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Sample records for pseudo-first-order reaction rate

  1. Ashkin-teller criticality and pseudo-first-order behavior in a frustrated Ising model on the square lattice.

    PubMed

    Jin, Songbo; Sen, Arnab; Sandvik, Anders W

    2012-01-27

    We study the challenging thermal phase transition to stripe order in the frustrated square-lattice Ising model with couplings J(1) < 0 (nearest-neighbor, ferromagnetic) and J(2) > 0 (second-neighbor, antiferromagnetic) for g = J(2)/|J(1| > 1/2. Using Monte Carlo simulations and known analytical results, we demonstrate Ashkin-Teller criticality for g ? g*; i.e., the critical exponents vary continuously between those of the 4-state Potts model at g = g* and the Ising model for g ? ?. Thus, stripe transitions offer a route to realizing a related class of conformal field theories with conformal charge c = 1 and varying exponents. The transition is first order for g < g* = 0.67 ± 0.01, much lower than previously believed, and exhibits pseudo-first-order behavior for |g* ? g

  2. Increasing PCB Radiolysis Rates in Transformer Oil

    SciTech Connect

    Mincher, Bruce Jay

    2002-11-01

    The kinetics of Aroclor 1242 radiolysis in transformer oil, using high-energy electrons, was found to be analogous to that previously measured for individual polychlorinated biphenyl (PCB) congeners irradiated with ó-rays. The plot of the pseudo-first-order rate constant for PCB decomposition versus initial PCB concentration is a power function, with high rate constants for low concentrations. The addition of alkaline isopropanol to transformer oil was found to increase the pseudo-first-order rate constant for PCB decomposition. The rate constant under these conditions is independent of concentration. This may be explained by the establishment of chain reaction dechlorination in the oil.

  3. Absolute rate constant of the reaction between chlorine /2P/ atoms and hydrogen peroxide from 298 to 424 K

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1980-01-01

    The absolute rate constant of the reaction between chlorine (2P) atoms and hydrogen peroxide was determined from 298 to 424 K, using the discharge flow resonance fluorescence technique. Pseudo-first-order conditions were used with hydrogen peroxide in large excess. A fast flow-sampling procedure limited hydrogen peroxide decomposition to less than 5% over the temperature range studied. At 298 K, the rate constant is (4.1 plus or minus 0.2) x 10 to the minus 13th cu cm/molecule-sec.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Kanavarioti, A.; Baird, E. E.

    1995-01-01

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

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

    SciTech Connect

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

    2000-01-20

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

  7. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

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

  8. EPR kinetic study of the reactions of F and Br atoms with H 2CO

    NASA Astrophysics Data System (ADS)

    Le Bras, G.; Foon, R.; Combourieu, J.

    1980-07-01

    The absolute rate constants of the reactions F + H 2CO ? HF + HCO (1) and Br + H 2CO ? HBr + HCO (2) have been measured using the discharge flow reactor-EPR method. Under pseudo-first-order conditions (¦H 2CO¦?¦F¦or¦Br¦), the following values were obtained at 298 K: k1 = (6.6 ± 1.1) × 10 -11 and k2 = (1.6± 0.3) × 10 -12, Units are cm 3 molecule -1s -1. The stratospheric implication of these data is discussed and the value obtained for k makes reaction (2) a possible sink for Br atoms in the stratosphere.

  9. 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.

  10. Reaction networks, kinetics, and inhibition in the hydroprocessing of simulated heavy coal liquids (Volumes I and II)

    SciTech Connect

    Girgis, M.J.

    1988-01-01

    The goals of this research included measurement of (1) rates of simultaneous disappearance of 5-8 reactants in mixtures representative of SRC-II heavy distillate, (2) rates of formation of each product, allowing determination of quantitative reaction networks, and (3) determination of effects of inhibitors on these networks. The mixture include quinoline, acridine, indole, 5,6,7,8-tetrahydro-1-naphthol, dibenzofuran, phenanthrene, fluoranthene, and pyrene. The experiments were conducted with a fixed-bed flow microreactor at 171 atm and 350 C using a commercial pre-sulfided Ni-Mo catalyst with a stoichiometric excess of hydrogen and low concentrations (ca. 0.25 wt%) of organic reactants in cyclohexane solvent. Quinoline represents the only significant inhibitor among the different functional groups. In its absence, the hydrodeoxygenation (HDO) of 5,6,7,8-tetrahydro-1-naphthol proceeds with a pseudo first-order rate constant greater than 10 l/(g of catalyst {center dot}h), requiring large hydrogen consumptions. The pseudo first-order rate constants for all the hydrocarbon hydrogenations are 0.4-1.8 l/(g of catalyst {center dot}). Fluoranthene is hydrogenated more rapidly than phenanthrene or pyrene. Dibenzothiophene HDS has a pseudo first-order rate constant of 0.260 l/(g of catalyst {center dot}h); dibenzofuran HDO is one order of magnitude slower. The quninoline feed concentration was varied by one order of magnitude to provide data for modeling the inhibitions. The reaction networks for phenanthrene, fluoranthene and dibenzothiophene coupled with the quinoline network were modeled with Langmuir-Hinshelwood-Hougen-Watson rate expressions. Such a characterization provides the basis for powerful predictive models for the hydroprocessing kinetics of heavy fossil fuels.

  11. Infrared spectroscopic studies of the heterogeneous reaction of ozone with maleic and fumaric acid aerosols

    NASA Astrophysics Data System (ADS)

    Najera, J.; Percival, C.; Horn, A. B.

    2009-04-01

    Dicarboxylic acids, either directly emitted or formed in chemical processes are found to be a significant component of tropospheric aerosols. To assess any potential role of short unsaturated dicarboxylic acids in tropospheric heterogeneous chemistry, maleic acid (MaH) and fumaric acid (FuH) were selected as surrogates in this study. A new aerosol flow tube apparatus is employed to perform kinetic studies of the oxidation of organic compounds containing aerosols by gas phase ozone. The system consists of a lab-made particle generation system, a vertically oriented glass flow tube with moveable injector and a multi-pass cross beam White cell for measurement of aerosol and gas phase composition via Fourier transform infrared (FTIR) spectroscopy. A flow of single component organic aerosols with mean diameters ranging between 0.8-2.1 m are introduced in a flow tube, in which the particles are subsequently exposed to a known concentration of ozone for a controlled period of time. These studies are complemented with offline analysis on the reaction products. Data from these studies were used to determine the kinetics of the reaction under a range of conditions. The reaction exhibited pseudo first order kinetics for gas product formation, and the pseudo first order rate coefficients displayed a Langmuir-Hinshelwood dependence on gas phase ozone concentration for both materials. By assuming Langmuir-Hinshelwood behaviour, the following parameters were found: for the reaction of MaH aerosols, KO3=(1.9+0.4)x10-16cm-3 and kmaxI=0.015+0.002; for the reaction of FuH aerosols, KO3= (3.4+0.4)x10-16cm-3 and kmaxI=0.0128+0.0005, where KO3 is a parameter that describes the partitioning of ozone to the particle surface and kmaxI is the maximum pseudo-first order coefficient at high ozone concentrations. Apparent reactive uptake coefficients were extracted from the pseudo first order rate coefficient and a slight trend of decreasing uptake coefficients with increasing ozone concentrations was observed. In general, we find that the values obtained for maleic and fumaric acid fall within the range of literature values reported by other published studies for other organic or organic-coated particles, although there are some unusual dependencies on RH%.

  12. QSARS FOR PREDICTING BIOTIC AND ABIOTIC REDUCTIVE TRANSFORMATION RATE CONSTANTS OF HALOGENATED HYDROCARBONS IN ANOXIC SEDIMENT SYSTEMS

    EPA Science Inventory

    Quantitative structure-activity relationships (QSARs) are developed relating biotic and abiotic pseudo-first-order disappearance rate constants of halogenated hydrocarbons in anoxic sediments to a number of readily available molecular descriptors. ased upon knowledge of the under...

  13. Method of controlling fusion reaction rates

    DOEpatents

    Kulsrud, Russell M. (Princeton, NJ); Furth, Harold P. (Princeton, NJ); Valeo, Ernest J. (Princeton Junction, NJ); Goldhaber, Maurice (Bayport, NY)

    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.

  14. 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…

  15. 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…

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

    PubMed

    Na??cz-Jawecki, Pawe?; Szyma?ska, Paulina; Kocha?czyk, Marek; Mi?kisz, Jacek; Lipniacki, Tomasz

    2015-12-01

    Biological signals in cells are transmitted with the use of reaction cycles, such as the phosphorylation-dephosphorylation cycle, in which substrate is modified by antagonistic enzymes. An appreciable share of such reactions takes place in crowded environments of two-dimensional structures, such as plasma membrane or intracellular membranes, and is expected to be diffusion-controlled. In this work, starting from the microscopic bimolecular reaction rate constants and using estimates of the mean first-passage time for an enzyme-substrate encounter, we derive diffusion-dependent effective macroscopic reaction rate coefficients (EMRRC) for a generic reaction cycle. Each EMRRC was found to be half of the harmonic average of the microscopic rate constant (phosphorylation c or dephosphorylation d), and the effective (crowding-dependent) motility divided by a slowly decreasing logarithmic function of the sum of the enzyme concentrations. This implies that when c and d differ, the two EMRRCs scale differently with the motility, rendering the steady-state fraction of phosphorylated substrate molecules diffusion-dependent. Analytical predictions are verified using kinetic Monte Carlo simulations on the two-dimensional triangular lattice at the single-molecule resolution. It is demonstrated that the proposed formulas estimate the steady-state concentrations and effective reaction rates for different sets of microscopic reaction rates and concentrations of reactants, including a non-trivial example where with increasing diffusivity the fraction of phosphorylated substrate molecules changes from 10% to 90%. PMID:26646890

  17. Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system

    NASA Astrophysics Data System (ADS)

    Farrukh, Muhammad Akhyar; Kauser, Robina; Adnan, Rohana

    2013-09-01

    The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5-4.5) and temperature (15-35°C) in the presence and absence of surfactant were investigated. Activation parameters, ? E a, ? H #, ? S #, ? G ?, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (?max), minimum area per surfactant molecule ( A min), average area occupied by each molecule of surfactant ( a), surface pressure at the CMC (?max), Gibb's energy of micellization (? G M°), Gibb's energy of adsorption (? G ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.

  18. CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.

    PubMed

    Papadimitriou, Vassileios C; Karafas, Emmanuel S; Gierczak, Tomasz; Burkholder, James B

    2015-07-16

    The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k?(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The present results are compared with results from previous studies and the discrepancies are discussed. PMID:25803714

  19. One- and two-dimensional chemical exchange nuclear magnetic resonance studies of the creatine kinase catalyzed reaction

    SciTech Connect

    Gober, J.R.

    1988-01-01

    The equilibrium chemical exchange dynamics of the creatine kinase enzyme system were studied by one- and two-dimensional {sup 31}P NMR techniques. Pseudo-first-order reaction rate constants were measured by the saturation transfer method under an array of experimental conditions of pH and temperature. Quantitative one-dimensional spectra were collected under the same conditions in order to calculate the forward and reverse reaction rates, the K{sub eq}, the hydrogen ion stoichiometry, and the standard thermodynamic functions. The pure absorption mode in four quadrant two-dimensional chemical exchange experiment was employed so that the complete kinetic matrix showing all of the chemical exchange process could be realized.

  20. Primordial nucleosynthesis and nuclear reaction rates uncertainties

    NASA Astrophysics Data System (ADS)

    Delbourgo-Salvador, P.; Vangioni-Flam, E.; Malinie, G.; Audouze, J.

