michael, J. V.

    2010-09-09

    The thermal decomposition of ethanol and its reactions with OH and D have been studied with both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for ethanol have been measured at high T in reflected shock waves using OH optical absorption and high-sensitivity H-atom ARAS detection. The three dissociation processes that are dominant at high T are: C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 4} + H{sub 2}O; C{sub 2}H{sub 5}OH {yields} CH{sub 3} + CH{sub 2}OH; C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 5} + OH. The rate coefficient for reaction C was measuredmore » directly with high sensitivity at 308 nm using a multipass optical White cell. Meanwhile, H-atom ARAS measurements yield the overall rate coefficient and that for the sum of reactions B and C, since H-atoms are instantaneously formed from the decompositions of CH{sub 2}OH and C{sub 2}H{sub 5} into CH{sub 2}O + H and C{sub 2}H{sub 4} + H, respectively. By difference, rate constants for reaction 1 could be obtained. One potential complication is the scavenging of OH by unreacted ethanol in the OH experiments, and therefore, rate constants for OH + C{sub 2}H{sub 5}OH {yields} products were measured using tert-butyl hydroperoxide (tBH) as the thermal source for OH. The present experiments can be represented by the Arrhenius expression k = (2.5 {+-} 0.43) x 10{sup -11} exp(- 911 {+-} 191 K/T) cm{sup 3} molecule{sup -1} s{sup -1} over the T range 857-1297 K. For completeness, we have also measured the rate coefficient for the reaction of D atoms with ethanol D + C{sub 2}H{sub 5}OH {yields} products whose H analogue is another key reaction in the combustion of ethanol. Over the T range 1054-1359 K, the rate constants from the present experiments can be represented by the Arrhenius expression, k = (3.98 {+-} 0.76) x 10{sup -10} exp(- 4494 {+-} 235 K/T) cm{sup 3} molecule{sup -1} s{sup -1}. The high-pressure rate coefficients for reactions B

  5. 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.

  6. Linking Comparisons of Absolute Gravimeters: A Proof of Concept for a new Global Absolute Gravity Reference System.

    NASA Astrophysics Data System (ADS)

    Wziontek, H.; Palinkas, V.; Falk, R.; Vaľko, M.

    2016-12-01

    Since decades, absolute gravimeters are compared on a regular basis on an international level, starting at the International Bureau for Weights and Measures (BIPM) in 1981. Usually, these comparisons are based on constant reference values deduced from all accepted measurements acquired during the comparison period. Temporal changes between comparison epochs are usually not considered. Resolution No. 2, adopted by IAG during the IUGG General Assembly in Prague 2015, initiates the establishment of a Global Absolute Gravity Reference System based on key comparisons of absolute gravimeters (AG) under the International Committee for Weights and Measures (CIPM) in order to establish a common level in the microGal range. A stable and unique reference frame can only be achieved, if different AG are taking part in different kind of comparisons. Systematic deviations between the respective comparison reference values can be detected, if the AG can be considered stable over time. The continuous operation of superconducting gravimeters (SG) on selected stations further supports the temporal link of comparison reference values by establishing a reference function over time. By a homogenous reprocessing of different comparison epochs and including AG and SG time series at selected stations, links between several comparisons will be established and temporal comparison reference functions will be derived. By this, comparisons on a regional level can be traced to back to the level of key comparisons, providing a reference for other absolute gravimeters. It will be proved and discussed, how such a concept can be used to support the future absolute gravity reference system.

  7. Quantum instanton calculation of rate constant for CH4 + OH → CH3 + H2O reaction: Torsional anharmonicity and kinetic isotope effect

    NASA Astrophysics Data System (ADS)

    Wang, Wenji; Zhao, Yi

    2012-12-01

    Thermal rate constants for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The results reveal that the quantum effect is remarkable for the reaction at both low and high temperatures, and the obtained rates are in good agreement with experimental measurements at high temperatures. Compared to the harmonic approximation, the torsional anharmonic effect of the internal rotation has a little influence on the rates at low temperatures, however, it enhances the rate by about 20% at 1000 K. In addition, the free energy barriers for the isotopic reactions and the temperature dependence of kinetic isotope effects are also investigated. Generally speaking, for the title reaction, the replacement of OH with OD will reduce the free energy barrier, while substituting D for H (connected to C) will increase the free energy barrier.

  8. Measurement of the Am 242 m neutron-induced reaction cross sections

    DOE PAGES

    Buckner, M. Q.; Wu, C. Y.; Henderson, R. A.; ...

    2017-02-17

    The neutron-induced reaction cross sections of 242mAm were measured at the Los Alamos Neutron Science Center using the Detector for Advanced Neutron-Capture Experiments array along with a compact parallel-plate avalanche counter for fission-fragment detection. A new neutron-capture cross section was determined, and the absolute scale was set according to a concurrent measurement of the well-known 242mAm(n,f) cross section. The (n,γ) cross section was measured from thermal energy to an incident energy of 1 eV at which point the data quality was limited by the reaction yield in the laboratory. Our new 242mAm fission cross section was normalized to ENDF/B-VII.1 tomore » set the absolute scale, and it agreed well with the (n,f) cross section from thermal energy to 1 keV. Lastly, the average absolute capture-to-fission ratio was determined from thermal energy to E n = 0.1 eV, and it was found to be 26(4)% as opposed to the ratio of 19% from the ENDF/B-VII.1 evaluation.« less

  9. Statistical analysis of activation and reaction energies with quasi-variational coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Black, Joshua A.; Knowles, Peter J.

    2018-06-01

    The performance of quasi-variational coupled-cluster (QV) theory applied to the calculation of activation and reaction energies has been investigated. A statistical analysis of results obtained for six different sets of reactions has been carried out, and the results have been compared to those from standard single-reference methods. In general, the QV methods lead to increased activation energies and larger absolute reaction energies compared to those obtained with traditional coupled-cluster theory.

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

    USGS Publications Warehouse

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

    2009-01-01

    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 A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta 72 (1), 36-68] 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 Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta 70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta 58 (9), 2011-2024], 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. Additionally, observed maximum clay abundances in the argillic horizons occur at

  11. A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3. [in troposphere

    NASA Technical Reports Server (NTRS)

    Kurylo, M. J.; Anderson, P. C.; Klais, O.

    1979-01-01

    The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.

  12. Effect of the gas flow rate on the spatiotemporal distribution of Ar(1s5) absolute densities in a ns pulsed plasma jet impinging on a glass surface

    NASA Astrophysics Data System (ADS)

    Gazeli, K.; Bauville, G.; Fleury, M.; Jeanney, P.; Neveu, O.; Pasquiers, S.; Santos Sousa, J.

    2018-06-01

    This work presents spatial (axial-z and transversal-y) and temporal distributions of Ar(1s5) metastable absolute densities in an atmospheric pressure argon micro-plasma jet impinging on an ungrounded glass surface. Guided streamers are generated with a DBD device driven by pulsed positive high voltages of 6 kV in amplitude, 224 +/- 3 ns in FWHM and 20 kHz in frequency. The argon flow rate is varied between 200 and 600 sccm. The glass plate is placed at 5 mm away from the reactor’s nozzle and perpendicular to the streamers propagation. At these conditions, a diffuse stable discharge is established after the passage of the streamers allowing the quantification of the Ar(1s5) absolute density by means of a conventional TDLAS technique coupled with emission spectroscopy and ICCD imaging. The good reproducibility of the absorption signals is demonstrated. The experiments show the strong dependence of the maximum density ({0.5-4}× {10}13 {{{cm}}}-3) on the gas flow rate and the axial and transversal position. At 200 sccm, high maximum densities (> 2.4× {10}13 {{{cm}}}-3) are obtained in a small area close to the plasma source, while with increasing flow rate this area expands towards the glass plate. In the transversal direction, density maxima are obtained in a small zone around the propagation axis of the streamers. Finally, a noticeable increase is measured on the Ar(1s5) effective lifetime close to the glass surface by varying the flow rate from 200 to 600 sccm. In overall, the effective lifetime varies between ∼25 and ∼550 ns, depending on the gas flow rate and the values of z and y coordinates. The results obtained suggest that the present system can be implemented in various applications and particularly in what concerns the detection of weakly volatile organic compounds present in trace amounts on different surfaces.

  13. Effect of hydrostatic pressure, temperature, and solvent on the rate of the Diels-Alder reaction between 9,10-anthracenedimethanol and maleic anhydride

    NASA Astrophysics Data System (ADS)

    Kiselev, V. D.; Kornilov, D. A.; Anikin, O. V.; Latypova, L. I.; Konovalov, A. I.

    2017-03-01

    The rate of the reaction between 9,10-anthracenedimethanol and maleic anhydride in 1,4-dioxane, acetonitrile, trichloromethane, and toluene is studied at 25, 35, 45°C in the pressure range of 1-1772 bar. The rate constants, enthalpies, entropies and activation volumes are determined. It is shown that the rate of reaction with 9,10-anthracenedimethanol is approximately one order of magnitude higher than with 9-anthracenemethanol.

  14. Investigating Absolute Value: A Real World Application

    ERIC Educational Resources Information Center

    Kidd, Margaret; Pagni, David

    2009-01-01

    Making connections between various representations is important in mathematics. In this article, the authors discuss the numeric, algebraic, and graphical representations of sums of absolute values of linear functions. The initial explanations are accessible to all students who have experience graphing and who understand that absolute value simply…

  15. Stimulus probability effects in absolute identification.

    PubMed

    Kent, Christopher; Lamberts, Koen

    2016-05-01

    This study investigated the effect of stimulus presentation probability on accuracy and response times in an absolute identification task. Three schedules of presentation were used to investigate the interaction between presentation probability and stimulus position within the set. Data from individual participants indicated strong effects of presentation probability on both proportion correct and response times. The effects were moderated by the ubiquitous stimulus position effect. The accuracy and response time data were predicted by an exemplar-based model of perceptual cognition (Kent & Lamberts, 2005). The bow in discriminability was also attenuated when presentation probability for middle items was relatively high, an effect that will constrain future model development. The study provides evidence for item-specific learning in absolute identification. Implications for other theories of absolute identification are discussed. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

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

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

    Lamia, L.; Spitaleri, C.; La Cognata, M.

    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 deuteriummore » ({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.« less

  17. The Effectiveness of a Rater Training Booklet in Increasing Accuracy of Performance Ratings

    DTIC Science & Technology

    1988-04-01

    subjects’ ratings were compared for accuracy. The dependent measure was the absolute deviation score of each individual’s rating from the "true score". The...subjects’ ratings were compared for accuracy. The dependent measure was the absolute deviation score of each individual’s rating from the "true score". The...r IS % _. Findings: The absolute deviation scores of each individual’s ratings from the "true score" provided by subject matter experts were analyzed

  18. Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF2-CaO-SiO2-based slags

    NASA Astrophysics Data System (ADS)

    Duan, Sheng-chao; Li, Chuang; Guo, Han-jie; Guo, Jing; Han, Shao-wei; Yang, Wen-sheng

    2018-04-01

    The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO-SiO2-MgO-FeO-MnO-Al2O3-TiO2-CaF2 was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step (RCS) for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide (MnO), the apparent activation energy of the demanganization reaction was estimated to be 189.46 kJ·mol-1 in the current study, which indicated that the mass transfer of MnO in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the "specific reaction interface" (SRI) value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.