    An attempt is made to determine to what extent discrepancies between theoretical and observed elemental abundances in the frame of the hot Standard big-bang may be accounted for by reaction rate uncertainties. Independent calculations of the abundances of elements of cosmological interest were made, taking into account the uncertainties in the nuclear reaction rates involved in these computations. A prediction is given regarding the maximum number of neutrino families. No discrepancy is found between the values for the present density of the Universe deduced from He-4 and D, only if the chemical evolution models allowing inflow of processed material in the considered zone are those which actually apply. In the case of discrepant density values, the consideration of uncertainties an the nuclear reaction rates cannot solve this difficulty.

  1. Reaction rates from electromagnetic gauge data

    SciTech Connect

    Vorthman, J.; Andrews, G.; Wackerle, J.

    1985-01-01

    The determination of reaction rates in explosives from experimental data is a task that requires a great deal of care, patience, and curve fitting. We have found that by measuring more quantities than are mathematically necessary for a complete Lagrange analysis, curve fits to experimental data do not have to be as exacting as otherwise required. We present an experimental technique specifically designed for the determination of global reaction rates which uses both embedded electromagnetic impulse and particle velocity gauges. The methods used to efficiently analyze the data, and the results and conclusions reached from several such studies are also presented. 16 refs., 9 figs.

  2. Reaction rates for mesoscopic reaction-diffusion kinetics.

    PubMed

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-01

    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

  3. Reaction rates for mesoscopic reaction-diffusion kinetics

    E-print Network

    Stefan Hellander; Andreas Hellander; Linda Petzold

    2015-01-28

    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 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 mixed boundary condition at the reaction radius of two molecules. We also establish fundamental limits for 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.

  4. Universal reaction rates for ultracold molecular collisions

    NASA Astrophysics Data System (ADS)

    Julienne, Paul; Idziaszek, Zbigniew

    2010-03-01

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

  5. Thermodynamic limitations on microbially catalyzed reaction rates

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  6. Nuclear reaction rates and the nova outburst

    SciTech Connect

    Starrfield, S.G.; Iliadis, C.

    2000-10-01

    In this paper we examined the consequences of improving the nuclear reaction library on our simulations of TNRs on 1.25M, WD and 1.35M, WDS. We have found that the changes in the rates have affected the nucleosynthesis predictions of our calculations but not, to any great extent, the gross features. In addition, we have used a lower mass accretion rate than in our previous studies in order to accrete (and eject) more material. This has, as expected, caused the peak values of some important parameters to increase over our previous studies at the same WD mass. However, because some important reaction rates have declined in the new compilation this has not increased the abundances for nuclei above aluminum and, in fact, they have declined while the abundances of both {sup 26}Al and {sup 27}Al have increased at both WD masses. In contrast, the abundance of {sup 22}Na has declined at both WD masses over the values predicted in our earlier work. This has important implications with respect to predictions of the observability of novae with INTEGRAL.

  7. DSMC Predictions of Chemical Reaction Rates between Atmospheric Species

    NASA Astrophysics Data System (ADS)

    Gallis, M. A.; Bond, R. B.; Torczynski, J. R.

    2009-11-01

    A recently proposed chemical reaction model based solely on molecular-level information is applied to calculate equilibrium and non-equilibrium chemical reaction rates for atmospheric reactions in hypersonic flows. The DSMC model is capable of reproducing measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular-level properties, the new model is inherently able to predict reaction rates for arbitrary non-equilibrium conditions. The DSMC-predicted chemical reaction rates are compared to theoretically calculated and experimentally measured reaction rates for non-equilibrium conditions. The observed agreement provides strong evidence that molecular-level modeling of chemical reactions provides an accurate method for predicting equilibrium and non-equilibrium chemical reaction rates. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  8. Basics of Chemical Kinetics -1 Rate of reaction = rate of disappearance of A =

    E-print Network

    Albert, Réka

    Basics of Chemical Kinetics - 1 Rate of reaction = rate of disappearance of A = # of moles of Chemical Kinetics - 3 Elementary Reaction: Reaction order of each species is identical reactions: Forward Reaction Backward Reaction CBA + 2 CBA + 2 CBA + 2 CBA + 2 #12;Basics of Chemical

  9. Astrophysical reaction rate for the 8 Li,,n, ...9

    E-print Network

    Horváth, Ákos

    Astrophysical reaction rate for the 8 Li,,n, ...9 Li reaction Hiroshi Kobayashi,1, * Kazuo Ieki,1 A reaction by performing the inverse reaction 9 Li( ,n)8 Li, with the equivalent photons in the electric field of nuclei in a Pb target providing the rays for the reaction. The energy spectrum of lithium

  10. 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…

  11. Photosensitized degradation kinetics of trace halogenated contaminants in natural waters using membrane introduction mass spectrometry as an in situ reaction monitor.

    PubMed

    Letourneau, Dane R; Gill, Chris G; Krogh, Erik T

    2015-10-28

    The photochemically mediated dechlorination of polyhalogenated compounds represents a potential decontamination strategy and a relevant environmental process in chemically reducing media. We report the UV irradiation of natural and artificial waters containing natural dissolved organic matter to effect the photo-sensitized degradation of chlorinated organic compounds, including tetrachloromethane, 1,1,1-tricloroethane, perchloroethene, 1,2-dibromo-3-chloropropane and chlorobenzene at trace (ppb) levels in aqueous solution. The degradation kinetics are followed in situ using membrane introduction mass spectrometry. By re-circulating the reaction mixture in a closed loop configuration over a semi-permeable hollow fiber polydimethylsiloxane membrane in a flow cell interface, volatile and semi-volatile compounds are continuously monitored using a quadrupole ion trap mass spectrometer. The time resolved quantitative information provides useful mechanistic insights, including kinetic data. Pseudo first-order rate constants for the degradation of contaminant mixtures in natural waters are reported. PMID:26439106

  12. Ligand substitution reactions of a dinuclear platinum(I) complex

    SciTech Connect

    Shimura, M.; Espenson, J.H.

    1984-11-21

    The complex Pt/sub 2/Br/sub 2/(..mu..-dppm)/sub 2/ when dppm = bis(diphenylphosphio)methane reacts with Et/sub 4/NCl in dichloromethane and dichloroethane to form Pt/sub 2/Cl/sub 2/(..mu..-dppm)/sub 2/. The reaction is reversible and proceeds via stepwise formation of the mixed-ligand (Br, Cl) complex. The reaction follows biphasic kinetics, and each step shows a linear dependence on (Et/sub 4/NCl), with rate constants 93 +/- 20 and 19.4 +/- 1.2 M/sup -1/ s/sup -1/ for the respective steps (10.0/sup 0/C in CH/sub 2/Cl/sub 2/). The identification of a rate constant with an individual step is a process that inherently admits of dual solutions; the assignment of values of h's was made on the basis that only this model gave a consistent and reasonable value for the molar absorptivity of the mixed-halide intermediate. The reaction in 1,2-dichloroethane shows a quite different kinetic pattern, with a single pseudo-first-order rate law and a more complex variation of the observed reaction constituent with (Et/sub 4/NCl).

  13. INITIAL TEST OF THE BENCHMARK CHEMICAL APPROACH FOR PREDICTING MICROBIAL TRANSFORMATION RATES IN AQUATIC ENVIRONMENTS

    EPA Science Inventory

    Using 2,4-dichlorophenoxyacetic acid methyl ester (2,4-DME) as a benchmark chemical, we determined relative pseudo-first-order rate coefficients for butoxyethyl ester of 2,4-dichlorophenoxyacetic acid (2,4-DBE), methyl parathion, and methyl-3-chlorobenzoate in a diversity of micr...

  14. Impact of THM reaction rates for astrophysics

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  15. Reaction rate calculations in dense stellar matter

    NASA Astrophysics Data System (ADS)

    Beard, Mary L.

    An interesting question in nuclear astrophysics is the fate of X-ray burst ashes as they descend under gravity to the deep layers of an accreting neutron star crust. As the ashes sink, they are subject to a range of nuclear reactions which transmute the nuclei. The primary of these reaction mechanisms are electron capture reactions, which are activated for different isotopes depending on the electron Fermi energy. At sufficiently high mass densities (rho =2.1x109 g cm-3 for 12C+12C and rho = 3.2 x1012 g cm -3 for 40Mg + 40Mg), density induced fusion reactions, known as pycnonuclear reactions, begin to occur. By combining existing electron capture formalism and a phenomenological expression for pycnonuclear reactions (specifically developed for a multi component plasma environment) with a network solver, the fate of the X-ray burst ashes have been addressed. In this context it has been found that with increasing mass density, the rigid Coulomb lattice of the neutron star crust dissolves into the isotopes 40Mg and 46Si, with an integrated energy release of between ˜ 1.8 MeV/u and ˜ 2.4 MeV/u, depending on lattice models. This result is fairly insensitive to the initial abundance distribution. The production of 46Si is determined to be the result of a cyclical pycnonuclear fusion, electron capture process. The magnitude of the pycnonuclear reactions have been found to be dependent on the mass fraction contained in the nuclei, and consequently to drop off quickly at mass densities greater than the neutron drip density. To large effect this halts the production cycle of 46Si.

  16. DSMC predictions of non-equilibrium reaction rates.

    SciTech Connect

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

    2010-04-01

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

  17. Transition state theory, Siegert eigenstates, and quantum mechanical reaction rates

    E-print Network

    Miller, William H.

    Transition state theory, Siegert eigenstates, and quantum mechanical reaction rates Tamar Seideman), on which a general semiclassical transition state theory is based, are shown to be the semiclassical, it is then shown how the exact quantum mechanical reaction rate can be expressed in terms of the Siegert

  18. On the rate of relativistic surface chemical reactions.

    PubMed

    Veitsman, E V

    2004-07-15

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

  19. Oxidative addition reaction of diarylplatinum(II) complexes with MeI in ionic liquid media: a kinetic study.

    PubMed

    Nabavizadeh, S Masoud; Shahsavari, Hamid R; Sepehrpour, Hajar; Hosseini, Fatemeh Niroomand; Jamali, Sirous; Rashidi, Mehdi

    2010-09-01

    A kinetic study of the oxidative addition reaction of diarylplatinum(II) complexes [Pt(p-MeC(6)H(4))(2)(NN)] (1a: NN = 1,10-phenanthroline (phen) and 1b: NN = 4,4'-di-tert-butyl-2,2'-bipyridine ((t)Bu(2)bpy)) with MeI in ionic liquids 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][bta]) or 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) is described. The reactions were investigated as a function of MeI concentration and temperature under pseudo-first-order conditions using UV-vis spectroscopy techniques. In general, the oxidative addition reactions in ionic liquids followed an S(N)2 mechanism, similar to that reported for the related reactions in conventional solvents, e.g. benzene or acetone. The reaction rates in different solvents followed the order acetone > ionic liquids > benzene. The trend in the values of k(2) clearly indicated that ionic liquids behave like conventional solvents and that no particular 'ionic liquid effect' was detected in this kind of reaction. The effect of solvent on the reactions was examined using a linear solvation energy relationship (LSER) based on the Kamlet-Taft solvent scale. The activation parameters, DeltaH(++) and DeltaS(++), were obtained for the reactions in each solvent and the investigation of enthalpy-entropy compensation confirmed that the mechanism operated in all solvents is similar. PMID:20664857

  20. Imaginary-time theory for triple-alpha reaction rate

    E-print Network

    T. Akahori; Y. Funaki; K. Yabana

    2014-01-17

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

  1. Monte-Carlo Reaction Rate Evaluation for Astrophysics

    SciTech Connect

    Coc, A.; Fitzgerald, R.