  19. A Conceptual Approach to Absolute Value Equations and Inequalities

    ERIC Educational Resources Information Center

    Ellis, Mark W.; Bryson, Janet L.

    2011-01-01

    The absolute value learning objective in high school mathematics requires students to solve far more complex absolute value equations and inequalities. When absolute value problems become more complex, students often do not have sufficient conceptual understanding to make any sense of what is happening mathematically. The authors suggest that the…

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

    PubMed

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

    2010-04-08

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

  1. Absolute pitch in a four-year-old boy with autism.

    PubMed

    Brenton, James N; Devries, Seth P; Barton, Christine; Minnich, Heike; Sokol, Deborah K

    2008-08-01

    Absolute pitch is the ability to identify the pitch of an isolated tone. We report on a 4-year-old boy with autism and absolute pitch, one of the youngest reported in the literature. Absolute pitch is thought to be attributable to a single gene, transmitted in an autosomal-dominant fashion. The association of absolute pitch with autism raises the speculation that this talent could be linked to a genetically distinct subset of children with autism. Further, the identification of absolute pitch in even young children with autism may lead to a lifelong skill.

  2. Absolute-gravity stations in Western Dronning Maud Land, Antarctica

    NASA Astrophysics Data System (ADS)

    Mäkinen, Jaakko; Rasindra, Ravik; Chand, Uttam; Tiwari, Virendra; Lukin, Valery; Anisimov, Michail; Melvaer, Yngve; Melland, Gudmund; Koivula, Hannu; Näränen, Jyri; Poutanen, Markku

    2013-04-01

    Absolute-gravity stations are an important part of the geodetic infrastructure of the Antarctic. They provide accurate starting values for gravity surveys performed e.g. for the determination of the geoid, for geological studies and for geophysical investigations. The time variation in gravity determined from repeated absolute-gravity measurements provides insights into the Glacial Isostatic Adjustment (GIA) and into solid Earth deformation due to variation in contemporary ice load. Given sufficient joint coverage with International Terrestrial Reference Frame (ITRF) sites, gravity rates in high latitudes could in principle provide an independent check of the geocentricity of the z-dot (velocities in the direction of the rotation axis of the Earth) of the ITRF. We review the absolute gravity stations in Western and Central Dronning Maud Land. The oldest station is at the Finnish base Aboa, with 5 measurements by the Finnish Geodetic Institute (FGI) starting with the FINNARP 1993 expedition. Measurements at Maitri (India) and Novolazarevskaya (Russia) were first performed in 2004 by the National Geophysical Research Institute (NGRI) of India, and by the FGI, respectively. In the season 2010/11 a new station was constructed at Troll (Norway). In the season 2011/12 the aforementioned four sites were occupied by the FG5-221 absolute gravimeter of the FGI. At Sanae IV (South Africa) there are previous occupations by the FG5-221, in 2003/4 and 2005/6. All these bases have continuous GNSS stations. Numerous supporting measurements have been made at the sites: microgravity networks, levelling and GNSS ties to excentres etc., for controlling the stability of the stations. At some sites, nearby glacier elevations were surveyed to monitor the attraction of the variable close-field snow and ice masses. We give a description of the sites and the measurements performed at them. The work has benefited from the co-operation in the COST Action ES0701 "Improved Constraints on Models

  3. The Cassini Reaction Wheels: Drag and Spin-Rate Trends from an Aging Interplanetary Spacecraft at Saturn

    NASA Technical Reports Server (NTRS)

    Brown, Todd S.

    2016-01-01

    The purpose of this paper is to provide a summary of the long-term trends of the estimated drag torque and spin-rates of the Cassini reaction wheel assemblies during eleven years of intensive science operations at Saturn..

  4. Thorough subcells diagnosis in a multi-junction solar cell via absolute electroluminescence-efficiency measurements

    PubMed Central

    Chen, Shaoqiang; Zhu, Lin; Yoshita, Masahiro; Mochizuki, Toshimitsu; Kim, Changsu; Akiyama, Hidefumi; Imaizumi, Mitsuru; Kanemitsu, Yoshihiko

    2015-01-01

    World-wide studies on multi-junction (tandem) solar cells have led to record-breaking improvements in conversion efficiencies year after year. To obtain detailed and proper feedback for solar-cell design and fabrication, it is necessary to establish standard methods for diagnosing subcells in fabricated tandem devices. Here, we propose a potential standard method to quantify the detailed subcell properties of multi-junction solar cells based on absolute measurements of electroluminescence (EL) external quantum efficiency in addition to the conventional solar-cell external-quantum-efficiency measurements. We demonstrate that the absolute-EL-quantum-efficiency measurements provide I–V relations of individual subcells without the need for referencing measured I–V data, which is in stark contrast to previous works. Moreover, our measurements quantify the absolute rates of junction loss, non-radiative loss, radiative loss, and luminescence coupling in the subcells, which constitute the “balance sheets” of tandem solar cells. PMID:25592484

  5. Structure dependence of the rate coefficients of hydroxyl radical+aromatic molecule reaction

    NASA Astrophysics Data System (ADS)

    Wojnárovits, László; Takács, Erzsébet

    2013-06-01

    The rate coefficients of hydroxyl radical addition to the rings of simple aromatic molecules (kOH) were evaluated based on the literature data. By analyzing the methods of kOH determination and the data obtained the most probable values were selected for the kOH's of individual compounds and thereby the most reliable dataset was created for monosubstituted aromatics and p-substituted phenols. For these compounds the rate coefficients fall in a narrow range between 2×109 mol-1 dm3 s-1 and 1×1010 mol-1 dm3 s-1. Although the values show some regular trend with the electron donating/withdrawing nature of the substituent, the log kOH-σp Hammett substituent constant plots do not give straight lines because these high kOH's are controlled by both, the chemical reactivity and the diffusion. However, the logarithms of the rate coefficients of the chemical reactivity controlled reactions (kchem), are calculated by the equation 1/kOH=1/kchem+1/kdiff, and accepting for the diffusion controlled rate coefficient kdiff=1.1×1010 mol-1 dm3 s-1, show good linear correlation with σp.

  6. A generalized population dynamics model for reproductive interference with absolute density dependence.

    PubMed

    Kyogoku, Daisuke; Sota, Teiji

    2017-05-17

    Interspecific mating interactions, or reproductive interference, can affect population dynamics, species distribution and abundance. Previous population dynamics models have assumed that the impact of frequency-dependent reproductive interference depends on the relative abundances of species. However, this assumption could be an oversimplification inappropriate for making quantitative predictions. Therefore, a more general model to forecast population dynamics in the presence of reproductive interference is required. Here we developed a population dynamics model to describe the absolute density dependence of reproductive interference, which appears likely when encounter rate between individuals is important. Our model (i) can produce diverse shapes of isoclines depending on parameter values and (ii) predicts weaker reproductive interference when absolute density is low. These novel characteristics can create conditions where coexistence is stable and independent from the initial conditions. We assessed the utility of our model in an empirical study using an experimental pair of seed beetle species, Callosobruchus maculatus and Callosobruchus chinensis. Reproductive interference became stronger with increasing total beetle density even when the frequencies of the two species were kept constant. Our model described the effects of absolute density and showed a better fit to the empirical data than the existing model overall.

  7. A study of the reaction Li+HCl by the technique of time-resolved laser-induced fluorescence spectroscopy of Li (2 2PJ-2 2S1/2, λ=670.7 nm) between 700 and 1000 K

    NASA Astrophysics Data System (ADS)

    Plane, John M. C.; Saltzman, Eric S.

    1987-10-01

    A kinetic study is presented of the reaction between lithium atoms and hydrogen chloride over the temperature range 700-1000 K. Li atoms are produced in an excess of HCl and He bath gas by pulsed photolysis of LiCl vapor. The concentration of the metal atoms is then monitored in real time by the technique of laser-induced fluorescence of Li atoms at λ=670.7 nm using a pulsed nitrogen-pumped dye laser and box-car integration of the fluorescence signal. Absolute second-order rate constants for this reaction have been measured at T=700, 750, 800, and 900 K. At T=1000 K the reverse reaction is sufficiently fast that equilibrium is rapidly established on the time scale of the experiment. A fit of the data between 700 and 900 K to the Arrhenius form, with 2σ errors calculated from the absolute errors in the rate constants, yields k(T)=(3.8±1.1)×10-10 exp[-(883±218)/T] cm3 molecule-1 s-1. This result is interpreted through a modified form of collision theory which is constrained to take account of the conservation of total angular momentum during the reaction. Thereby we obtain an estimate for the reaction energy threshold, E0=8.2±1.4 kJ mol-1 (where the error arises from uncertainty in the exothermicity of the reaction), in very good agreement with a crossed molecular beam study of the title reaction, and substantially lower than estimates of E0 from both semiempirical and ab initio calculations of the potential energy surface.

  8. 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

  9. Classical Wigner method with an effective quantum force: application to reaction rates.

    PubMed

    Poulsen, Jens Aage; Li, Huaqing; Nyman, Gunnar

    2009-07-14

    We construct an effective "quantum force" to be used in the classical molecular dynamics part of the classical Wigner method when determining correlation functions. The quantum force is obtained by estimating the most important short time separation of the Feynman paths that enter into the expression for the correlation function. The evaluation of the force is then as easy as classical potential energy evaluations. The ideas are tested on three reaction rate problems. The resulting transmission coefficients are in much better agreement with accurate results than transmission coefficients from the ordinary classical Wigner method.

  10. The Absolute Spectrum Polarimeter (ASP)

    NASA Technical Reports Server (NTRS)

    Kogut, A. J.

    2010-01-01

    The Absolute Spectrum Polarimeter (ASP) is an Explorer-class mission to map the absolute intensity and linear polarization of the cosmic microwave background and diffuse astrophysical foregrounds over the full sky from 30 GHz to 5 THz. The principal science goal is the detection and characterization of linear polarization from an inflationary epoch in the early universe, with tensor-to-scalar ratio r much greater than 1O(raised to the power of { -3}) and Compton distortion y < 10 (raised to the power of{-6}). We describe the ASP instrument and mission architecture needed to detect the signature of an inflationary epoch in the early universe using only 4 semiconductor bolometers.

  11. The absolute disparity anomaly and the mechanism of relative disparities.

    PubMed

    Chopin, Adrien; Levi, Dennis; Knill, David; Bavelier, Daphne

    2016-06-01

    There has been a long-standing debate about the mechanisms underlying the perception of stereoscopic depth and the computation of the relative disparities that it relies on. Relative disparities between visual objects could be computed in two ways: (a) using the difference in the object's absolute disparities (Hypothesis 1) or (b) using relative disparities based on the differences in the monocular separations between objects (Hypothesis 2). To differentiate between these hypotheses, we measured stereoscopic discrimination thresholds for lines with different absolute and relative disparities. Participants were asked to judge the depth of two lines presented at the same distance from the fixation plane (absolute disparity) or the depth between two lines presented at different distances (relative disparity). We used a single stimulus method involving a unique memory component for both conditions, and no extraneous references were available. We also measured vergence noise using Nonius lines. Stereo thresholds were substantially worse for absolute disparities than for relative disparities, and the difference could not be explained by vergence noise. We attribute this difference to an absence of conscious readout of absolute disparities, termed the absolute disparity anomaly. We further show that the pattern of correlations between vergence noise and absolute and relative disparity acuities can be explained jointly by the existence of the absolute disparity anomaly and by the assumption that relative disparity information is computed from absolute disparities (Hypothesis 1).

  12. The absolute disparity anomaly and the mechanism of relative disparities

    PubMed Central

    Chopin, Adrien; Levi, Dennis; Knill, David; Bavelier, Daphne

    2016-01-01

    There has been a long-standing debate about the mechanisms underlying the perception of stereoscopic depth and the computation of the relative disparities that it relies on. Relative disparities between visual objects could be computed in two ways: (a) using the difference in the object's absolute disparities (Hypothesis 1) or (b) using relative disparities based on the differences in the monocular separations between objects (Hypothesis 2). To differentiate between these hypotheses, we measured stereoscopic discrimination thresholds for lines with different absolute and relative disparities. Participants were asked to judge the depth of two lines presented at the same distance from the fixation plane (absolute disparity) or the depth between two lines presented at different distances (relative disparity). We used a single stimulus method involving a unique memory component for both conditions, and no extraneous references were available. We also measured vergence noise using Nonius lines. Stereo thresholds were substantially worse for absolute disparities than for relative disparities, and the difference could not be explained by vergence noise. We attribute this difference to an absence of conscious readout of absolute disparities, termed the absolute disparity anomaly. We further show that the pattern of correlations between vergence noise and absolute and relative disparity acuities can be explained jointly by the existence of the absolute disparity anomaly and by the assumption that relative disparity information is computed from absolute disparities (Hypothesis 1). PMID:27248566

  13. Surface reaction rate and probability of ozone and alpha-terpineol on glass, polyvinyl chloride, and latex paint surfaces.

    PubMed

    Shu, Shi; Morrison, Glenn C

    2011-05-15

    Ozone can react homogeneously with unsaturated organic compounds in buildings to generate undesirable products. However, these reactions can also occur on indoor surfaces, especially for low-volatility organics. Conversion rates of ozone with α-terpineol, a representative low-volatility compound, were quantified on surfaces that mimic indoor substrates. Rates were measured for α-terpineol adsorbed to beads of glass, polyvinylchloride (PVC), and dry latex paint, in a plug flow reactor. A newly defined second-order surface reaction rate coefficient, k(2), was derived from the flow reactor model. The value of k(2) ranged from 0.68 × 10(-14) cm(4)s(-1)molecule(-1) for α-terpineol adsorbed to PVC to 3.17 × 10(-14) cm(4)s(-1)molecule(-1) for glass, but was insensitive to relative humidity. Further, k(2) is only weakly influenced by the adsorbed mass but instead appears to be more strongly related to the interfacial activity α-terpineol. The minimum reaction probability ranged from 3.79 × 10(-6) for glass at 20% RH to 6.75 × 10(-5) for PVC at 50% RH. The combination of high equilibrium surface coverage and high reactivity for α-terpineol suggests that surface conversion rates are fast enough to compete with or even overwhelm other removal mechanisms in buildings such as gas-phase conversion and air exchange.

  14. Aircraft noise-induced awakenings are more reasonably predicted from relative than from absolute sound exposure levels.

    PubMed

    Fidell, Sanford; Tabachnick, Barbara; Mestre, Vincent; Fidell, Linda

    2013-11-01

    Assessment of aircraft noise-induced sleep disturbance is problematic for several reasons. Current assessment methods are based on sparse evidence and limited understandings; predictions of awakening prevalence rates based on indoor absolute sound exposure levels (SELs) fail to account for appreciable amounts of variance in dosage-response relationships and are not freely generalizable from airport to airport; and predicted awakening rates do not differ significantly from zero over a wide range of SELs. Even in conjunction with additional predictors, such as time of night and assumed individual differences in "sensitivity to awakening," nominally SEL-based predictions of awakening rates remain of limited utility and are easily misapplied and misinterpreted. Probabilities of awakening are more closely related to SELs scaled in units of standard deviates of local distributions of aircraft SELs, than to absolute sound levels. Self-selection of residential populations for tolerance of nighttime noise and habituation to airport noise environments offer more parsimonious and useful explanations for differences in awakening rates at disparate airports than assumed individual differences in sensitivity to awakening.

  15. Absolute bioavailability and pharmacokinetics of avosentan in man.

    PubMed

    Dieterle, W; Hengelage, T

    2009-09-01

    Avosentan is a potent, selective endothelin A receptor blocker. The pharmacokinetics of avosentan were investigated in healthy male and female volunteers, following oral and i.v. administration of single doses of avosentan and its absolute bioavailability was determined. In a randomized, balanced open-label, three-period oral crossover study, 26 healthy subjects (19 males and 7 females) received Treatments A, B and C. Treatment A consisted of a single dose of a 25 mg film-coated tablet of avosentan, Treatment B of a single dose of a 50 mg film-coated tablet of avosentan and Treatment C of 10 mg avosentan in 20 ml solution for infusion for 20 minutes (10 mg avosentan in 20 ml phosphate buffer pH 9.0 containing 1% polysorbate 20). Plasma concentrations of avosentan and its hydroxymethyl metabolite Ro 68-5925 were measured by liquid chromatography-tandem mass spectrometry. The absolute bioavailability values (compared with i.v. infusion) for the 25 and 50 mg film-coated tablets were 81% and 72%, respectively. The extent of absorption, as measured by partial and total AUC, increased almost proportionally with the dose. The estimated proportionality coefficient for AUC0- yen was 1.12 (90% CI 1.06, 1.18). For the rate of absorption (Cmax) strict dose-proportionality was not demonstrated (proportionality coefficient 1.13 (90% CI 1.0, 1.28)). No relevant gender differences in the pharmacokinetic characteristics were evident after a single i.v. dose and at an oral dose of 25 mg, whereas after oral administration of 50 mg of avosentan differences were seen in Cmax and t1/2. The absolute bioavailability of avosentan film-coated tablets is high, i.e. 70 - 80%.

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

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

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

    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 inmore » 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

  17. Reductive transformation of dioxins: An assessment of the contribution of dissolved organic matter to dechlorination reactions

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

    Fu, Q.S.; Barkovskii, A.L.; Adriaens, P.

    1999-11-01

    The susceptibility of dioxins to dissolved organic carbon (DOC)-mediated dechlorination reactions was investigated using 1,2,3,4,6,7,9-heptachlorodibenzo-p-dioxin (HpCDD), Aldrich humic acid (AHA), and polymaleic acid (PMA) as model compounds. The dechlorination yields were on the order of 4--20% which, when normalized to phenolic acidity, was comparable to yields observed in the presence of the humic constituents catechol and resorcinol. Based on the ratio of dechlorination yields as a function of phenolic acidity and electron transfer capacity, differences in electron transfer efficiency to dioxins are likely combined effects of specific interactions with the functional groups and nonspecific hydrophobic interactions. Hexa- and pentaCDD homologuesmore » were dominant in all incubations, and diCDD constituted the final product of dechlorination. The rates of appearance of lesser chlorinated products were similar to those observed in sediment systems and followed thermodynamic considerations as they decreased with a decrease in level of chlorination. Generally, both absolute and phenolic acidity-normalized rate constants for AHA-mediated reactions were up to 2-fold higher than those effected by PMA. These results indicate that the electron shuttling capacity of sediment DOC may significantly affect the fate of dioxins, in part through dechlorination reactions.« less

  18. A novel approach for human whole transcriptome analysis based on absolute gene expression of microarray data.

    PubMed

    Bikel, Shirley; Jacobo-Albavera, Leonor; Sánchez-Muñoz, Fausto; Cornejo-Granados, Fernanda; Canizales-Quinteros, Samuel; Soberón, Xavier; Sotelo-Mundo, Rogerio R; Del Río-Navarro, Blanca E; Mendoza-Vargas, Alfredo; Sánchez, Filiberto; Ochoa-Leyva, Adrian

    2017-01-01

    In spite of the emergence of RNA sequencing (RNA-seq), microarrays remain in widespread use for gene expression analysis in the clinic. There are over 767,000 RNA microarrays from human samples in public repositories, which are an invaluable resource for biomedical research and personalized medicine. The absolute gene expression analysis allows the transcriptome profiling of all expressed genes under a specific biological condition without the need of a reference sample. However, the background fluorescence represents a challenge to determine the absolute gene expression in microarrays. Given that the Y chromosome is absent in female subjects, we used it as a new approach for absolute gene expression analysis in which the fluorescence of the Y chromosome genes of female subjects was used as the background fluorescence for all the probes in the microarray. This fluorescence was used to establish an absolute gene expression threshold, allowing the differentiation between expressed and non-expressed genes in microarrays. We extracted the RNA from 16 children leukocyte samples (nine males and seven females, ages 6-10 years). An Affymetrix Gene Chip Human Gene 1.0 ST Array was carried out for each sample and the fluorescence of 124 genes of the Y chromosome was used to calculate the absolute gene expression threshold. After that, several expressed and non-expressed genes according to our absolute gene expression threshold were compared against the expression obtained using real-time quantitative polymerase chain reaction (RT-qPCR). From the 124 genes of the Y chromosome, three genes (DDX3Y, TXLNG2P and EIF1AY) that displayed significant differences between sexes were used to calculate the absolute gene expression threshold. Using this threshold, we selected 13 expressed and non-expressed genes and confirmed their expression level by RT-qPCR. Then, we selected the top 5% most expressed genes and found that several KEGG pathways were significantly enriched. Interestingly

  19. A novel approach for human whole transcriptome analysis based on absolute gene expression of microarray data

    PubMed Central

    Bikel, Shirley; Jacobo-Albavera, Leonor; Sánchez-Muñoz, Fausto; Cornejo-Granados, Fernanda; Canizales-Quinteros, Samuel; Soberón, Xavier; Sotelo-Mundo, Rogerio R.; del Río-Navarro, Blanca E.; Mendoza-Vargas, Alfredo; Sánchez, Filiberto

    2017-01-01

    Background In spite of the emergence of RNA sequencing (RNA-seq), microarrays remain in widespread use for gene expression analysis in the clinic. There are over 767,000 RNA microarrays from human samples in public repositories, which are an invaluable resource for biomedical research and personalized medicine. The absolute gene expression analysis allows the transcriptome profiling of all expressed genes under a specific biological condition without the need of a reference sample. However, the background fluorescence represents a challenge to determine the absolute gene expression in microarrays. Given that the Y chromosome is absent in female subjects, we used it as a new approach for absolute gene expression analysis in which the fluorescence of the Y chromosome genes of female subjects was used as the background fluorescence for all the probes in the microarray. This fluorescence was used to establish an absolute gene expression threshold, allowing the differentiation between expressed and non-expressed genes in microarrays. Methods We extracted the RNA from 16 children leukocyte samples (nine males and seven females, ages 6–10 years). An Affymetrix Gene Chip Human Gene 1.0 ST Array was carried out for each sample and the fluorescence of 124 genes of the Y chromosome was used to calculate the absolute gene expression threshold. After that, several expressed and non-expressed genes according to our absolute gene expression threshold were compared against the expression obtained using real-time quantitative polymerase chain reaction (RT-qPCR). Results From the 124 genes of the Y chromosome, three genes (DDX3Y, TXLNG2P and EIF1AY) that displayed significant differences between sexes were used to calculate the absolute gene expression threshold. Using this threshold, we selected 13 expressed and non-expressed genes and confirmed their expression level by RT-qPCR. Then, we selected the top 5% most expressed genes and found that several KEGG pathways were

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

    NASA Astrophysics Data System (ADS)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

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

  1. 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.