    2010-06-01

    We present a new evaluation of thermonuclear reaction rates for astrophysics involving proton and alpha-particle induced reactions, in the target mass range between A = 14 and 40, including many radioactive targets. A method based on Monte Carlo techniques is used to evaluate thermonuclear reaction rates and their uncertainties. At variance with previous evaluations, the low, median and high rates are statistically defined and a lognormal approximation to the rate distribution is given. This provides improved input for astrophysical model calculations using also the Monte Carlo method to estimate uncertainties on isotopic abundances.

  2. Imaginary-time formalism for triple-? reaction rates

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

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

    NASA Technical Reports Server (NTRS)

    Rizvi, Farheen

    2013-01-01

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

  4. Charged-Particle Thermonuclear Reaction Rates: III. Nuclear Physics Input

    E-print Network

    Christian Iliadis; Richard Longland; Art Champagne; Alain Coc

    2010-04-23

    The nuclear physics input used to compute the Monte Carlo reaction rates and probability density functions that are tabulated in the second paper of this series (Paper II) is presented. Specifically, we publish the input files to the Monte Carlo reaction rate code RatesMC, which is based on the formalism presented in the first paper of this series (Paper I). This data base contains overwhelmingly experimental nuclear physics information. The survey of literature for this review was concluded in November 2009.

  5. A New Approach to Determining Gas-Particle Reaction Probabilities and Application to the Heterogeneous Reaction of Deliquesced Sodium Chloride Particles with Gas-Phase Hydroxyl Radicals

    SciTech Connect

    Laskin, Alexander; Wang, Hai; Robertson, William H.; Cowin, James P.; Ezell, Michael J.; Finlayson-Pitts, Barbara J.

    2006-09-14

    The reaction kinetics for gaseous hydroxyl radicals (OH) with deliquesced sodium chloride particles (NaClaq) were investigated using a novel experimental approach. The technique utilizes the exposure of substrate-deposited aerosol particles to reactive gases followed by chemical analysis of the particles using computer-controlled scanning electron microscopy with energy-dispersive analysis of X-rays (CCSEM/EDX) capability. Experiments were performed at room temperature and atmospheric pressure with deliquesced NaCl particles in the micron size range at 70-80% RH and with OH concentrations in the range of 1 to 7?109 cm-3. The apparent, pseudo first-order rate constant for the reaction was determined from measurements of changes in the chloride concentration of individual particles upon reaction with OH as a function of the particle loading on the substrate. Quantitative treatment of the data using a model that incorporates both diffusion and reaction kinetics yields a lower-limit to the net reaction probability of ?net > 0.1, with an overall uncertainty of a factor of two.

  6. Urea degradation by electrochemically generated reactive chlorine species: products and reaction pathways.

    PubMed

    Cho, Kangwoo; Hoffmann, Michael R

    2014-10-01

    This study investigated the transformation of urea by electrochemically generated reactive chlorine species (RCS). Solutions of urea with chloride ions were electrolyzed using a bismuth doped TiO2 (BiOx/TiO2) anode coupled with a stainless steel cathode at applied anodic potentials (Ea) of either +2.2 V or +3.0 V versus the normal hydrogen electrode. In NaCl solution, the current efficiency of RCS generation was near 30% at both potentials. In divided cell experiments, the pseudo-first-order rate of total nitrogen decay was an order of magnitude higher at Ea of +3.0 V than at +2.2 V, presumably because dichlorine radical (Cl2(-)·) ions facilitate the urea transformation primary driven by free chlorine. Quadrupole mass spectrometer analysis of the reactor headspace revealed that N2 and CO2 are the primary gaseous products of the oxidation of urea, whose urea-N was completely transformed into N2 (91%) and NO3(-) (9%). The higher reaction selectivity with respect to N2 production can be ascribed to a low operational ratio of free available chlorine to N. The mass-balance analysis recovered urea-C as CO2 at 77%, while CO generation most likely accounts for the residual carbon. In light of these results, we propose a reaction mechanism involving chloramines and chloramides as reaction intermediates, where the initial chlorination is the rate-determining step in the overall sequence of reactions. PMID:25219459

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

    SciTech Connect

    Murphy, M J

    2010-03-08

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

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

    NASA Astrophysics Data System (ADS)

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

    1992-06-01

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

  9. Shock tube kinetic study of the CH sub 3 + H sub 2 r equilibrium H + CH sub 4 reaction and the methane dissociation reaction

    SciTech Connect

    Klemm, R.B.; Sutherland, J.W.; Tao, Wen.

    1992-01-01

    In this kinetic study of (1) the reaction of CH{sub 3} radicals with H{sub 2} and (2) the thermal dissociation of methane, primary product H atoms were monitored directly using the sensitive atomic resonance absorption detection technique. The detection limit for the (H) was about 3{times}10{sup 10} atoms cm{sup {minus}3}. Rate constants for both reactions were obtained under pseudo-first-order conditions. In addition, computer simulations verified that kinetic complications were avoided. For the reaction of CH{sub 3}+H{sub 2}, experiments were performed using either acetone or ethane to generate CH{sub 3} radicals rapidly by thermal dissociation in argon. Twenty-four experiments were performed over the temperature range 1346K to 1793K and a rate constant expression derived using linear least-squares analysis: k{sub {minus}2}(T) = (6.0{plus minus}0.7){times}10{sup {minus}12} exp ({minus}5920{plus minus}190K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. 46 refs., 5 figs., 5 tabs.

  10. Shock tube kinetic study of the CH{sub 3} + H{sub 2} {r_equilibrium} H + CH{sub 4} reaction and the methane dissociation reaction

    SciTech Connect

    Klemm, R.B.; Sutherland, J.W.; Tao, Wen

    1992-02-01

    In this kinetic study of (1) the reaction of CH{sub 3} radicals with H{sub 2} and (2) the thermal dissociation of methane, primary product H atoms were monitored directly using the sensitive atomic resonance absorption detection technique. The detection limit for the [H] was about 3{times}10{sup 10} atoms cm{sup {minus}3}. Rate constants for both reactions were obtained under pseudo-first-order conditions. In addition, computer simulations verified that kinetic complications were avoided. For the reaction of CH{sub 3}+H{sub 2}, experiments were performed using either acetone or ethane to generate CH{sub 3} radicals rapidly by thermal dissociation in argon. Twenty-four experiments were performed over the temperature range 1346K to 1793K and a rate constant expression derived using linear least-squares analysis: k{sub {minus}2}(T) = (6.0{plus_minus}0.7){times}10{sup {minus}12} exp ({minus}5920{plus_minus}190K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. 46 refs., 5 figs., 5 tabs.

  11. Revisiting catalytic model reaction p-nitrophenol/NaBH4 using metallic nanoparticles coated on polymeric spheres

    NASA Astrophysics Data System (ADS)

    Li, Maolin; Chen, Guofang

    2013-11-01

    The early reported pseudo-first-order reaction kinetics of the polymer-supported metallic nanocatalysts for the model reaction of p-nitrophenol (p-NP)/NaBH4 were probably oversimplified. Here a detailed study of p-NP reduction by NaBH4 in the presence of the raspberry-like poly(allylamine hydrochloride)-modified polymer poly(glycidyl methacrylate) composite sub-microspheres with tunable gold nanoparticles (PGMA@PAH@AuNPs) was presented. Effects of polyelectrolyte concentration, the ratio of polymer spheres to gold nanoparticles, and the solution pH value for composite synthesis on the induction period, reaction time, average reaction rate and average turnover frequency were systematically investigated. Experimental results in all cases of our study revealed an nth order (n > 1) of the p-NP/NaBH4 catalytic reaction by the prepared polymer composite particles. The apparent order of reaction, n, is dependent on the total surface area of the coated gold nanoparticles on the polymer spheres, which can be closely correlated with the tunable gold nanoparticle surface coverage. The mechanism of the observed catalytic activity enhancement was proposed based on active epoxy groups of the polymer spheres and a large adsorption of p-nitrophenolate anions onto the positively-charged spheres.

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

    SciTech Connect

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

    2014-05-02

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

  13. Rate of reaction between molecular hydrogen and molecular oxygen

    NASA Technical Reports Server (NTRS)

    Brokaw, R. S.

    1973-01-01

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

  14. 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.

  15. Stellar Evolution Constraints on the Triple-Alpha Reaction Rate

    E-print Network

    Takuma Suda; Raphael Hirschi; Masayuki Y. Fujimoto

    2011-07-25

    We investigate the quantitative constraint on the triple-alpha reaction rate based on stellar evolution theory, motivated by the recent significant revision of the rate proposed by nuclear physics calculations. Targeted stellar models were computed in order to investigate the impact of that rate in the mass range of 0.8 evolution of low- and intermediate-mass stars, while its influence on the evolution of massive stars (M >~ 10 Msun) 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 10 at T = 1 - 1.2 x 10^8 K where the cross section is proportional to T^{nu}. We also derive the helium ignition curve to estimate the maximum cross section to retain the low-mass first red giants. The semi-analytically derived ignition curves suggest that the reaction rate should be less than ~ 10^{-29} cm^6 s^{-1} mole^{-2} at ~ 10^{7.8} K, which corresponds to about three orders of magnitude larger than that of the NACRE compilation. In an effort to compromise with the revised rates, we calculate and analyze models with enhanced CNO cycle reaction rates to increase the maximum luminosity of the first giant branch. However, it is impossible to reach the typical RGB tip luminosity even if all the reaction rates related to CNO cycles are enhanced by more than ten orders of magnitude.

  16. General properties of astrophysical reaction rates in explosive nucleosynthesis

    E-print Network

    T. Rauscher

    2012-09-25

    Fundamental differences in the prediction of reaction rates with intermediate and heavy target nuclei compared to the ones with light nuclei are discussed, with special emphasis on stellar modifications of the rates. Ground and excited state contributions to the stellar rates are quantified, deriving a linear weighting of excited state contributions despite of a Boltzmann population of the nuclear states. A Coulomb suppression effect of the excited state contributions is identified, acting against the usual Q-value rule in some reactions. The proper inclusion of experimental data in revised stellar rates is shown, containing revised uncertainties. An application to the s-process shows that the actual uncertainties in the neutron capture rates are larger than would be expected from the experimental errors alone. Sensitivities of reaction rates and cross sections are defined and their application in reaction studies is discussed. The conclusion provides a guide to experiment as well as theory on how to best improve the rates used in astrophysical simulations and how to assess their uncertainties.