  2. Introducing the Mean Absolute Deviation "Effect" Size

    ERIC Educational Resources Information Center

    Gorard, Stephen

    2015-01-01

    This paper revisits the use of effect sizes in the analysis of experimental and similar results, and reminds readers of the relative advantages of the mean absolute deviation as a measure of variation, as opposed to the more complex standard deviation. The mean absolute deviation is easier to use and understand, and more tolerant of extreme…

  3. Monolithically integrated absolute frequency comb laser system

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

    Wanke, Michael C.

    2016-07-12

    Rather than down-convert optical frequencies, a QCL laser system directly generates a THz frequency comb in a compact monolithically integrated chip that can be locked to an absolute frequency without the need of a frequency-comb synthesizer. The monolithic, absolute frequency comb can provide a THz frequency reference and tool for high-resolution broad band spectroscopy.

  4. Activation barriers for series of exothermic homologous reactions. V. Boron group diatomic species reactions

    NASA Astrophysics Data System (ADS)

    Blue, Alan S.; Belyung, David P.; Fontijn, Arthur

    1997-09-01

    Semiempirical configuration interaction (SECI) theory is used to predict activation barriers E, as defined by k(T)=ATn exp(-E/RT). Previously SECI has been applied to homologous series of oxidation reactions of s1, s2, and s2p1 metal atoms. Here it is extended to oxidation reactions of diatomic molecules containing one s2p1 atom. E values are calculated for the reactions of BH, BF, BCl, AlF, AlCl, AlBr, GaF, GaI, InCl, InBr, InI, TlF, TlCl, TlBr, and TlI with O2, CO2, SO2, or N2O. These values correlate with the sums of the ionization potentials and Σ-Π promotion energies of the former minus the electron affinities of the latter. In the earlier work n was chosen somewhat arbitrarily, which affected the absolute values of E. Here it is shown that examination of available experimental and theoretical results allows determination of the best values of n. Using this approach yields n=1.9 for the present series. For the seven reactions which have been studied experimentally, the average deviation of the SECI activation barrier prediction from experiment is 4.0 kJ mol-1. Energy barriers are calculated for another 52 reactions.

  5. An absolute cavity pyrgeometer to measure the absolute outdoor longwave irradiance with traceability to international system of units, SI

    NASA Astrophysics Data System (ADS)

    Reda, Ibrahim; Zeng, Jinan; Scheuch, Jonathan; Hanssen, Leonard; Wilthan, Boris; Myers, Daryl; Stoffel, Tom

    2012-03-01

    This article describes a method of measuring the absolute outdoor longwave irradiance using an absolute cavity pyrgeometer (ACP), U.S. Patent application no. 13/049, 275. The ACP consists of domeless thermopile pyrgeometer, gold-plated concentrator, temperature controller, and data acquisition. The dome was removed from the pyrgeometer to remove errors associated with dome transmittance and the dome correction factor. To avoid thermal convection and wind effect errors resulting from using a domeless thermopile, the gold-plated concentrator was placed above the thermopile. The concentrator is a dual compound parabolic concentrator (CPC) with 180° view angle to measure the outdoor incoming longwave irradiance from the atmosphere. The incoming irradiance is reflected from the specular gold surface of the CPC and concentrated on the 11 mm diameter of the pyrgeometer's blackened thermopile. The CPC's interior surface design and the resulting cavitation result in a throughput value that was characterized by the National Institute of Standards and Technology. The ACP was installed horizontally outdoor on an aluminum plate connected to the temperature controller to control the pyrgeometer's case temperature. The responsivity of the pyrgeometer's thermopile detector was determined by lowering the case temperature and calculating the rate of change of the thermopile output voltage versus the changing net irradiance. The responsivity is then used to calculate the absolute atmospheric longwave irradiance with an uncertainty estimate (U95) of ±3.96 W m-2 with traceability to the International System of Units, SI. The measured irradiance was compared with the irradiance measured by two pyrgeometers calibrated by the World Radiation Center with traceability to the Interim World Infrared Standard Group, WISG. A total of 408 readings were collected over three different nights. The calculated irradiance measured by the ACP was 1.5 W/m2 lower than that measured by the two

  6. 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.

  7. Redefinition of the crater-density and absolute-age boundaries for the chronostratigraphic system of Mars

    USGS Publications Warehouse

    Werner, S.C.; Tanaka, K.L.

    2011-01-01

    For the boundaries of each chronostratigraphic epoch on Mars, we present systematically derived crater-size frequencies based on crater counts of geologic referent surfaces and three proposed " standard" crater size-frequency production distributions as defined by (a) a simple -2 power law, (b) Neukum and Ivanov, (c) Hartmann. In turn, these crater count values are converted to model-absolute ages based on the inferred cratering rate histories. We present a new boundary definition for the Late Hesperian-Early Amazonian transition. Our fitting of crater size-frequency distributions to the chronostratigraphic record of Mars permits the assignment of cumulative counts of craters down to 100. m, 1. km, 2. km, 5. km, and 16. km diameters to martian epochs. Due to differences in the " standard" crater size-frequency production distributions, a generalized crater-density-based definition to the chronostratigraphic system cannot be provided. For the diameter range used for the boundary definitions, the resulting model absolute age fits vary within 1.5% for a given set of production function and chronology model ages. Crater distributions translated to absolute ages utilizing different curve descriptions can result in absolute age differences exceeding 10%. ?? 2011 Elsevier Inc.

  8. Electronic Absolute Cartesian Autocollimator

    NASA Technical Reports Server (NTRS)

    Leviton, Douglas B.

    2006-01-01

    An electronic absolute Cartesian autocollimator performs the same basic optical function as does a conventional all-optical or a conventional electronic autocollimator but differs in the nature of its optical target and the manner in which the position of the image of the target is measured. The term absolute in the name of this apparatus reflects the nature of the position measurement, which, unlike in a conventional electronic autocollimator, is based absolutely on the position of the image rather than on an assumed proportionality between the position and the levels of processed analog electronic signals. The term Cartesian in the name of this apparatus reflects the nature of its optical target. Figure 1 depicts the electronic functional blocks of an electronic absolute Cartesian autocollimator along with its basic optical layout, which is the same as that of a conventional autocollimator. Referring first to the optical layout and functions only, this or any autocollimator is used to measure the compound angular deviation of a flat datum mirror with respect to the optical axis of the autocollimator itself. The optical components include an illuminated target, a beam splitter, an objective or collimating lens, and a viewer or detector (described in more detail below) at a viewing plane. The target and the viewing planes are focal planes of the lens. Target light reflected by the datum mirror is imaged on the viewing plane at unit magnification by the collimating lens. If the normal to the datum mirror is parallel to the optical axis of the autocollimator, then the target image is centered on the viewing plane. Any angular deviation of the normal from the optical axis manifests itself as a lateral displacement of the target image from the center. The magnitude of the displacement is proportional to the focal length and to the magnitude (assumed to be small) of the angular deviation. The direction of the displacement is perpendicular to the axis about which the

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

    NASA Astrophysics Data System (ADS)

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

    2017-08-01

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

  10. Origin of the Non-Arrhenius Behavior of the Rates of Enzymatic Reactions.

    PubMed

    Roy, Subhendu; Schopf, Patrick; Warshel, Arieh

    2017-07-13

    The origin of the non-Arrhenius behavior of the rate constant for hydride transfer enzymatic reactions has been a puzzling problem since its initial observation. This effect has been used originally to support the idea that enzymes work by dynamical effects and more recently to suggest an entropy funnel model. Our analysis, however, has advanced the idea that the reason for the non-Arrhenius trend reflects the temperature dependence of the rearrangements of the protein polar groups in response to the change in the charge distribution of the reacting system during the transition from the ground state (GS) to the transition state (TS). Here we examine the validity of our early proposal by simulating the catalytic reaction of alcohol dehydrogenase (ADH) and determine the microscopic origin of the entropic and enthalpic contributions to the activation barrier. The corresponding analysis establishes the origin of the non-Arrhenius behaviors and quantifies our original suggestion that the classical effect is due to the entropic contributions of the environment. We also find that the quantum effects reflect in part the temperature dependence of the donor-acceptor distance.

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

    NASA Astrophysics Data System (ADS)

    Bunkan, Arne; Amédro, Damien; Crowley, John

    2017-04-01

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

  12. MEERCAT: Multiplexed Efficient Cell Free Expression of Recombinant QconCATs For Large Scale Absolute Proteome Quantification*

    PubMed Central

    Takemori, Nobuaki; Takemori, Ayako; Tanaka, Yuki; Endo, Yaeta; Hurst, Jane L.; Gómez-Baena, Guadalupe; Harman, Victoria M.; Beynon, Robert J.

    2017-01-01

    A major challenge in proteomics is the absolute accurate quantification of large numbers of proteins. QconCATs, artificial proteins that are concatenations of multiple standard peptides, are well established as an efficient means to generate standards for proteome quantification. Previously, QconCATs have been expressed in bacteria, but we now describe QconCAT expression in a robust, cell-free system. The new expression approach rescues QconCATs that previously were unable to be expressed in bacteria and can reduce the incidence of proteolytic damage to QconCATs. Moreover, it is possible to cosynthesize QconCATs in a highly-multiplexed translation reaction, coexpressing tens or hundreds of QconCATs simultaneously. By obviating bacterial culture and through the gain of high level multiplexing, it is now possible to generate tens of thousands of standard peptides in a matter of weeks, rendering absolute quantification of a complex proteome highly achievable in a reproducible, broadly deployable system. PMID:29055021

  13. Comparison of Nernst-Planck and reaction rate models for multiply occupied channels.

    PubMed Central

    Levitt, D G

    1982-01-01

    The Nernst-Planck continuum equation for a channel that can be occupied by at most two ions is solved for two different physical cases. The first case is for the assumption that the water and ion cannot get around each other anywhere in the channel, so that if there are two ions in the channel the distance between them is fixed by the number of water molecules between them. The second case is for the assumption that there are regions at he ends of the channel where the ions and water can get around each other. For these two cases, the validity of the simple two-site reaction-rate approximation when there is a continuously varying central energy barrier was evaluated by comparing it with the exact Nernst-Planck solution. For the first continuum case, the kinetics for the continuum and reaction-rate models are nearly identical. For the second case, the agreement depends on the strength of the ion-ion interaction energy. For a low interaction energy (large channel diameter) a high ion concentrations, there is a large difference in the flux as a function of voltage for the two models-with the continuum flux becoming more than four times larger at 250 mV. Simple analytical expressions are derived for the two-ion continuum channel for the case where the ends are in equilibrium with the bulk solution and for the case where ion mobility becomes zero when there are two ions in the channel. The implications of these results for biological channels are discussed. PMID:6280783

  14. Monte carlo simulations of Yttrium reaction rates in Quinta uranium target

    NASA Astrophysics Data System (ADS)

    Suchopár, M.; Wagner, V.; Svoboda, O.; Vrzalová, J.; Chudoba, P.; Tichý, P.; Kugler, A.; Adam, J.; Závorka, L.; Baldin, A.; Furman, W.; Kadykov, M.; Khushvaktov, J.; Solnyshkin, A.; Tsoupko-Sitnikov, V.; Tyutyunnikov, S.; Bielewicz, M.; Kilim, S.; Strugalska-Gola, E.; Szuta, M.

    2017-03-01

    The international collaboration Energy and Transmutation of Radioactive Waste (E&T RAW) performed intensive studies of several simple accelerator-driven system (ADS) setups consisting of lead, uranium and graphite which were irradiated by relativistic proton and deuteron beams in the past years at the Joint Institute for Nuclear Research (JINR) in Dubna, Russia. The most recent setup called Quinta, consisting of natural uranium target-blanket and lead shielding, was irradiated by deuteron beams in the energy range between 1 and 8 GeV in three accelerator runs at JINR Nuclotron in 2011 and 2012 with yttrium samples among others inserted inside the setup to measure the neutron flux in various places. Suitable activation detectors serve as one of possible tools for monitoring of proton and deuteron beams and for measurements of neutron field distribution in ADS studies. Yttrium is one of such suitable materials for monitoring of high energy neutrons. Various threshold reactions can be observed in yttrium samples. The yields of isotopes produced in the samples were determined using the activation method. Monte Carlo simulations of the reaction rates leading to production of different isotopes were performed in the MCNPX transport code and compared with the experimental results obtained from the yttrium samples.

  15. Integer, fractional, and anomalous quantum Hall effects explained with Eyring's rate process theory and free volume concept.

    PubMed

    Hao, Tian

    2017-02-22

    The Hall effects, especially the integer, fractional and anomalous quantum Hall effects, have been addressed using Eyring's rate process theory and free volume concept. The basic assumptions are that the conduction process is a common rate controlled "reaction" process that can be described with Eyring's absolute rate process theory; the mobility of electrons should be dependent on the free volume available for conduction electrons. The obtained Hall conductivity is clearly quantized as with prefactors related to both the magnetic flux quantum number and the magnetic quantum number via the azimuthal quantum number, with and without an externally applied magnetic field. This article focuses on two dimensional (2D) systems, but the approaches developed in this article can be extended to 3D systems.

  16. Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth.

    PubMed

    Sutter, Eli A; Sutter, Peter W

    2014-12-03

    In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important, as they provide direct insight into processes in liquids, such as solution growth of nanoparticles, among others. In liquid cell TEM/STEM redox reaction experiments, the hydrated electrons e(-)aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e(-)aq generated by the electron beam during in situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e(-)aq]. By comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e(-)aq] but also the rate of reduction of a metal-ion complex to zerovalent metal atoms in solution.

  17. Applying constraints on model-based methods: Estimation of rate constants in a second order consecutive reaction

    NASA Astrophysics Data System (ADS)

    Kompany-Zareh, Mohsen; Khoshkam, Maryam

    2013-02-01

    This paper describes estimation of reaction rate constants and pure ultraviolet/visible (UV-vis) spectra of the component involved in a second order consecutive reaction between Ortho-Amino benzoeic acid (o-ABA) and Diazoniom ions (DIAZO), with one intermediate. In the described system, o-ABA was not absorbing in the visible region of interest and thus, closure rank deficiency problem did not exist. Concentration profiles were determined by solving differential equations of the corresponding kinetic model. In that sense, three types of model-based procedures were applied to estimate the rate constants of the kinetic system, according to Levenberg/Marquardt (NGL/M) algorithm. Original data-based, Score-based and concentration-based objective functions were included in these nonlinear fitting procedures. Results showed that when there is error in initial concentrations, accuracy of estimated rate constants strongly depends on the type of applied objective function in fitting procedure. Moreover, flexibility in application of different constraints and optimization of the initial concentrations estimation during the fitting procedure were investigated. Results showed a considerable decrease in ambiguity of obtained parameters by applying appropriate constraints and adjustable initial concentrations of reagents.

  18. Sleeve reaction chamber system

    DOEpatents

    Northrup, M Allen [Berkeley, CA; Beeman, Barton V [San Mateo, CA; Benett, William J [Livermore, CA; Hadley, Dean R [Manteca, CA; Landre, Phoebe [Livermore, CA; Lehew, Stacy L [Livermore, CA; Krulevitch, Peter A [Pleasanton, CA

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  19. Absolute rate constants for O + NO + M /= He, Ne, Ar, Kr/ yields NO2 + M from 217-500 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Payne, W. A.; Whytock, D. A.

    1976-01-01

    Rate constants for the reaction O + NO + M yields NO2 + M have been obtained at temperatures from 217-500 K in four different rare gases by a method combining flash photolysis with time resolved detection of O(3-P) by resonance fluorescence. The measured rate constants in Arrhenius form are (10.8 plus or minus 1.2) x 10 to the -33rd exp(1040 plus or minus 60/1.987 T) for helium; (9.01 plus or minus 1.16) x 10 to the -33rd exp(1180 plus or minus 70/1.987 T) for argon; (9.33 plus or minus 1.10) x 10 to the -33rd exp(1030 plus or minus 60/1.987 T) for neon; and (9.52 plus or minus 1.10) x 10 to the -33rd exp(1140 plus or minus 70/1.987 T) for krypton in units of cm to the 6th/sq molecule/s.

  20. On rates and mechanisms of OH and O3 reactions with isoprene-derived hydroxy nitrates.

    PubMed

    Lee, Lance; Teng, Alex P; Wennberg, Paul O; Crounse, John D; Cohen, Ronald C

    2014-03-06

    Eight distinct hydroxy nitrates are stable products of the first step in the atmospheric oxidation of isoprene by OH. The subsequent chemical fate of these molecules affects global and regional production of ozone and aerosol as well as the location of nitrogen deposition. We synthesized and purified 3 of the 8 isoprene hydroxy nitrate isomers: (E/Z)-2-methyl-4-nitrooxybut-2-ene-1-ol and 3-methyl-2-nitrooxybut-3-ene-1-ol. Oxidation of these molecules by OH and ozone was studied using both chemical ionization mass spectrometry and thermo-dissociation laser induced fluorescence. The OH reaction rate constants at 300 K measured relative to propene at 745 Torr are (1.1 ± 0.2) × 10(-10) cm(3) molecule(-1) s(-1) for both the E and Z isomers and (4.2 ± 0.7) × 10(-11) cm(3) molecule(-1) s(-1) for the third isomer. The ozone reaction rate constants for (E/Z)-2-methyl-4-nitrooxybut-2-ene-1-ol are (2.7 ± 0.5) × 10(-17) and (2.9 ± 0.5) × 10(-17) cm(3) molecule(-1) s(-1), respectively. 3-Methyl-2-nitrooxybut-3-ene-1-ol reacts with ozone very slowly, within the range of (2.5-5) × 10(-19) cm(3) molecule(-1) s(-1). Reaction pathways, product yields, and implications for atmospheric chemistry are discussed. A condensed mechanism suitable for use in atmospheric chemistry models is presented.

  1. Geraniol (2,6-dimethyl-2,6-octadien-8-ol) reactions with ozone and OH radical: Rate constants and gas-phase products

    NASA Astrophysics Data System (ADS)

    Forester, Crystal D.; Ham, Jason E.; Wells, J. R.

    The bimolecular rate constants, kOH+geraniol, (231±58)×10 -12 cm 3 molecule -1 s -1 and k+geraniol, (9.3±2.3)×10 -16 cm 3 molecule -1 s -1, were measured using the relative rate technique for the reaction of the hydroxyl radical (OH) and ozone (O 3) with 2,6-dimethyl-2,6-octadien-8-ol (geraniol) at (297±3) K and 1 atmosphere total pressure. To more clearly define part of geraniol's indoor environment degradation mechanism, the products of the geraniol+OH and geraniol+O 3 reactions were also investigated. The identified geraniol+OH and geraniol+O 3 reaction products were: acetone, hydroxyacetaldehyde (glycolaldehyde, HC( dbnd O)CH 2OH), ethanedial (glyoxal, HC( dbnd O)C( dbnd O)H), and 2-oxopropanal (methylglyoxal, CH 3C( dbnd O)C( dbnd O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose 4-oxopentanal as the other major geraniol+OH and geraniol+O 3 reaction product. The elucidation of this other reaction product was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible geraniol+OH and geraniol+O 3 reaction mechanisms based on previously published volatile organic compound+OH and volatile organic compound+O 3 gas-phase reaction mechanisms.

  2. Numerical calculation of protein-ligand binding rates through solution of the Smoluchowski equation using smooth particle hydrodynamics

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

    Pan, Wenxiao; Daily, Michael D.; Baker, Nathan A.

    2015-12-01

    We demonstrate the accuracy and effectiveness of a Lagrangian particle-based method, smoothed particle hydrodynamics (SPH), to study diffusion in biomolecular systems by numerically solving the time-dependent Smoluchowski equation for continuum diffusion. The numerical method is first verified in simple systems and then applied to the calculation of ligand binding to an acetylcholinesterase monomer. Unlike previous studies, a reactive Robin boundary condition (BC), rather than the absolute absorbing (Dirichlet) boundary condition, is considered on the reactive boundaries. This new boundary condition treatment allows for the analysis of enzymes with "imperfect" reaction rates. Rates for inhibitor binding to mAChE are calculated atmore » various ionic strengths and compared with experiment and other numerical methods. We find that imposition of the Robin BC improves agreement between calculated and experimental reaction rates. Although this initial application focuses on a single monomer system, our new method provides a framework to explore broader applications of SPH in larger-scale biomolecular complexes by taking advantage of its Lagrangian particle-based nature.« less

  3. Response to the Comment on Paper 'Water vapor Enhancement of Rates of Peroxy Radical Reactions', Int. J. Chem. Kinetics, 47, 395, 2015

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

    Kumbhani, Sambhav R.; Cline, Taylor S.; Killian, Marie C.

    Comments provided here aid in understanding the effect of water vapor on the rate of the self-reaction of HOCH2CH2O2 recently reported by Kumbhani et al. [1] Kumbhani et al. asserts that water vapor increases the rate of the HOCH2CH2O2 self-reaction by formation of an HOCH2CH2O2-H2O complex.

  4. The effect of viscous flow and thermal flux on the rate of chemical reaction in dilute gases

    NASA Astrophysics Data System (ADS)

    Cukrowski, A. S.; Popielawski, J.

    1986-11-01

    Expression for the corrections describing the effect of viscous flow and thermal flux on the rate of chemical reaction have been derived for the reaction A + A = B + C described by Prigogine-Xhrouet and Present. These corrections are calculated for the velocity distribution function up to the second-order approximation for the Chapman-Enskog solution of the Boltzmann equation. These corrections are shown to be the same as those which would follow after application of the method of linearized-moments equations described by Eu and Li. The effects of viscous flow and thermal flux are presented as functions of activation energy of chemical reaction, temperature, density, coefficients of shear viscosity of thermal conductivity, and relevant gradients of mean molecular velocity or temperature. It is pointed out that for very slow reactions and for very large gradients (e.g. in shock waves) these effects can be quite significant.