  17. Rate coefficients, binding probabilities, and related quantities for area reactivity models

    PubMed Central

    Prüstel, Thorsten; Meier-Schellersheim, Martin

    2014-01-01

    We further develop the general theory of the area reactivity model that describes the diffusion-influenced reaction of an isolated receptor-ligand pair in terms of a generalized Feynman-Kac equation and that provides an alternative to the classical contact reactivity model. Analyzing both the irreversible and reversible reaction, we derive the equation of motion of the survival probability as well as several relationships between single pair quantities and the reactive flux at the encounter distance. Building on these relationships, we derive the equation of motion of the many-particle survival probability for irreversible pseudo-first-order reactions. Moreover, we show that the usual definition of the rate coefficient as the reactive flux is deficient in the area reactivity model. Numerical tests for our findings are provided through Brownian Dynamics simulations. We calculate exact and approximate expressions for the irreversible rate coefficient and show that this quantity behaves differently from its classical counterpart. Furthermore, we derive approximate expressions for the binding probability as well as the average lifetime of the bound state and discuss on- and off-rates in this context. Throughout our approach, we point out similarities and differences between the area reactivity model and its classical counterpart, the contact reactivity model. The presented analysis and obtained results provide a theoretical framework that will facilitate the comparison of experiment and model predictions. PMID:25416882

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

    NASA Astrophysics Data System (ADS)

    Arshadi, Masoud; Rajaram, Harihar

    2015-09-01

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

  19. Study of Reaction NH3 + H NH2 + H2 by a Simple Program to Determine the Reaction Rate

    E-print Network

    Study of Reaction NH3 + H NH2 + H2 by a Simple Program to Determine the Reaction Rate Patr´icia R developed a simple program to determine the reaction rate by using conventional transition state theory abstraction in the reaction NH3 + H NH2 + H2 is used as a model to demonstrate usage of the program. The rate

  20. Imaginary-time method for radiative capture reaction rate

    E-print Network

    Kazuhiro Yabana; Yasuro Funaki

    2012-02-15

    We propose a new computational method for astrophysical reaction rate of radiative capture process. In the method, an evolution of a wave function is calculated along the imaginary-time axis which is identified as the inverse temperature. It enables direct evaluation of reaction rate as a function of temperature without solving any scattering problem. The method is tested for two-body radiative capture reaction, ${^{16}{\\rm O}}(\\alpha,\\gamma){^{20}{\\rm Ne}}$, showing that it gives identical results to that calculated by the ordinary procedure. The new method will be suited for calculation of triple-alpha radiative capture rate for which an explicit construction of the scattering solution is difficult.

  1. A reaction class approach for modeling gas phase reaction rates Thanh N. Truong,* Wendell T. Duncan and Max Tirtowidjojo

    E-print Network

    Truong, Thanh N.

    A reaction class approach for modeling gas phase reaction rates Thanh N. Truong,* Wendell T. Duncan present a series of new tunneling models based on a reaction class approach. Reaction class consists of all reactions that have the same reactive moiety. One can expect that reactions in the same class

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

    SciTech Connect

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

    2010-06-01

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

  3. Mechanistic elucidation of linker and ancillary ligand substitution reactions in Pt(II) dinuclear complexes.

    PubMed

    Ongoma, Peter O; Jaganyi, Deogratius

    2013-02-28

    The rate of substitution of aqua ligands by three nucleophiles, thiourea (TU), N,N-dimethylthiourea (DMTU) and N,N,N,N-tetramethylthiourea (TMTU), for the complexes [cis-{PtOH2(NH3)2}2-?-pyrazine](ClO4)2 (pzn), [cis-{PtOH2(NH3)2}2-?-2,3-dimethylpyrazine](ClO4)2 (2,3pzn), [cis-{PtOH2(NH3)2}2-?-2,5-pyrazine](ClO4)2 (2,5pzn) and [cis-{PtOH2(NH3)2}2-?-2,6-dimethylpyrazine](ClO4)2 (2,6pzn) was investigated under pseudo first-order conditions as a function of concentration and temperature by stopped-flow and UV-Visible spectrophotometry. The reaction proceeded in three consecutive steps; each step follows first order kinetics with respect to each complex and nucleophile. The pseudo first-order rate constants, k(obs(1/2/3)), for sequential substitution of the aqua ligands and subsequent displacement of the linker obeyed the rate law: k(obs(1/2/3)) = k((1/2/3))[nucleophile]. The steric hindrance properties of the pyrazine-bridging ligand control the overall reaction pattern. The order of reactivity of the complexes is 2,3pzn ? 2,5pzn < 2,6pzn < pzn. The difference in reactivity attributed to the steric crowding at the Pt(II) centre imposed by the methyl groups reduces the lability of the aqua complexes. The order of reactivity of the nucleophiles decreases with the increase in steric demand TU > DMTU > TMTU. 1H and 195Pt NMR spectroscopic results confirmed the observed dissociation of the bridging ligand from the metal centre of the cis-dinuclear complexes and its derivatives in the third step. The dissociation process is accelerated by the introduction of the steric effect on the linker in conjunction with the increased ligand field strength imparted by additional thiourea ligands at each metal centre. The large negative entropy of activation ?S(?) values in all cases support an associative substitution mechanism. PMID:23223554

  4. Dissipation Scale Fluctuations and Chemical Reaction Rates in Turbulent Flows

    E-print Network

    Victor Yakhot

    2007-06-29

    Small separation between reactants, not exceeding $10^{-8}-10^{-7}cm$, is the necessary condition for various chemical reactions. It is shown that random advection and stretching by turbulence leads to formation of scalar-enriched sheets of {\\it strongly fluctuating thickness} $\\eta_{c}$. The molecular-level mixing is achieved by diffusion across these sheets (interfaces) separating the reactants. Since diffusion time scale is $\\tau_{d}\\propto \\eta_{c}^{2}$, the knowledge of probability density $Q(\\eta_{c},Re)$ is crucial for evaluation of chemical reaction rates. In this paper we derive the probability density $Q(\\eta_{c},Re,Sc)$ and predict a transition in the reaction rate behavior from ${\\cal R}\\propto \\sqrt{Re}$ ($Re\\leq 10^{4}$) to the high-Re asymptotics ${\\cal R}\\propto Re^{0}$. The theory leads to an approximate universality of transitional Reynolds number $Re_{tr}\\approx 10^{4}$. It is also shown that if chemical reaction involves short-lived reactants, very strong anomalous fluctuations of the length-scale $\\eta_{c}$ may lead to non-negligibly small reaction rates.

  5. Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates

    PubMed Central

    Bentley, T. William

    2015-01-01

    Hydrolyses of acid derivatives (e.g., carboxylic acid chlorides and fluorides, fluoro- and chloroformates, sulfonyl chlorides, phosphorochloridates, anhydrides) exhibit pseudo-first order kinetics. Reaction mechanisms vary from those involving a cationic intermediate (SN1) to concerted SN2 processes, and further to third order reactions, in which one solvent molecule acts as the attacking nucleophile and a second molecule acts as a general base catalyst. A unified framework is discussed, in which there are two reaction channels—an SN1-SN2 spectrum and an SN2-SN3 spectrum. Third order rate constants (k3) are calculated for solvolytic reactions in a wide range of compositions of acetone-water mixtures, and are shown to be either approximately constant or correlated with the Grunwald-Winstein Y parameter. These data and kinetic solvent isotope effects, provide the experimental evidence for the SN2-SN3 spectrum (e.g., for chloro- and fluoroformates, chloroacetyl chloride, p-nitrobenzoyl p-toluenesulfonate, sulfonyl chlorides). Deviations from linearity lead to U- or V-shaped plots, which assist in the identification of the point at which the reaction channel changes from SN2-SN3 to SN1-SN2 (e.g., for benzoyl chloride). PMID:26006228

  6. Elucidating Latent Mechanistic Complexity in Competing Acid-Catalyzed Reactions of Salicylaldehyde-Derived Baylis-Hillman Adducts.

    PubMed

    Olomola, Temitope O; Klein, Rosalyn; Caira, Mino R; Kaye, Perry T

    2016-01-01

    (1)H NMR-based kinetic studies have revealed the latent mechanistic complexity of deceptively simple hydrochloric acid-catalyzed reactions of salicylaldehyde-derived Baylis-Hillman adducts. Reactions conducted at 0 °C afforded 2-(chloromethyl)cinnamic acid derivatives as the major products and the corresponding 3-(chloromethyl)coumarin derivatives as the minor products. In reactions conducted in refluxing acetic acid, however, the 3-(chloromethyl)coumarin derivatives are the sole products. Variable-temperature (1)H NMR analysis permitted the determination of the rate constants and kinetic parameters involved in the pseudo-first-order formation of (Z)-2-(chloromethyl)-3-(2-hydroxyphenyl)-2-propenoic acid. The kinetic data clearly preclude the operation of classical kinetic versus thermodynamic control and indicate the operation of three independent reaction pathways. Theoretical studies of these pathways undertaken at the B3LYP/6-31G(d) level permitted rationalization of the experimental data and provided insights into the possible mechanism of the enzymic E-Z isomerization and cyclization of (E)-cinnamic acid analogues to afford coumarins. PMID:26655750

  7. 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.

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

    SciTech Connect

    Froehlich, C.; Rauscher, T.

    2012-11-12

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

  9. Introduction Intracellular reaction rates are dependent both on the catalytic

    E-print Network

    Kinsey, Stephen

    function. Key words: muscle fiber, fiber growth, diffusion, metabolic modeling, reaction of metabolic processes. In mammalian skeletal muscle, this view is supported by the close matching of purely of metabolic processes increase (Weisz, 1973). The maximal aerobic metabolic rate in muscle is largely

  10. Nuclear fusion in dense matter: Reaction rate and carbon burning

    E-print Network

    L. R. Gasques; A. V. Afanasjev; E. F. Aguilera; M. Beard; L. C. Chamon; P. Ring; M. Wiescher; D. G. Yakovlev

    2005-06-16

    In this paper we analyze the nuclear fusion rate between equal nuclei for all five different nuclear burning regimes in dense matter (two thermonuclear regimes, two pycnonuclear ones, and the intermediate regime). The rate is determined by Coulomb barrier penetration in dense environments and by the astrophysical S-factor at low energies. We evaluate previous studies of the Coulomb barrier problem and propose a simple phenomenological formula for the reaction rate which covers all cases. The parameters of this formula can be varied, taking into account current theoretical uncertainties in the reaction rate. The results are illustrated for the example of the ^{12}C+^{12}C fusion reaction. This reaction is very important for the understanding of nuclear burning in evolved stars, in exploding white dwarfs producing type Ia supernovae, and in accreting neutron stars. The S-factor at stellar energies depends on a reliable fit and extrapolation of the experimental data. We calculate the energy dependence of the S-factor using a recently developed parameter-free model for the nuclear interaction, taking into account the effects of the Pauli nonlocality. For illustration, we analyze the efficiency of carbon burning in a wide range of densities and temperatures of stellar matter with the emphasis on carbon ignition at densities rho > 10^9 g/cc.

  11. 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.

  12. Scaling of geochemical reaction rates via advective solute transport

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    PubMed

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

    2015-07-01

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

  14. Suitable combination of promoter and micellar catalyst for kilo fold rate acceleration on benzaldehyde to benzoic acid conversion in aqueous media at room temperature: A kinetic approach

    NASA Astrophysics Data System (ADS)

    Ghosh, Aniruddha; Saha, Rumpa; Ghosh, Sumanta K.; Mukherjee, Kakali; Saha, Bidyut

    2013-05-01

    The kinetics of oxidation of benzaldehyde by chromic acid in aqueous and aqueous surfactant (sodium dodecyl sulfate, SDS, alkyl phenyl polyethylene glycol, Triton X-100 and N-cetylpyridinium chloride, CPC) media have been investigated in the presence of promoter at 303 K. The pseudo-first-order rate constants (kobs) were determined from a logarithmic plot of absorbance as a function time. The rate constants were found to increase with introduction of heteroaromatic nitrogen base promoters such as Picolinic acid (PA), 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen). The product benzoic acid has been characterized by conventional melting point experiment, NMR, HRMS and FTIR spectral analysis. The mechanism of both unpromoted and promoted reaction path has been proposed for the reaction. In presence of the anionic surfactant SDS, cationic surfactant CPC and neutral surfactant TX-100 the reaction can undergo simultaneously in both aqueous and micellar phase with an enhanced rate of oxidation in the micellar phase. Both SDS and TX-100 produce normal micellar effect whereas CPC produce reverse micellar effect in the presence of benzaldehyde. The observed net enhancement of rate effects has been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. SDS and bipy combination is the suitable one for benzaldehyde oxidation.