  5. Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

    PubMed

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

    Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P < 10 Torr with the high pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

  6. Ultrahigh-Repetition Pulse Train with Absolute-Phase Control Produced by AN Adiabatic Raman Process

    NASA Astrophysics Data System (ADS)

    Katsuragawa, M.; Suzuki, T.; Shiraga, K.; Arakawa, M.; Onose, T.; Yokoyama, K.; Hong, F. L.; Misawa, K.

    2010-02-01

    We describe the generation of an ultrahigh-repetition-rate train of ultrashort pulses on the basis of an adiabatic Raman process. We also describe recent progress in studies toward the ultimate regime: realization of an ultrahigh-repetition-rate train of monocycle pulses with control of the absolute phase. We comment on the milestones expected in the near future in terms of the study of such novel light sources and the new field of optical science stimulated by their development.

  7. Temperature Dependent Rate Coefficients for the Gas-Phase Reaction of the OH Radical with Linear (L2, L3) and Cyclic (D3, D4) Permethylsiloxanes.

    PubMed

    Bernard, François; Papanastasiou, Dimitrios K; Papadimitriou, Vassileios C; Burkholder, James B

    2018-05-03

    Permethylsiloxanes are emitted into the atmosphere during production and use as personal care products, lubricants, and cleaning agents. The predominate atmospheric loss process for permethylsiloxanes is expected to be via gas-phase reaction with the OH radical. In this study, rate coefficients, k(T), for the OH radical gas-phase reaction with the two simplest linear and cyclic permethylsiloxanes were measured using a pulsed laser photolysis-laser induced fluorescence technique over the temperature range of 240-370 K and a relative rate method at 294 K: hexamethyldisiloxane ((CH 3 ) 3 SiOSi(CH 3 ) 3 , L 2 ), k 1 ; octamethyltrisiloxane ([(CH 3 ) 3 SiO] 2 Si(CH 3 ) 2 , L 3 ), k 2 ; hexamethylcyclotrisiloxane ([-Si(CH 3 ) 2 O-] 3 , D 3 ), k 3 ; and octamethylcyclotetrasiloxane ([-Si(CH 3 ) 2 O-] 4 , D 4 ), k 4 . The obtained k(294 K) values and temperature-dependence expressions for the 240-370 K temperature range are (cm 3 molecule -1 s -1 , 2σ absolute uncertainties): k 1 (294 K) = (1.28 ± 0.08) × 10 -12 , k 1 ( T) = (1.87 ± 0.18) × 10 -11 exp(-(791 ± 27)/ T); k 2 (294 K) = (1.72 ± 0.10) × 10 -12 , k 2 ( T) = 1.96 × 10 -13 (T/298) 4.34 exp(657/ T); k 3 (294 K) = (0.82 ± 0.05) × 10 -12 , k 3 ( T) = (1.29 ± 0.19) × 10 -11 exp(-(805 ± 43)/ T); and k 4 (294 K) = (1.12 ± 0.10) × 10 -12 , k 4 ( T) = (1.80 ± 0.26) × 10 -11 exp(-(816 ± 43)/ T). The cyclic molecules were found to be less reactive than the analogous linear molecule with the same number of -CH 3 groups, while the linear and cyclic permethylsiloxane reactivity both increase with the increasing number of CH 3 - groups. The present results are compared with previous rate coefficient determinations where available. The permethylsiloxanes included in this study are atmospherically short-lived compounds with estimated atmospheric lifetimes of 11, 8, 17, and 13 days, respectively.

  8. Constraining the astrophysical 23Mg(p, γ)24Al reaction rate using the 23Na(d,p)24Na reaction

    NASA Astrophysics Data System (ADS)

    Bennett, E. A.; Catford, W. N.; Christian, G.; Dede, S.; Hallam, S.; Lotay, G.; Ota, S.; Saastamoinen, A.; Wilkinson, R.

    2017-09-01

    The 23Mg(p, γ)24Al reaction provides an escape from the Ne-Na cycle in classical novae and is therefore important in understanding nova nucleosynthesis in the A > 20 mass range. Although several resonances may contribute to the overall rate at novae temperatures, the resonance at 475 keV is thought to be dominant. The strength of this resonance has been directly measured using a radioactive 23Mg beam impinging on a windowless H2 gas target; however, recent high-precision 24Al mass measurements have called this result into question. Here we make an indirect measurement using the 23Na(d,p)24Na reaction in inverse kinematics to study the mirror state of the 475 keV resonance in 24Na. The experiment, performed at the Texas A&M Cyclotron Institute, utilized the TIARA silicon array, four HPGe detectors, and the MDM spectrometer to measure the excited states of the 24Na nucleus. Preliminary results from the experiment will be presented along with progress from the ongoing analysis.

  9. Studying Electron-Capture on ^64Zn in Supernovae with the (t,^3He) Charge-Exchange Reaction

    NASA Astrophysics Data System (ADS)

    Hitt, G. W.; Austin, Sam M.; Bazin, D.; Gade, A.; Guess, C. J.; Galaviz-Redondo, D.; Shimbara, Y.; Tur, C.; Zegers, R. G. T.; Horoi, M.; Howard, M. E.; Smith, E. E.

    2008-10-01

    A secondary, 115 MeV/u triton beam has been developed at NSCL for use in (t,^3He) charge-exchange(CE) reaction studies. This (n,p)-type CE reaction is useful for extracting the full Gamow-Teller (GT) response of the nucleus, overcoming Q-value restrictions present in conventional beta-decay studies. The strength (B(GT)) in ^64Cu has been determined from the absolute cross section measurement of ^64Zn(t,^3He) near zero-degrees, exploiting an empirical proportionality between cross section and B(GT). The detailed features of the B(GT) distribution in a nucleus has an important impact on electron-capture (EC) rates in Type Ia and Core-Collapse supernovae. The measured B(GT) in ^64Cu is directly compared with the results of modern shell model interactions which are used to calculate the GT contribution to EC on nuclei in supernova simulations.

  10. Determination of the thermal rate coefficient, products, and branching ratios for the reaction of O/+/ /D-2/ with N2

    NASA Technical Reports Server (NTRS)

    Torr, D. G.; Torr, M. R.

    1980-01-01

    Atmosphere Explorer-C satellite measurements are used to determine rate coefficients (RCs) for the following reactions: O(+)(D-2) + N2 yields N2(+) + O (reaction 1), O(+)(D-2) + N2 yields O(+)(S-4) + N2 (reaction 2), and O(+)(D-2) + N2 yields NO(+) + N (reaction 3). Results show the RC for reaction 1 to be 1 (plus 1 or minus 0.5) x 10 to the -10th cu cm per sec, for reaction 2 to be 3 (plus 1 or minus 2) x 10 to the -11th cu cm per sec, and 3 to be less than 5.5 x 10 to the -11th cu cm per sec. It is also found that the reaction of O(+)(D-2) with N2 does not constitute a detectable source of NO(+) ions in the thermosphere.

  11. Uncertainty quantification of reaction mechanisms accounting for correlations introduced by rate rules and fitted Arrhenius parameters

    DOE PAGES

    Prager, Jens; Najm, Habib N.; Sargsyan, Khachik; ...

    2013-02-23

    We study correlations among uncertain Arrhenius rate parameters in a chemical model for hydrocarbon fuel-air combustion. We consider correlations induced by the use of rate rules for modeling reaction rate constants, as well as those resulting from fitting rate expressions to empirical measurements arriving at a joint probability density for all Arrhenius parameters. We focus on homogeneous ignition in a fuel-air mixture at constant-pressure. We also outline a general methodology for this analysis using polynomial chaos and Bayesian inference methods. Finally, we examine the uncertainties in both the Arrhenius parameters and in predicted ignition time, outlining the role of correlations,more » and considering both accuracy and computational efficiency.« less

  12. Patch testing with serial dilutions and thin-layer chromatograms of oak moss absolutes containing high and low levels of atranol and chloroatranol.

    PubMed

    Mowitz, Martin; Zimerson, Erik; Svedman, Cecilia; Bruze, Magnus

    2013-12-01

    Oak moss absolute (Evernia prunastri extract) contains a large number of substances, among them the potent allergens atranol and chloroatranol. Since 2008, their content in oak moss absolute has been restricted by the International Fragrance Association to a maximum level of 100 ppm each. To compare the elicitation capacities of a traditional (sample A) and a treated (sample B) oak moss absolute containing, in total, 27 000 and 66 ppm of atranol and chloroatranol, respectively, and to investigate reactions to components of oak moss absolute separated by thin-layer chromatography (TLC). Fifteen oak moss-allergic subjects were patch tested with serial dilutions and TLC strips of samples A and B. Fifteen subjects reacted to sample A at concentrations ≤ 2.0%, and 2 subjects reacted to sample B at 2.0% but not to lower concentrations. Among 13 subjects reacting to the TLC strip of sample A, 11 reacted to spots with retardation factor values corresponding to those of atranol and/or chloroatranol, and 11 reacted to other areas on the TLC strip. Only one subject reacted to the TLC strip of sample B. The patch test reactivity of sample B was significantly lower than that of sample A. The TLC patch tests indicate the presence of sensitizers other than atranol and chloroatranol in oak moss absolute. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  13. Co-solvent effects on reaction rate and reaction equilibrium of an enzymatic peptide hydrolysis.

    PubMed

    Wangler, A; Canales, R; Held, C; Luong, T Q; Winter, R; Zaitsau, D H; Verevkin, S P; Sadowski, G

    2018-04-25

    This work presents an approach that expresses the Michaelis constant KaM and the equilibrium constant Kth of an enzymatic peptide hydrolysis based on thermodynamic activities instead of concentrations. This provides KaM and Kth values that are independent of any co-solvent. To this end, the hydrolysis reaction of N-succinyl-l-phenylalanine-p-nitroanilide catalysed by the enzyme α-chymotrypsin was studied in pure buffer and in the presence of the co-solvents dimethyl sulfoxide, trimethylamine-N-oxide, urea, and two salts. A strong influence of the co-solvents on the measured Michaelis constant (KM) and equilibrium constant (Kx) was observed, which was found to be caused by molecular interactions expressed as activity coefficients. Substrate and product activity coefficients were used to calculate the activity-based values KaM and Kth for the co-solvent free reaction. Based on these constants, the co-solvent effect on KM and Kx was predicted in almost quantitative agreement with the experimental data. The approach presented here does not only reveal the importance of understanding the thermodynamic non-ideality of reactions taking place in biological solutions and in many technological applications, it also provides a framework for interpreting and quantifying the multifaceted co-solvent effects on enzyme-catalysed reactions that are known and have been observed experimentally for a long time.

  14. Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

    NASA Technical Reports Server (NTRS)

    Hoobler, Ray J.; Leone, Stephen R.

    1997-01-01

    Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

  15. Using, Seeing, Feeling, and Doing Absolute Value for Deeper Understanding

    ERIC Educational Resources Information Center

    Ponce, Gregorio A.

    2008-01-01

    Using sticky notes and number lines, a hands-on activity is shared that anchors initial student thinking about absolute value. The initial point of reference should help students successfully evaluate numeric problems involving absolute value. They should also be able to solve absolute value equations and inequalities that are typically found in…

  16. Numerical calculation of protein-ligand binding rates through solution of the Smoluchowski equation using smoothed particle hydrodynamics

    DOE PAGES

    Pan, Wenxiao; Daily, Michael; Baker, Nathan A.

    2015-05-07

    Background: The calculation of diffusion-controlled ligand binding rates is important for understanding enzyme mechanisms as well as designing enzyme inhibitors. Methods: We demonstrate the accuracy and effectiveness of a Lagrangian particle-based method, smoothed particle hydrodynamics (SPH), to study diffusion in biomolecular systems by numerically solving the time-dependent Smoluchowski equation for continuum diffusion. Unlike previous studies, a reactive Robin boundary condition (BC), rather than the absolute absorbing (Dirichlet) BC, is considered on the reactive boundaries. This new BC treatment allows for the analysis of enzymes with “imperfect” reaction rates. Results: The numerical method is first verified in simple systems and thenmore » applied to the calculation of ligand binding to a mouse acetylcholinesterase (mAChE) monomer. Rates for inhibitor binding to mAChE are calculated at various ionic strengths and compared with experiment and other numerical methods. We find that imposition of the Robin BC improves agreement between calculated and experimental reaction rates. Conclusions: Although this initial application focuses on a single monomer system, our new method provides a framework to explore broader applications of SPH in larger-scale biomolecular complexes by taking advantage of its Lagrangian particle-based nature.« less

  17. Pulsed EPR measurements on reaction rate constants for addition of photo-generated radicals to double bonds of diethyl fumarate and diethyl maleate

    NASA Astrophysics Data System (ADS)

    Takahashi, Hirona; Hagiwara, Kenta; Kawai, Akio

    2016-11-01

    Addition reaction of photo-generated radicals to double bonds of diethyl fumarate (deF) and diethyl maleate (deM), which are geometrical isomers, was studied by means of time-resolved- (TR-) and pulsed-electron paramagnetic resonance (EPR). Analysis of TR-EPR spectra indicates that adduct radicals from deF and deM should have the same structure. The double bonds of these monomers are converted to single ones by addition reaction, which allows hindered internal rotation to give the same structure of adduct radical. The rate constants for addition reaction of photo-generated radicals were determined by Stern-Volmer analysis of the decay time of electron spin-echo intensity of these radicals measured by the pulsed EPR method. Rate constants for deF were found to be larger than those for deM. This relation is in good consistent with efficiency of polymerisation of deF and deM. Experimentally determined rate constants were evaluated by introducing the addition reaction model on the basis of two important factors enthalpy and polar effects.

  18. Absolute nuclear material assay using count distribution (LAMBDA) space

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

    Prasad, Mano K.; Snyderman, Neal J.; Rowland, Mark S.

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  19. Planck absolute entropy of a rotating BTZ black hole

    NASA Astrophysics Data System (ADS)

    Riaz, S. M. Jawwad

    2018-04-01

    In this paper, the Planck absolute entropy and the Bekenstein-Smarr formula of the rotating Banados-Teitelboim-Zanelli (BTZ) black hole are presented via a complex thermodynamical system contributed by its inner and outer horizons. The redefined entropy approaches zero as the temperature of the rotating BTZ black hole tends to absolute zero, satisfying the Nernst formulation of a black hole. Hence, it can be regarded as the Planck absolute entropy of the rotating BTZ black hole.

  20. Absolute nuclear material assay using count distribution (LAMBDA) space

    DOEpatents

    Prasad, Manoj K [Pleasanton, CA; Snyderman, Neal J [Berkeley, CA; Rowland, Mark S [Alamo, CA

    2012-06-05

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

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

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

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

    2015-11-12

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

  2. 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.

  3. Absolute and relative reliability of acute effects of aerobic exercise on executive function in seniors.

    PubMed

    Donath, Lars; Ludyga, Sebastian; Hammes, Daniel; Rossmeissl, Anja; Andergassen, Nadin; Zahner, Lukas; Faude, Oliver

    2017-10-25

    Aging is accompanied by a decline of executive function. Aerobic exercise training induces moderate improvements of cognitive domains (i.e., attention, processing, executive function, memory) in seniors. Most conclusive data are obtained from studies with dementia or cognitive impairment. Confident detection of exercise training effects requires adequate between-day reliability and low day-to-day variability obtained from acute studies, respectively. These absolute and relative reliability measures have not yet been examined for a single aerobic training session in seniors. Twenty-two healthy and physically active seniors (age: 69 ± 3 y, BMI: 24.8 ± 2.2, VO 2peak : 32 ± 6 mL/kg/bodyweight) were enrolled in this randomized controlled cross-over study. A repeated between-day comparison [i.e., day 1 (habituation) vs. day 2 & day 2 vs. day 3] of executive function testing (Eriksen-Flanker-Test, Stroop-Color-Test, Digit-Span, Five-Point-Test) before and after aerobic cycling exercise at 70% of the heart rate reserve [0.7 × (HR max - HR rest )] was conducted. Reliability measures were calculated for pre, post and change scores. Large between-day differences between day 1 and 2 were found for reaction times (Flanker- and Stroop Color testing) and completed figures (Five-Point test) at pre and post testing (0.002 < p < 0.05, 0.16 < ɳ p 2  < 0.38). These differences notably declined when comparing day 2 and 3. Absolute between days variability (CoV) dropped from 10 to 5% when comparing day 2 vs. day 3 instead of day 1 vs. day 2. Also ICC ranges increased from day 1 vs. day 2 (0.65 < ICC < 0.87) to day 2 vs. day 3 (0.40 < ICC < 0.93). Interestingly, reliability measures for pre-post change scores were low (0.02 < ICC < 0.71). These data did not improve when comparing day 2 with day 3. During inhibition tests, reaction times showed excellent reliability values compared to the poor to fair reliability of accuracy. Notable habituation to the

  4. Solutions to a reduced Poisson–Nernst–Planck system and determination of reaction rates

    PubMed Central

    Li, Bo; Lu, Benzhuo; Wang, Zhongming; McCammon, J. Andrew

    2010-01-01

    We study a reduced Poisson–Nernst–Planck (PNP) system for a charged spherical solute immersed in a solvent with multiple ionic or molecular species that are electrostatically neutralized in the far field. Some of these species are assumed to be in equilibrium. The concentrations of such species are described by the Boltzmann distributions that are further linearized. Others are assumed to be reactive, meaning that their concentrations vanish when in contact with the charged solute. We present both semi-analytical solutions and numerical iterative solutions to the underlying reduced PNP system, and calculate the reaction rate for the reactive species. We give a rigorous analysis on the convergence of our simple iteration algorithm. Our numerical results show the strong dependence of the reaction rates of the reactive species on the magnitude of its far field concentration as well as on the ionic strength of all the chemical species. We also find non-monotonicity of electrostatic potential in certain parameter regimes. The results for the reactive system and those for the non-reactive system are compared to show the significant differences between the two cases. Our approach provides a means of solving a PNP system which in general does not have a closed-form solution even with a special geometrical symmetry. Our findings can also be used to test other numerical methods in large-scale computational modeling of electro-diffusion in biological systems. PMID:20228879

  5. Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

    PubMed

    Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco B C; Hase, William L

    2018-05-31

    The reaction of 3 CH 2 with 3 O 2 is of fundamental importance in combustion, and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K, and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH 2 OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H 2 CO + O( 3 P), while the singlet surface leads to eight product channels with their relative importance as CO + H 2 O > CO + OH + H ∼ H 2 CO + O( 1 D) > HCO + OH ∼ CO 2 + H 2 ∼ CO + H 2 + O( 1 D) > CO 2 + H + H > HCO + O( 1 D) + H. The reaction on the singlet PES is barrierless, consistent with experiment, and the total rate constant on the singlet surface is (0.93 ± 0.22) × 10 -12 cm 3 molecule -1 s -1 in comparison to the recommended experimental rate constant of 3.3 × 10 -12 cm 3 molecule -1 s -1 . The simulation product yields for the singlet PES are compared with experiment, and the most significant differences are for H, CO 2 , and H 2 O. The reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address (1) the barrier on the triplet PES for 3 CH 2 + 3 O 2 → 3 CH 2 OO, (2) the temperature dependence of the 3 CH 2 + 3 O 2 reaction rate constant and product branching ratios, and (3) the possible non-RRKM dynamics of the 1 CH 2 OO Criegee intermediate.

  6. Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

    NASA Technical Reports Server (NTRS)

    Gokoglu, Suleyman A.

    1988-01-01

    This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

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

  8. Kinetics of the Reactions between the Criegee Intermediate CH2OO and Alcohols.

    PubMed

    Tadayon, Sara V; Foreman, Elizabeth S; Murray, Craig

    2018-01-11

    Reactions of the simplest Criegee intermediate (CH 2 OO) with a series of alcohols have been studied in a flash photolysis flow reactor. Laser photolysis of diiodomethane at 355 nm in the presence of molecular oxygen was used to produce CH 2 OO, and the absolute number densities were determined as a function of delay time from analysis of broadband transient absorption spectra obtained using a pulsed LED. The kinetics for the reactions of CH 2 OO with methanol, ethanol, and 2-propanol were measured under pseudo-first-order conditions at 295 K, yielding rate constants of (1.4 ± 0.4) × 10 -13 cm 3 s -1 , (2.3 ± 0.6) × 10 -13 cm 3 s -1 , and (1.9 ± 0.5) × 10 -13 cm 3 s -1 , respectively. Complementary ab initio calculations were performed at the CCSD(T)/aug-cc-pVTZ//CCSD/cc-pVDZ level of theory to characterize stationary points on the reaction enthalpy and free energy surfaces and to elucidate the thermochemistry and mechanisms. The reactions proceed over free energy barriers of ∼8 kcal mol -1 to form geminal alkoxymethyl hydroperoxides: methoxymethyl hydroperoxide (MMHP), ethoxymethyl hydroperoxide (EMHP), and isopropoxymethyl hydroperoxide (PMHP). The experimental and theoretical results are compared to reactions of CH 2 OO with other hydroxylic compounds, such as water and carboxylic acids, and trends in reactivity are discussed.

  9. 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.

  10. Novalis' Poetic Uncertainty: A "Bildung" with the Absolute

    ERIC Educational Resources Information Center

    Mika, Carl

    2016-01-01

    Novalis, the Early German Romantic poet and philosopher, had at the core of his work a mysterious depiction of the "absolute." The absolute is Novalis' name for a substance that defies precise knowledge yet calls for a tentative and sensitive speculation. How one asserts a truth, represents an object, and sets about encountering things…

  11. Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Wells, J. R.; Nicovich, J. M.

    1997-01-01

    The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

  12. Population-based absolute risk estimation with survey data

    PubMed Central

    Kovalchik, Stephanie A.; Pfeiffer, Ruth M.