  15. Suitable combination of promoter and micellar catalyst for kilo fold rate acceleration on benzaldehyde to benzoic acid conversion in aqueous media at room temperature: a kinetic approach.

    PubMed

    Ghosh, Aniruddha; Saha, Rumpa; Ghosh, Sumanta K; Mukherjee, Kakali; Saha, Bidyut

    2013-05-15

    The kinetics of oxidation of benzaldehyde by chromic acid in aqueous and aqueous surfactant (sodium dodecyl sulfate, SDS, alkyl phenyl polyethylene glycol, Triton X-100 and N-cetylpyridinium chloride, CPC) media have been investigated in the presence of promoter at 303 K. The pseudo-first-order rate constants (kobs) were determined from a logarithmic plot of absorbance as a function time. The rate constants were found to increase with introduction of heteroaromatic nitrogen base promoters such as Picolinic acid (PA), 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen). The product benzoic acid has been characterized by conventional melting point experiment, NMR, HRMS and FTIR spectral analysis. The mechanism of both unpromoted and promoted reaction path has been proposed for the reaction. In presence of the anionic surfactant SDS, cationic surfactant CPC and neutral surfactant TX-100 the reaction can undergo simultaneously in both aqueous and micellar phase with an enhanced rate of oxidation in the micellar phase. Both SDS and TX-100 produce normal micellar effect whereas CPC produce reverse micellar effect in the presence of benzaldehyde. The observed net enhancement of rate effects has been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. SDS and bipy combination is the suitable one for benzaldehyde oxidation. PMID:23501718

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

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

    SciTech Connect

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

    1980-10-02

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

  18. A model for reaction rates in turbulent reacting flows

    NASA Technical Reports Server (NTRS)

    Chinitz, W.; Evans, J. S.

    1984-01-01

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

  19. Updating the nuclear reaction rate library REACLIB. (I. Experimental reaction rates of the proton-proton chain)

    E-print Network

    Theodore E. Liolios

    2005-02-03

    REACLIB is one of the most comprehensive and popular astrophysical reaction rate libraries. However, its experimentally obtained rates for light isotopes still rely mainly on the Caughlan & Fowler (1988) compilation and have never been updated despite the progress in many relevant nuclear astrophysics experiments. Moreover, due to fitting errors REACLIB is not reliable at temperatures lower than 10^{7}K. In this work we establish the formalism for updating the obsolete Caughlan-Fowler experimental rates of REACLIB. Then we use the NACRE compilation and results from the LUNA experiments to update some important charged-particle induced rates of REACLIB focusing on the proton-proton chain. The updated rates (available also in digital form) can now be used in the low temperature regime (below 10^{7}K) which was forbidden to the old version of REACLIB.

  20. Application of semiclassical methods to reaction rate theory

    SciTech Connect

    Hernandez, R.

    1993-11-01

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

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

    ERIC Educational Resources Information Center

    Lombardo, Anthony

    1982-01-01

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

  2. Effect of Finite-rate Chemical Reactions on Turbulence in Hypersonic Turbulent Boundary Layers

    E-print Network

    Martín, Pino

    Effect of Finite-rate Chemical Reactions on Turbulence in Hypersonic Turbulent Boundary Layers Lian reaction. The influence of chemical reactions on temperature fluctuation variance, Reynolds stresses that the recombination reaction enhances turbulence, while the dissociation reaction damps turbulence. Chemical reactions

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    We observed the growth of spinel sensu stricto (MgAl2O4) between periclase (MgO) and corundum (Al2O3) in thin films deposited by the pulsed laser deposition method on crystallographically oriented single crystal substrates. The starting samples consisted of cut and ultra polished single crystals of either corundum (parallel (0001)) or periclase (parallel (111)) and an amorphous source layer of the respective reactant that in the very first stages of the experiments became polycrystalline. The cutting direction in the substrate minerals ensures that the substrate phases start to react along their close-packed hexagonal oxygen layers which allows topotactical growth of the newly formed spinel. The entire layer setup on the substrate crystals was only a few 100 nm thick. The growth of these spinel product layers was monitored in-situ using a heating attachment and synchrotron X-ray diffraction. From the reacted samples we took electron transparent foils by the focused ion beam method and analysed them ex-situ by TEM. At 1000°C we found a difference in spinel growth rate between one and two orders of magnitude between the two substrates, all other parameters held constant. At 900 and 1000 °C spinel had formed after one hour by 0.004 nm/s (900°C) and 0.034 nm/s (1000°C) on corundum substrate, while on periclase substrate the reaction had gone completely through the Al2O3 source layer transforming it to spinel by at least 15-30 times higher reaction rates (boundary values) and probably even faster. At 800°C no reaction occurred between periclase layers and corundum single crystals, whereas spinel crystallized at a (linearized) rate of 46 nm/h on periclase single crystals. We explain our findings by the local reaction volume at the periclase-corundum interface. Many studies (including this one) have established that spinel grows by cation exchange in a rather immobile oxygen sublattice. This mechanism implies a negative volume change at the Sp-Per interface (by -13 %) and a positive volume change at the Sp-Cor interface (by +17 %). We observed in TEM images formation of porosity at the Sp-Per substrate interface and lattice strain in the polycrystalline corundum substrate at the Sp-Cor substrate interface, both observations being fully in line with the respective local volume changes. We infer that the local stress field between the growing reaction layer and the rigid single crystal substrate is responsible for the dramatic effect on both the nucleation and reaction rates. With respect to minerals growing at dry conditions in the Earth's crust (granulite facies) we infer that rates of reactions might strongly depend on local volume changes at interfaces, that reactions are impeded by compressive reaction-induced stress applied to rigid neighboring grains, and that nucleation of thermodynamically stable phases on grain boundaries might be suppressed by a positive reaction volume.

  5. Reaction of argininosuccinase with bromomesaconic acid: role of an essential lysine in the active site

    SciTech Connect

    Lusty, C.J.; Ratner, S.

    1987-05-01

    We have undertaken studies on bovine liver argininosuccinase (L-argininosuccinate arginine-lyase with the active site-directed reagent bromo(U-/sup 14/C)mesaconic acid, an analogue of fumaric acid. Reactivity, measured by enzyme inactivation, followed pseudo-first-order kinetics, and the rate increased with reagent concentration. Argininosuccinate completely protected the enzyme against inactivation, but neither arginine nor fumarate was protective. A plot of the degree of inactivation as a function of alkyl groups incorporated was extrapolated to 4 mol per mol of enzyme, or 1 mol per active site. After large-scale alkylation of the enzyme (and digestion with trypsin), two /sup 14/C-labeled tryptic peptides were isolated. These were chemically sequenced by the Edman method. The amino acid sequences proved to be identical with regions of the deduced amino acid sequences or argininosuccinases from human and yeast sources The /sup 14/C-labeled tryptic peptide in the active site region had the sequence Gly-Leu-Glu-Xaa-Ala-Gly-Leu-Leu-Thr-Lys; Xaa represents an unknown phenylthiohydantoin derivative detected in cycle 4. The corresponding amino acid was identified as lysine-51 on the basis of sequence similarity with human and yeast amino acid sequences in this region. The reaction of the enzyme with the alkylating agent and the specific protection against inactivation by argininosuccinate suggest that this lysine residue has an essential role in the binding of argininosuccinate to the enzyme and, consequently, is essential for catalysis.

  6. 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.

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

    ERIC Educational Resources Information Center

    Copper, Christine L.; Koubeck, Edward

    1999-01-01

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

  8. Reaction rate calculation with time-dependent invariant manifolds Thomas Bartsch,1

    E-print Network

    Reaction rate calculation with time-dependent invariant manifolds Thomas Bartsch,1 F. Revuelta,2 R mechanism, and provides at the same time a simple approximation to the reaction rate. More specifically, TST 2012) The identification of trajectories that contribute to the reaction rate is the crucial dynamical

  9. 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.

  10. Laser flash photolysis studies of radical-radical reaction kinetics: The HO{sub 2} + IO reaction

    SciTech Connect

    Cronkhite, J.M.; Stickel, R.E.; Nicovich, J.M.; Wine, P.H.

    1999-04-29

    Reactive iodine as a potential tropospheric O{sub 3} sink has received considerable attention recently. Laser flash photolysis of Cl{sub 2}/CH{sub 3}OH/O{sub 2}/I{sub 2}/NO{sub 2}/SF{sub 6}N{sub 2} mixtures at 308 nm has been coupled with simultaneous time-resolved detection of HO{sub 2} (by infrared tunable diode laser absorption spectroscopy) and IO (by visible absorption spectroscopy) to investigate the kinetics of the atmospherically important reaction HO{sub 2} + IO {r_arrow} products over the temperature range 274--373 K in N{sub 2} buffer gas at pressures of 12 and 25 Torr. All experiments were performed under near pseudo-first-order conditions with HO{sub 2} in excess over IO. At 298 K, the rate coefficient was determined to be (9.7 {+-} 2.9) {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}, with the primary source of uncertainty being knowledge of the infrared line strength(s) required to convert measured HO{sub 2} absorbances to absolute concentrations. The temperature dependence of the HO{sub 2} + IO rate coefficient was found to be adequately described by the Arrhenius expression k = 9.3 {times} 10{sup {minus}12} exp(680/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The results reported in this study are compared with other recent studies of HO{sub 2} + IO kinetics, and the potential roles of this reaction in atmospheric chemistry are discussed.

  11. Insights into solar photo-Fenton reaction parameters in the oxidation of a sanitary landfill leachate at lab-scale.

    PubMed

    Silva, Tânia F C V; Ferreira, Rui; Soares, Petrick A; Manenti, Diego R; Fonseca, Amélia; Saraiva, Isabel; Boaventura, Rui A R; Vilar, Vítor J P

    2015-12-01

    This work evaluates the effect of the main photo-Fenton (PF) reaction variables on the treatment of a sanitary landfill leachate collected at the outlet of a leachate treatment plant, which includes aerated lagooning followed by aerated activated sludge and a final coagulation-flocculation step. The PF experiments were performed in a lab-scale compound parabolic collector (CPC) photoreactor using artificial solar radiation. The photocatalytic reaction rate was determined while varying the total dissolved iron concentration (20-100 mg Fe(2+)/L), solution pH (2.0-3.6), operating temperature (10-50 °C), type of acid used for acidification (H2SO4, HCl and H2SO4 + HCl) and UV irradiance (22-68 W/m(2)). This work also tries to elucidate the role of ferric hydroxides, ferric sulphate and ferric chloride species, by taking advantage of ferric speciation diagrams, in the efficiency of the PF reaction when applied to leachate oxidation. The molar fraction of the most photoactive ferric species, FeOH(2+), was linearly correlated with the PF pseudo-first order kinetic constants obtained at different solution pH and temperature values. Ferric ion speciation diagrams also showed that the presence of high amounts of chloride ions negatively affected the PF reaction, due to the decrease of ferric ions solubility and scavenging of hydroxyl radicals for chlorine radical formation. The increment of the PF reaction rates with temperature was mainly associated with the increase of the molar fraction of FeOH(2+). The optimal parameters for the photo-Fenton reaction were: pH = 2.8 (acidification agent: H2SO4); T = 30 °C; [Fe(2+)] = 60 mg/L and UV irradiance = 44 WUV/m(2), achieving 72% mineralization after 25 kJUV/L of accumulated UV energy and 149 mM of H2O2 consumed. PMID:26342264

  12. Kinetics of tetrabromobisphenol A (TBBPA) reactions with H?SO?, HNO? and HCl: implication for hydrometallurgy of electronic wastes.