    2013-01-01

    Absolute risk is the probability that a cause-specific event occurs in a given time interval in the presence of competing events. We present methods to estimate population-based absolute risk from a complex survey cohort that can accommodate multiple exposure-specific competing risks. The hazard function for each event type consists of an individualized relative risk multiplied by a baseline hazard function, which is modeled nonparametrically or parametrically with a piecewise exponential model. An influence method is used to derive a Taylor-linearized variance estimate for the absolute risk estimates. We introduce novel measures of the cause-specific influences that can guide modeling choices for the competing event components of the model. To illustrate our methodology, we build and validate cause-specific absolute risk models for cardiovascular and cancer deaths using data from the National Health and Nutrition Examination Survey. Our applications demonstrate the usefulness of survey-based risk prediction models for predicting health outcomes and quantifying the potential impact of disease prevention programs at the population level. PMID:23686614

  13. Absolute marine gravimetry with matter-wave interferometry.

    PubMed

    Bidel, Y; Zahzam, N; Blanchard, C; Bonnin, A; Cadoret, M; Bresson, A; Rouxel, D; Lequentrec-Lalancette, M F

    2018-02-12

    Measuring gravity from an aircraft or a ship is essential in geodesy, geophysics, mineral and hydrocarbon exploration, and navigation. Today, only relative sensors are available for onboard gravimetry. This is a major drawback because of the calibration and drift estimation procedures which lead to important operational constraints. Atom interferometry is a promising technology to obtain onboard absolute gravimeter. But, despite high performances obtained in static condition, no precise measurements were reported in dynamic. Here, we present absolute gravity measurements from a ship with a sensor based on atom interferometry. Despite rough sea conditions, we obtained precision below 10 -5  m s -2 . The atom gravimeter was also compared with a commercial spring gravimeter and showed better performances. This demonstration opens the way to the next generation of inertial sensors (accelerometer, gyroscope) based on atom interferometry which should provide high-precision absolute measurements from a moving platform.

  14. HO + CO reaction rates and H/D kinetic isotope effects: master equation models with ab initio SCTST rate constants.

    PubMed

    Weston, Ralph E; Nguyen, Thanh Lam; Stanton, John F; Barker, John R

    2013-02-07

    Ab initio microcanonical rate constants were computed using Semi-Classical Transition State Theory (SCTST) and used in two master equation formulations (1D, depending on active energy with centrifugal corrections, and 2D, depending on total energy and angular momentum) to compute temperature-dependent rate constants for the title reactions using a potential energy surface obtained by sophisticated ab initio calculations. The 2D master equation was used at the P = 0 and P = ∞ limits, while the 1D master equation with centrifugal corrections and an empirical energy transfer parameter could be used over the entire pressure range. Rate constants were computed for 75 K ≤ T ≤ 2500 K and 0 ≤ [He] ≤ 10(23) cm(-3). For all temperatures and pressures important for combustion and for the terrestrial atmosphere, the agreement with the experimental rate constants is very good, but at very high pressures and T ≤ 200 K, the theoretical rate constants are significantly smaller than the experimental values. This effect is possibly due to the presence in the experiments of dimers and prereactive complexes, which were not included in the model calculations. The computed H/D kinetic isotope effects are in acceptable agreement with experimental data, which show considerable scatter. Overall, the agreement between experimental and theoretical H/D kinetic isotope effects is much better than in previous work, and an assumption of non-RRKM behavior does not appear to be needed to reproduce experimental observations.

  15. Single cell digital polymerase chain reaction on self-priming compartmentalization chip.

    PubMed

    Zhu, Qiangyuan; Qiu, Lin; Xu, Yanan; Li, Guang; Mu, Ying

    2017-01-01

    Single cell analysis provides a new framework for understanding biology and disease, however, an absolute quantification of single cell gene expression still faces many challenges. Microfluidic digital polymerase chain reaction (PCR) provides a unique method to absolutely quantify the single cell gene expression, but only limited devices are developed to analyze a single cell with detection variation. This paper describes a self-priming compartmentalization (SPC) microfluidic digital polymerase chain reaction chip being capable of performing single molecule amplification from single cell. The chip can be used to detect four single cells simultaneously with 85% of sample digitization. With the optimized protocol for the SPC chip, we first tested the ability, precision, and sensitivity of our SPC digital PCR chip by assessing β-actin DNA gene expression in 1, 10, 100, and 1000 cells. And the reproducibility of the SPC chip is evaluated by testing 18S rRNA of single cells with 1.6%-4.6% of coefficient of variation. At last, by detecting the lung cancer related genes, PLAU gene expression of A549 cells at the single cell level, the single cell heterogeneity was demonstrated. So, with the power-free, valve-free SPC chip, the gene copy number of single cells can be quantified absolutely with higher sensitivity, reduced labor time, and reagent. We expect that this chip will enable new studies for biology and disease.

  16. Single cell digital polymerase chain reaction on self-priming compartmentalization chip

    PubMed Central

    Zhu, Qiangyuan; Qiu, Lin; Xu, Yanan; Li, Guang; Mu, Ying

    2017-01-01

    Single cell analysis provides a new framework for understanding biology and disease, however, an absolute quantification of single cell gene expression still faces many challenges. Microfluidic digital polymerase chain reaction (PCR) provides a unique method to absolutely quantify the single cell gene expression, but only limited devices are developed to analyze a single cell with detection variation. This paper describes a self-priming compartmentalization (SPC) microfluidic digital polymerase chain reaction chip being capable of performing single molecule amplification from single cell. The chip can be used to detect four single cells simultaneously with 85% of sample digitization. With the optimized protocol for the SPC chip, we first tested the ability, precision, and sensitivity of our SPC digital PCR chip by assessing β-actin DNA gene expression in 1, 10, 100, and 1000 cells. And the reproducibility of the SPC chip is evaluated by testing 18S rRNA of single cells with 1.6%–4.6% of coefficient of variation. At last, by detecting the lung cancer related genes, PLAU gene expression of A549 cells at the single cell level, the single cell heterogeneity was demonstrated. So, with the power-free, valve-free SPC chip, the gene copy number of single cells can be quantified absolutely with higher sensitivity, reduced labor time, and reagent. We expect that this chip will enable new studies for biology and disease. PMID:28191267

  17. Absolute GPS Positioning Using Genetic Algorithms

    NASA Astrophysics Data System (ADS)

    Ramillien, G.

    A new inverse approach for restoring the absolute coordinates of a ground -based station from three or four observed GPS pseudo-ranges is proposed. This stochastic method is based on simulations of natural evolution named genetic algorithms (GA). These iterative procedures provide fairly good and robust estimates of the absolute positions in the Earth's geocentric reference system. For comparison/validation, GA results are compared to the ones obtained using the classical linearized least-square scheme for the determination of the XYZ location proposed by Bancroft (1985) which is strongly limited by the number of available observations (i.e. here, the number of input pseudo-ranges must be four). The r.m.s. accuracy of the non -linear cost function reached by this latter method is typically ~10-4 m2 corresponding to ~300-500-m accuracies for each geocentric coordinate. However, GA can provide more acceptable solutions (r.m.s. errors < 10-5 m2), even when only three instantaneous pseudo-ranges are used, such as a lost of lock during a GPS survey. Tuned GA parameters used in different simulations are N=1000 starting individuals, as well as Pc=60-70% and Pm=30-40% for the crossover probability and mutation rate, respectively. Statistical tests on the ability of GA to recover acceptable coordinates in presence of important levels of noise are made simulating nearly 3000 random samples of erroneous pseudo-ranges. Here, two main sources of measurement errors are considered in the inversion: (1) typical satellite-clock errors and/or 300-metre variance atmospheric delays, and (2) Geometrical Dilution of Precision (GDOP) due to the particular GPS satellite configuration at the time of acquisition. Extracting valuable information and even from low-quality starting range observations, GA offer an interesting alternative for high -precision GPS positioning.

  18. Pharmacometric Analysis of the Relationship Between Absolute Lymphocyte Count and Expanded Disability Status Scale and Relapse Rate, Efficacy End Points, in Multiple Sclerosis Trials.

    PubMed

    Novakovic, A M; Thorsted, A; Schindler, E; Jönsson, S; Munafo, A; Karlsson, M O

    2018-05-10

    The aim of this work was to assess the relationship between the absolute lymphocyte count (ALC), and disability (as measured by the Expanded Disability Status Scale [EDSS]) and occurrence of relapses, 2 efficacy endpoints, respectively, in patients with remitting-relasping multiple sclerosis. Data for ALC, EDSS, and relapse rate were available from 1319 patients receiving placebo and/or cladribine tablets. Pharmacodynamic models were developed to characterize the time course of the endpoints. ALC-related measures were then evaluated as predictors of the efficacy endpoints. EDSS data were best fitted by a model where the logit-linear disease progression is affected by the dynamics of ALC change from baseline. Relapse rate data were best described by the Weibull hazard function, and the ALC change from baseline was also found to be a significant predictor of time to relapse. Presented models have shown that once cladribine exposure driven ALC-derived measures are included in the model, the need for drug effect components is of less importance (EDSS) or disappears (relapse rate). This simplifies the models and theoretically makes them mechanism specific rather than drug specific. Having a reliable mechanism-specific model would allow leveraging historical data across compounds, to support decision making in drug development and possibly shorten the time to market. © 2018, The American College of Clinical Pharmacology.

  19. The absolute dynamic ocean topography (ADOT)

    NASA Astrophysics Data System (ADS)

    Bosch, Wolfgang; Savcenko, Roman

    The sea surface slopes relative to the geoid (an equipotential surface) basically carry the in-formation on the absolute velocity field of the surface circulation. Pure oceanographic models may remain unspecific with respect to the absolute level of the ocean topography. In contrast, the geodetic approach to estimate the ocean topography as difference between sea level and the geoid gives by definition an absolute dynamic ocean topography (ADOT). This approach requires, however, a consistent treatment of geoid and sea surface heights, the first being usually derived from a band limited spherical harmonic series of the Earth gravity field and the second observed with much higher spectral resolution by satellite altimetry. The present contribution shows a procedure for estimating the ADOT along the altimeter profiles, preserving as much sea surface height details as the consistency w.r.t. the geoid heights will allow. The consistent treatment at data gaps and the coast is particular demanding and solved by a filter correction. The ADOT profiles are inspected for their innocent properties towards the coast and compared to external estimates of the ocean topography or the velocity field of the surface circulation as derived, for example, by ARGO floats.

  20. Overcoming interference with the detection of a stable isotopically labeled microtracer in the evaluation of beclabuvir absolute bioavailability using a concomitant microtracer approach.

    PubMed

    Jiang, Hao; Titsch, Craig; Zeng, Jianing; Jones, Barry; Joyce, Philip; Gandhi, Yash; Turley, Wesley; Burrell, Richard; Aubry, Anne F; Arnold, Mark E

    2017-09-05

    The oral absolute bioavailability of beclabuvir in healthy subjects was determined using a microdose (100μg) of the stable isotopically labeled tracer via intravenous (IV) infusion started after oral dosing of beclabuvir (150mg). To simultaneously analyze the concentrations of the IV microtracer ([ 13 C 6 ]beclabuvir) and beclabuvir in plasma samples, a liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) method was initially developed. Surprisingly beclabuvir significantly interfered with the IV microtracer detection when using the selected reaction monitoring (SRM) in the assay. An interfering component from the drug substance was observed using a high resolution mass spectrometer (HRMS). The mass-to-charge (m/z) of the interfering component was -32ppm different from the nominal value for the IV microtracer and thus could not be differentiated in the SRM assay by the unit mass resolution. To overcome this interference, we evaluated two approaches by either monitoring an alternative product ion using the SRM assay or isolating the interfering component using the parallel reaction monitoring (PRM) assay on the HRMS. This case study has demonstrated two practical approaches for overcoming interferences with the detection of stable isotopically labeled IV microtracers in the evaluation of absolute bioavailability, which provides users the flexibility in using either LC-MS/MS or HRMS to mitigate unpredicted interferences in the assay to support microtracer absolute bioavailability studies. Copyright © 2017 Elsevier B.V. All rights reserved.