    PubMed

    Zhong, Yin; Li, Dan; Mao, Zhe; Huang, Weilin; Peng, Ping'an; Chen, Pei; Mei, Jun

    2014-04-15

    Hydrometallurgy is an acid leaching based process widely used for recovering precious metals from electronic wastes (e-wastes). The effects of acid leaching on the fate of brominated flame retardants (BFRs) in typical hydrometallurgical processes remain largely unknown. This study was aimed at evaluating the fate of tetrabromobisphenol A (TBBPA), a commonly used BFR, in three acid leaching reagents (i.e. H2SO4, HNO3, and HCl) commonly used in hydrometallurgy. It was found that the reactions of TBBPA with concentrated H2SO4 followed a pseudo-zero-order rate and the reaction rates declined rapidly as the concentrations of H2SO4 decreased. In contrast, TBBPA could be easily transformed in less concentrated HNO3 solutions (<21.7 wt%) and the reactions followed a pseudo-first-order rate. The reaction products identified by GC-MS indicated different transformation pathways of TBBPA in H2SO4 and HNO3. HCl or HCl/H2SO4 mixtures (3:1, v/v) did not appear to react with TBBPA, while aqua regia (3:1 HCl/HNO3, v/v) reacted violently with TBBPA and led to almost complete disappearance of TBBPA within a minute. It suggested that HNO3 significantly affected the fate of TBBPA and the use of HNO3 as leaching reagents in hydrometallurgy of e-wastes should be carefully evaluated. Collectively, our findings of distinct fate of TBBPA in different acid leaching reagents provided fundamental information for design of hydrometallurgical treatment of e-wastes to minimize acid reactions with BFRs within plastics matrix and to maximize acid leaching efficiency for metals recycling processes. PMID:24594840

  13. An Improved Reaction Rate Formulation for Charged-Particle Induced Thermonuclear Reaction of 2H(d,?)4He

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

    The reaction rate formula utilized in compilations such as the Nuclear Astrophysics Compilation of Reaction Rates (NACRE) uses low energy approximation due to temperatures in stars are in the region of a few keVs. Most nuclear reaction experiments were done in MeV range and the interior temperatures of massive stars are ˜109 K. Hence an improved formulation for calculating the nuclear reaction rate that is applicable to high temperatures is discussed in this work. The exact tunneling probability that is applicable for all energies is obtained by solving the Schrödinger equation. This yields an enhanced expression for the astrophysical S-factor for calculating the thermonuclear reaction rate at high temperature. The thermonuclear reaction rate from this work is applied to the 2H(d,?)4He reaction and is compared with the NACRE compilation. This improved reaction rate can be included in the nuclear reaction network in a Big Bang nucleosynthesis (BBN) code or a stellar nuclear network code.

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

    SciTech Connect

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

    2009-08-01

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

  15. The influence of steric hindrance on kinetics and isotope effects in the reaction of 2,2-bis(4-dimethylaminophenyl)-1-nitro-1-(4-nitrophenyl)ethane with DBU base in acetonitrile

    NASA Astrophysics Data System (ADS)

    Nowak, Iwona; Jarczewski, Arnold

    2014-11-01

    The pKa value for 2,2-bis(4-dimethylaminophenyl)-1-nitro-1-(4-nitrophenyl)ethane, (dmap)2 (pKa = 25.11) has been measured spectrophotometrically using buffer solutions of a few strong amine bases: 1,8-diazabicyclo[5.4.0]undec-7-ene, (DBU); 1,1,3,3-tetramethylguanidine, (TMG); 1,5,7-triazabicyclo[4.4.0]dec-5-ene, (TBD); 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, (MTBD) and their salts. The low energy conformers of nitrophenyl nitroalkanes have been determined using the semiempirical PM6 methods, (B3-LYP) density functional theory (DFT) together with the 6-31G(d,p) basis set. The participation of the low energy conformer in the proton transfer reaction to DBU base has been discussed. The kinetic data for proton transfer reactions between (dmap)2 and DBU in acetonitrile (MeCN) at pseudo-first order conditions have been presented. The influence of steric hindrance brought by reacting C-acid and organic base on the stability of the transition state has been discussed. The rates of second-order rate constants for series of nitrophenyl nitroalkanes, NO2PhCHRNO2 (R = Me; Et; iPr; dimethylaminophenyl = (dmap)2) are presented and discussed.

  16. Rate of Mixing Controls Rate and Outcome of Autocatalytic Processes: Theory and Microfluidic Experiments with Chemical Reactions and

    E-print Network

    Ismagilov, Rustem F.

    Experiments with Chemical Reactions and Blood Coagulation Rebecca R. Pompano, Hung-Wing Li, and Rustem F of both biological and nonbiological autocatalytic reaction systems that display a threshold response to the concentration of an activator. Plug-based microfluidics was used to control the timing of reactions, the rate

  17. Reactions of sulfur-nitrosyl iron complexes of "g=2.03" family with hemoglobin (Hb): kinetics of Hb-NO formation in aqueous solutions.

    PubMed

    Sanina, N A; Syrtsova, L A; Shkondina, N I; Rudneva, T N; Malkova, E S; Bazanov, T A; Kotel'nikov, A I; Aldoshin, S M

    2007-03-01

    NO-donating ability of nitrosyl [Fe-S] complexes, namely, mononuclear dinitrosyl complexes of anionic type [Fe(S2O3)2(NO)2]-(I) and neutral [Fe2(SL1)2(NO)2] with L1=1H-1,2,4-triazole-3-yl (II); tetranitrosyl binuclear neutral complexes [Fe2(SL2)2(NO)4] with L2=5-amino-1,2,4-triazole-3-yl (III); 1-methyl-1H-tetrazole-5-yl (IV); imidazole-2-yl (V) and 1-methyl-imidazole-2-yl (VI) has been studied. In addition, Roussin's "red salt" Na2[Fe2S2(NO)4] x 8H2O (VII) and Na2[Fe(CN)5NO] x H2O (VIII) have been investigated. The method for research has been based on the formation of Hb-NO adduct upon the interaction of hemoglobin with NO generated by complexes I-VIII in aqueous solutions. Kinetics of NO formation was studied by registration of absorption spectra of the reaction systems containing Hb and the complex under study. For determination of HbNO concentration, the experimental absorption spectra were processed during the reaction using standard program MATHCAD to determine the contribution of individual Hb and HbNO spectra in each spectrum. The reaction rate constants were obtained by analyzing kinetic dependence of Hb interaction with NO donors under study. All kinetic dependences for complexes I-VI were shown to be described well in the frame of formalism of pseudo first-order reactions. The effective first-order rate constants for the studied reactions have been determined. As follows from the values of rate constants, the rate of interaction of sulfur-nitrosyl iron complexes (I-VI) with Hb is limited by the stage of NO release in the solution. PMID:17140821

  18. 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.

  19. Influence of Chemical Kinetics on Postcolumn Reaction in a Capillary Taylor Reactor with Catechol Analytes and Photoluminescence Following Electron Transfer

    PubMed Central

    Jung, Moon Chul; Weber, Stephen G.

    2006-01-01

    Postcolumn derivatization reactions can enhance detector sensitivity and selectivity, but their successful combination with capillary liquid chromatography has been limited because of the small peak volumes in capillary chromatography. A capillary Taylor reactor (CTR), developed in our laboratory, provides simple and effective mixing and reaction in a 25-?m-radius postcolumn capillary. Homogenization of reactant streams occurs by radial diffusion, and a chemical reaction follows. Three characteristic times for a given reaction process can be predicted using simple physical and chemical parameters. Two of these times are the homogenization time, which governs how long it takes the molecules in the analyte and reagent streams to mix, and the reaction time, which governs how long the molecules in a homogeneous solution take to react. The third characteristic time is an adjustment to the reaction time called the start time, which represents an estimate of the average time the analyte stream spends without exposure to reagent. In this study, laser-induced fluorescence monitored the extent of the postcolumn reaction (reduction of Os(bpy)33+ by analyte to the photoluminescent Os(bpy)32+) in a CTR. The reaction time depends on the reaction rates. Analysis of product versus time data yielded second-order reaction rate constants between the PFET reagent, tris(2,2?-bipyridine)osmium, and standards ((ferrocenylmethyl)trimethylammonium cation and p-hydroquinone) or catechols (dopamine, epinephrine, norepinephrine, 3, 4-dihydroxyphenylacetic acid. The extent of the reactions in a CTR were then predicted from initial reaction conditions and compared to experimental results. Both the theory and experimental results suggested the reactions of catechols were generally kinetically controlled, while those of the standards were controlled by mixing time (1–2 s). Thus, the extent of homogenization can be monitored in a CTR using the relatively fast reaction of the reagent and p-hydroquinone. Kinetically controlled reactions of catechols, however, could be also completed in a reasonable time at increased reagent concentration. A satisfactory reactor, operating at 1.7 cm/s (2 ?L/min) velocity with solutes having diffusion coefficients in the 5 × 10?6 cm2/s range, can be constructed from 8.0 cm of 25-?m-radius capillary. Slower reactions require longer reaction times, but theoretical calculations expect that a CTR does not broaden a chromatographic peak (N = 14 000) from a 100-?m-capillary chromatography column by 10% if the pseudo-first-order rate constant is larger than 0.1 s?1. PMID:15858975

  20. Big-Bang reaction rates within the R-matrix model

    NASA Astrophysics Data System (ADS)

    Descouvemont, P.; Adahchour, A.; Angulo, C.; Coc, A.; Vangioni-Flam, E.

    2005-07-01

    We use the R-matrix theory to fit S-factor data on nuclear reactions involved in Big Bang nucleosynthesis. We derive the reaction rates with associated uncertainties, which are evaluated on statistical grounds. We provide S factors and reaction rates in tabular and graphical formats (available at http://pntpm3.ulb.ac.be/bigbang).

  1. Enhanced reaction rates in NDP analysis with neutron scattering

    SciTech Connect

    Downing, R. Gregory

    2014-04-15

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

  2. Neutron detector for fusion reaction-rate measurements

    SciTech Connect

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

    1993-09-03

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

  3. Heterogeneous reactions of SO2 with HOCl and HOBr on ice surfaces.

    PubMed

    Jin, Ronghua; Chu, Liang T

    2006-07-20

    The heterogeneous reactions of SO2 + HOX (X = Cl or Br) --> products on ice surfaces at low temperature have been investigated in a flow reactor coupled with a differentially pumped quadrupole mass spectrometer. Pseudo-first-order loss of SO2 over the ice surfaces has been measured under the conditions of concurrent HOX flow. The initial uptake coefficient of SO2 reaction with HOX has been determined as a function of HOX surface coverage, theta(HOX), on the ice. The initial uptake coefficients increase as the HOX coverage increases. The uptake coefficient can be expressed as gamma(t) = k(h)theta(HOX), where k(h) is an overall rate constant of SO2 + HOCl, which was determined to be (2.3 +/- 0.6) x 10(-19) and (1.7 +/- 0.5) x 10(-19) molecules(-1) x cm2 at 190 and 210 K, and k(h) of SO2 + HOBr is (6.1 +/- 2.0) x 10(-18) molecules(-1) x cm2 at 190 K. theta( HOX) is in the range 8.1 x 10(13)-9.1 x 10(14) molecules x cm(-2). The kinetic results of the heterogeneous reaction of SO2 + HOX on ice surface are interpreted using the Eley-Rideal mechanism. The activation energy of the heterogeneous reaction of SO2 with HOCl on ice surface was determined to be about -37 +/- 10 kJ/mol in the 190-238 K range. PMID:16836433

  4. The surface reaction kinetics of salicylate on alumina

    SciTech Connect

    Wang, Z.; Ainsworth, C.C.; Friedrich, D.M.; Joly, A.G.; Gassman, P.L.

    1997-12-31

    The kinetics of reaction of salicylate with colloidal alumina in aqueous suspension and with Al(III) in homogeneous aqueous solution were studied by stopped-flow laser fluorescence spectroscopy. The emission spectra confirmed the formation of both monodentate complexes and more stable bidentate chelates. Temporal evolution of the spectra indicated that the reaction was fast (within first few minutes) for both the homogeneous and heterogeneous reactions but slowed down afterwards for the latter. Reactions completed within 10 minutes in homogeneous phase at pH 3.3 but took more than 12 hours in alumina suspension. Analysis of the fluorescence intensity within first four minutes showed that in homogeneous phase the reaction followed a single pseudo-first-order kinetics. In alumina suspension log plots were nonlinear and characteristic of multiple heterogeneous reaction paths. The kinetics are interpreted in terms of the simultaneous formation of multiple species as well as subsequent conversion between species.

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

    SciTech Connect

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

    1994-10-27

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

  6. Kinetics of CH2OO reactions with SO2, NO2, NO, H2O and CH3CHO as a function of pressure.

    PubMed

    Stone, Daniel; Blitz, Mark; Daubney, Laura; Howes, Neil U M; Seakins, Paul

    2014-01-21

    Kinetics of CH2OO Criegee intermediate reactions with SO2, NO2, NO, H2O and CH3CHO and CH2I radical reactions with NO2 are reported as a function of pressure at 295 K. Measurements were made under pseudo-first-order conditions using flash photolysis of CH2I2-O2-N2 gas mixtures in the presence of excess co-reagent combined with monitoring of HCHO reaction products by laser-induced fluorescence (LIF) spectroscopy and, for the reaction with SO2, direct detection of CH2OO by photoionisation mass spectrometry (PIMS). Rate coefficients for CH2OO + SO2 and CH2OO + NO2 are independent of pressure in the ranges studied and are (3.42 ± 0.42) × 10(-11) cm(3) s(-1) (measured between 1.5 and 450 Torr) and (1.5 ± 0.5) × 10(-12) cm(3) s(-1) (measured between 25 and 300 Torr), respectively. The rate coefficient for CH2OO + CH3CHO is pressure dependent, with the yield of HCHO decreasing with increasing pressure. Upper limits of 2 × 10(-13) cm(3) s(-1) and 9 × 10(-17) cm(3) s(-1) are placed on the rate coefficients for CH2OO + NO and CH2OO + H2O, respectively. The upper limit for the rate coefficient for CH2OO + H2O is significantly lower than has been reported previously, with consequences for modelling of atmospheric impacts of CH2OO chemistry. PMID:24287566

  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. Rate constants of reactions of ?-carrageenan with hydrated electron and hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Abad, L. V.; Saiki, S.; Kudo, H.; Muroya, Y.; Katsumura, Y.; de la Rosa, A. M.

    2007-12-01

    The rate constants for the reactions of ?-carrageenan with hydrated electron and hydroxyl radical was investigated by pulse radiolysis and laser photolysis. The kinetics of the reaction of hydrated electron indicates no seeming reaction with ?-carrageenan. On the other hand, hydroxyl radical reacts very rapidly with ?-carrageenan at a rate constant of approximately 1.2 × 10 9 M -1 s -1. This rate constant varies with pH.

  9. Cross sections and reaction rates of relevance to aeronomy

    SciTech Connect

    Fox, J.L. )

    1991-01-01

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

  10. Structural and kinetic studies of the polymerization reactions of ?-caprolactone catalyzed by (pyrazol-1-ylmethyl)pyridine Cu(II) and Zn(II) complexes.

    PubMed

    Ojwach, Stephen O; Okemwa, Teddy T; Attandoh, Nelson W; Omondi, Bernard

    2013-08-14

    The structural and kinetic studies of polymerization reactions of ?-caprolactone (?-CL) using (pyrazolylmethyl)pyridine Cu(II) and Zn(II) complexes as initiators is described. Reactions of 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L1) and 2-(3,5-diphenylpyrazol-1-ylmethyl)pyridine (L2) with Zn(Ac)2·2H2O or Cu(Ac)2·2H2O produced the corresponding complexes [Zn(Ac)2(L1)] (1), [Cu(Ac)2(L1)] (2), [Zn(Ac)2(L2)] (3) and [Cu2(Ac)4(L2)2] (4) respectively. Solid state structures of 1 and 4 confirmed that complexes 1 and 4 are monomeric and dimeric respectively and that L1 is bidentate in 1 while L2 is monodentate in 4. X-band EPR spectra of 2 and 4 revealed that complex 2 is monomeric both in solid and solution state, while the paddle-wheel structure of 4 is retained in solution. Complexes 1-4 formed active initiators in the ring opening polymerization of ?-CL. Zn(II) complexes 1 and 3 exhibited higher rate constants of 0.044 h(-1) and 0.096 h(-1) respectively compared to rate constants of 0.017 h(-1) and 0.031 h(-1) observed for the corresponding Cu(II) complexes 2 and 4 respectively at 110 °C. All the polymerization reactions follow pseudo first-order kinetic with respect to ?-CL monomer. Initiator 1 showed first-order dependency on the polymerization reactions and utilizes only one active site as the initiating group. The molecular weights of the polymers produced range from 1982 g mol(-1) to 14,568 g mol(-1) and exhibited relatively broad molecular weight distributions associated with transesterification reactions. PMID:23774962

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

    NASA Technical Reports Server (NTRS)

    Eberstein, I. J.

    1974-01-01

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

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

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Bayes, K.

    1998-01-01

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

  13. SHEAR LOCALIZATION AND CHEMICAL REACTION IN HIGH-STRAIN, HIGH-STRAIN-RATE DEFORMATION OF

    E-print Network

    Meyers, Marc A.

    SHEAR LOCALIZATION AND CHEMICAL REACTION IN HIGH-STRAIN, HIGH-STRAIN-RATE DEFORMATION OF Ti regions can initiate chemical reaction inside a reac- tive powder mixture. The shear band spacing was H0-induced chemical reactions in silicide systems have been investigated in recent years. Vreeland and coworkers [7

  14. Automated Discovery of Reaction Pathways, Rate Constants, and Transition States Using Reactive Molecular Dynamics Simulations.

    PubMed

    Döntgen, Malte; Przybylski-Freund, Marie-Dominique; Kröger, Leif C; Kopp, Wassja A; Ismail, Ahmed E; Leonhard, Kai

    2015-06-01

    We provide a methodology for deducing quantitative reaction models from reactive molecular dynamics simulations by identifying, quantifying, and evaluating elementary reactions of classical trajectories. Simulations of the inception stage of methane oxidation are used to demonstrate our methodology. The agreement of pathways and rates with available literature data reveals the potential of reactive molecular dynamics studies for developing quantitative reaction models. PMID:26575551

  15. Quick and Easy Rate Equations for Multistep Reactions

    ERIC Educational Resources Information Center

    Savage, Phillip E.

    2008-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1987-04-01

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

  18. Manganese peroxidase from the lignin-degrading basidiomycete Phanerochaete chrysosporium: Transient state kinetics and reaction mechanism

    SciTech Connect

    Wariishi, Hiroyuki; Gold, M.H. ); Dunford, H.B.; MacDonald, I.D. )

    1989-02-25

    Stopped-flow techniques were used to investigate the kinetics of the formation of manganese peroxidase compound I (MnPI) and of the reactions of MnPI and manganese peroxidase compound II (MnPII) with p-cresol and Mn{sup II}. All of the rate data were obtained from single turnover experiments under pseudo-first order conditions. In the presence of H{sub 2}O{sub 2} the formation of MnPI is independent of pH over the range 3.12-8.29 with a second-order rate constant of (2.0{+-}0.1) {times} 10{sup 6} M{sup {minus}1} s{sup {minus}1}. The activation energy for MnPI formation is 20 kJ mol{sup {minus}1}. MnPI formation also occurs with organic peroxides such as peracetic acid, m-chloroperoxybenzoic acid, and p-nitroperoxybenzoic acid with second-order rate constants of 9.7 x 10{sup 5}, 9.5 {times} 10{sup 4}, and 5.9 {times} 10{sup 4} M{sup {minus}1} s{sup {minus}1}, respectively. The reactions of MnPI and MnPII with p-cresol strictly obeyed second-order kinetics. The second-order rate constant for the reaction of MnPII with p-cresol is extremely low, (9.5{+-}0.5) m{sup {minus}1} s{sup {minus}1}. Kinetic analysis of the reaction of Mn{sup II} with MnPI and MnPII showed a binding interaction with the oxidized enzymes which led to saturation kinetics. The first-order dissociation rate constants for the reaction of Mn{sup II} with MnPI and MnPII are (0.7{+-}0.1) and (0.14{+-}0.01) s{sup {minus}1}, respectively, when the reaction is conducted in lactate buffer. Rate constants are considerably lower when the reactions are conducted in succinate buffer. Single turnover experiments confirmed that Mn{sup II} serves as an obligatory substrate for MnPII and that both oxidized forms of the enzyme form productive complexes with Mn{sup II}. Finally, these results suggest the {alpha}-hydroxy acids such as lactate facilitate the dissociation of Mn{sup II} from the enzyme.

  19. Malonic acid concentration as a control parameter in the kinetic analysis of the Belousov-Zhabotinsky reaction under batch conditions.

    PubMed

    Blagojevi?, Slavica M; Ani?, Slobodan R; Cupi?, Zeljko D; Peji?, Natasa D; Kolar-Ani?, Ljiljana Z

    2008-11-28

    The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained. PMID:18989478

  20. Rate of diffusiondimited reactions in dispersions of spherical traps via multipole scattering

    E-print Network

    Rate of diffusiondimited reactions in dispersions of spherical traps via multipole scattering R. T, California 91125 (Received 31 May 1990;accepted27 September1990) The elective reaction rate is calculated-range interactions, plus direct addition of exact two-body interactions is employed. It is found that the addition

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

    NASA Technical Reports Server (NTRS)

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

    1974-01-01

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

  2. Prediction of Astrophysical Reaction Rates: Methods, Data Needs, and

    E-print Network

    Rauscher, Thomas

    . This is also important if one wants to disentangle stellar #12; physics and nuclear effects in the comparison, CA 95064 Abstract. The majority of nuclear reactions in astrophysics involve unstable nuclei which of the statistical model (Hauser­ Feshbach). The global parametrizations of the nuclear properties needed

  3. Using the Power-Law Rate Expression for Assessment of Rate Data and Detection of Infeasible Mechanisms for Reversible Reactions

    E-print Network

    Brauner, Neima

    -Aviv, 69978 Israel A procedure for analysis of experimental data and model discrimination in regression the following mechanistic model discrimination process conclusive. The parameter values of the power-law rate. Introduction The design of a catalytic reactor involves the need for a correlation relating the reaction rates

  4. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Thanh, Vo Hong; Priami, Corrado

    2015-08-01

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

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

    NASA Astrophysics Data System (ADS)

    Copper, Christine L.; Koubek, Edward

    1999-12-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    DOE PAGESBeta

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-07-01

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

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

    PubMed

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

    2012-08-01

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

  12. Reaction Rate Uncertainties: NeNa and MgAl in AGB Stars

    E-print Network

    Robert Izzard; Maria Lugaro; Christian Iliadis; Amanda Karakas

    2006-07-24

    We study the effect of uncertainties in the proton-capture reaction rates of the NeNa and MgAl chains on nucleosynthesis due to the operation of hot bottom burning (HBB) in intermediate-mass asymptotic giant branch (AGB) stars. HBB nucleosynthesis is associated with the production of sodium, radioactive Al26 and the heavy magnesium isotopes, and it is possibly responsible for the O, Na, Mg and Al abundance anomalies observed in globular cluster stars. We model HBB with an analytic code based on full stellar evolution models so we can quickly cover a large parameter space. The reaction rates are varied first individually, then all together. This creates a knock-on effect, where an increase of one reaction rate affects production of an isotope further down the reaction chain. We find the yields of Ne22, Na23 and Al26 to be the most susceptible to current nuclear reaction rate uncertainties.

  13. Upper atmosphere research: Reaction rate and optical measurements

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Nagypál, István; Epstein, Irving R.

    1988-12-01

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

  15. Sensitivity study of explosive nucleosynthesis in Type Ia supernovae: I. Modification of individual thermonuclear reaction rates

    E-print Network

    Eduardo Bravo; Gabriel Martínez-Pinedo

    2012-04-09

    We explore the sensitivity of the nucleosynthesis due to type Ia supernovae with respect to uncertainties in nuclear reaction rates. We have adopted a standard one-dimensional delayed detonation model of the explosion of a Chandrasekhar-mass white dwarf, and have post-processed the thermodynamic trajectories of every mass-shell with a nucleosynthetic code, with increases (decreases) by a factor of ten on the rates of 1196 nuclear reactions. We have computed as well hydrodynamic models for different rates of the fusion reactions of 12C and of 16O. For selected reactions, we have recomputed the nucleosynthesis with alternative prescriptions for their rates taken from the JINA REACLIB database, and have analyzed the temperature ranges where modifications of their rates have the strongest effect on nucleosynthesis. 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 12C nuclei. The energy of the explosion changes by less than \\sim4%. The changes in the nucleosynthesis due to the modification of the rates of fusion reactions are as well quite modest, for instance no species with a mass fraction larger than 0.02 experiences a variation of its yield larger than a factor of two. We provide the sensitivity of the yields of the most abundant species with respect to the rates of the most intense reactions with protons, neutrons, and alphas. In general, the yields of Fe-group nuclei are more robust than the yields of intermediate-mass elements. Among the charged particle reactions, the most influential on supernova nucleosynthesis are 30Si + p \\rightleftarrows 31P + {\\gamma}, 20Ne + {\\alpha} \\rightleftarrows 24Mg + {\\gamma}, and 24Mg + {\\alpha} \\rightleftarrows 27Al + p. The temperatures at which a modification of their rate has a larger impact are in the range 2 < T < 4 GK. (abridged)

  16. 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 ? ?(-1), deviates widely for many reactions studied. In most cases, the deviation simulates a power law k ? ?(-n), where the exponent n assumes fractional values. In rate-viscosity studies presented here, results for two reactions, unfolding of cytochrome c and cysteine protease activity of human ribosomal protein S4, show an exceedingly overdamped rate over a wide viscosity range, registering n values up to 2.4. Although the origin of this extraordinary reaction friction is not known at present, the results indicate that the viscosity exponent need not be bound by the 0-1 limit as generally suggested. For the third reaction studied here, thermal dissociation of CO from nativelike cytochrome c, the rate-viscosity behavior can be explained using Grote-Hynes theory of time-dependent friction in conjunction with correlated motions intrinsic to the protein. Analysis of the glycerol viscosity-dependent rate for the CO dissociation reaction in the presence of urea as the second variable shows that the protein stabilizing effect of subdenaturing amounts of urea is not affected by the bulk viscosity. It appears that a myriad of factors as diverse as parameter uncertainty due to the difficulty of knowing the exact reaction friction and both mode and consequences of protein-solvent interaction work in a complex manner to convey as though Kramers rate equation is not absolute. PMID:26135219

  17. Characterization of Shock-dependent Reaction Rates in Non-ideal Perfluoropolyether-Aluminum Explosives

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    Explosive 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 - shock strength, shock duration, and shock ``planarity'' - upon the reaction rate of the explosive. The following conditions were varied in a series of sixty-four (64) reaction rate experiments: PFPE-Al composition; 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  19. Time-Resolved O3 Chemical Chain Reaction Kinetics Via High-Resolution IR Laser Absorption Methods

    NASA Technical Reports Server (NTRS)

    Kulcke, Axel; Blackmon, Brad; Chapman, William B.; Kim, In Koo; Nesbitt, David J.

    1998-01-01

    Excimer laser photolysis in combination with time-resolved IR laser absorption detection of OH radicals has been used to study O3/OH(v = 0)/HO2 chain reaction kinetics at 298 K, (i.e.,(k(sub 1) is OH + 03 yields H02 + 02 and (k(sub 2) is H02 + 03 yields OH + 202). From time-resolved detection of OH radicals with high-resolution near IR laser absorption methods, the chain induction kinetics have been measured at up to an order of magnitude higher ozone concentrations ([03] less than or equal to 10(exp 17) molecules/cu cm) than accessible in previous studies. This greater dynamic range permits the full evolution of the chain induction, propagation, and termination process to be temporally isolated and measured in real time. An exact solution for time-dependent OH evolution under pseudo- first-order chain reaction conditions is presented, which correctly predicts new kinetic signatures not included in previous OH + 03 kinetic analyses. Specifically, the solutions predict an initial exponential loss (chain "induction") of the OH radical to a steady-state level ([OH](sub ss)), with this fast initial decay determined by the sum of both chain rate constants, k(sub ind) = k(sub 1) + k(sub 2). By monitoring the chain induction feature, this sum of the rate constants is determined to be k(sub ind) = 8.4(8) x 10(exp -14) cu cm/molecule/s for room temperature reagents. This is significantly higher than the values currently recommended for use in atmospheric models, but in excellent agreement with previous results from Ravishankara et al.

  20. 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.

  1. PHYSICAL REVIEW C 72, 025806 (2005) Nuclear fusion in dense matter: Reaction rate and carbon burning

    E-print Network

    2005-01-01

    PHYSICAL REVIEW C 72, 025806 (2005) Nuclear fusion in dense matter: Reaction rate and carbon August 2005) In this paper we analyze the nuclear fusion rates among equal nuclei for all five different.025806 PACS number(s): 26.50.+x, 25.60.Pj, 97.10.Cv I. INTRODUCTION We study nuclear fusion rates of identical

  2. 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 ×0.1. The changes in the nucleosynthesis owing to the modification of the rates of these fusion reactions are also quite modest; for instance, no species with a mass fraction larger than 0.02 experiences a variation of its yield larger than a factor of 2. We provide the sensitivity of the yields of the most abundant species with respect to the rates of the most intense reactions with protons, neutrons, and ?. In general, the yields of Fe-group nuclei are more robust than the yields of intermediate-mass elements. Among the species with yields larger than 10-8M?, 35S has the largest sensitivity to the nuclear reaction rates. It is remarkable that the reactions involving elements with Z>22 have a tiny influence on the supernova nucleosynthesis. Among the charged-particle reactions, the most influential on supernova nucleosynthesis are 30Si+p?31P+?, 20Ne+??24Mg+?, and 24Mg+??27Al+p. The temperatures at which a modification of their rate has a larger impact are in the range 2?T?4 GK.Conclusions: The explosion model (i.e., the assumed conditions and propagation of the flame) chiefly determines the element production of type Ia supernovae and derived quantities such as their luminosity, while the nuclear reaction rates used in the simulations have a small influence on the kinetic energy and final chemical composition of the ejecta. Our results show that the uncertainty in individual thermonuclear reaction rates cannot account for discrepancies of a factor of 2 between isotopic ratios in type Ia supernovae and those in the solar system, especially within the Fe group.

  3. Microscopic theory of protein folding rates. II. Local reaction coordinates and chain dynamics

    E-print Network

    Takada, Shoji

    Microscopic theory of protein folding rates. II. Local reaction coordinates and chain dynamics John involved in barrier crossing for protein folding are investigated in terms of the chain dynamics paper. Local reaction coordinates are identified as collective growth modes of the unstable fluctuations

  4. Efficient ab initio sampling methods in rate constant calculations for proton-transfer reactions

    E-print Network

    Schofield, Jeremy

    Efficient ab initio sampling methods in rate constant calculations for proton-transfer reactions, 2000 is applied to an ab initio simulation of the proton transfer tautomerization reaction covalent chemical bonds are formed or broken. In such instances, ab initio methods of calculating

  5. Effects of arsenic incorporation on jarosite dissolution rates and reaction products

    E-print Network

    Hu, Qinhong "Max"

    Effects of arsenic incorporation on jarosite dissolution rates and reaction products Matthew R to hematite with time in ultra-pure water, but increasing arsenic concentrations slow this transition. At pH >3.5, arsenic from the dissolution of arsenojarosite adsorbs onto newly formed reaction products

  6. Integrated rate equations for irreversible enzyme-catalysed first-order and second-order reactions.

    PubMed Central

    Boeker, E A

    1985-01-01

    Integrated rate equations are presented that describe irreversible enzyme-catalysed first-order and second-order reactions. The equations are independent of the detailed mechanism of the reaction, requiring only that it be hyperbolic and unbranched. The results should be directly applicable in the laboratory. PMID:3977872

  7. PHYSICAL REVIEW C 80, 014611 (2009) Nuclear fusion reaction rates for strongly coupled ionic mixtures

    E-print Network

    2009-01-01

    PHYSICAL REVIEW C 80, 014611 (2009) Nuclear fusion reaction rates for strongly coupled ionic.014611 PACS number(s): 26.30.-k I. INTRODUCTION Nuclear fusion in dense stellar matter is most important the nuclear interaction. We will mostly focus on the Coulomb barrier penetration problem. Fusion reactions

  8. 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.

  9. Mean reaction rate closures for nanoparticle formation in turbulent reacting flow

    E-print Network

    Akroyd, Jethro

    2012-11-08

    , particle population dynamics and turbulent flow, and offer the potential to improve the understanding of a range of industrial processes. The numerical behaviour of a mean reaction rate closure based on the direct quadrature method of moments using...

  10. 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.

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

    SciTech Connect

    Skakun, Ye.; Rauscher, T.

    2010-08-12

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

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

    SciTech Connect

    Lindquist, W Brent

    2009-03-03

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

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

    SciTech Connect

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

    2009-02-06

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

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

    SciTech Connect

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

    2015-09-01

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

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

    SciTech Connect

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

    2013-07-15

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

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

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

  17. 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.

  18. The nuclear fusion reaction rate based on relativistic equilibrium velocity distribution

    E-print Network

    Jian-Miin Liu

    2002-10-20

    The Coulomb barrier is in general much higher than thermal energy. Nuclear fusion reactions occur only among few protons and nuclei with higher relative energies than Coulomb barrier. It is the equilibrium velocity distribution of these high-energy protons and nuclei that participates in determining the rate of nuclear fusion reactions. In the circumstance it is inappropriate to use the Maxwellian velocity distribution for calculating the nuclear fusion reaction rate. We use the relativistic equilibrium velocity distribution for this purpose. The rate based on the relativistic equilibrium velocity distribution has a reduction factor with respect to that based on the Maxwellian distribution, which factor depends on the temperature, reduced mass and atomic numbers of the studied nuclear fusion reactions. This signifies much to the solar neutrino problem.

  19. Metabolic control analysis of biochemical pathways based on a thermokinetic description of reaction rates.

    PubMed Central

    Nielsen, J

    1997-01-01

    Metabolic control analysis is a powerful technique for the evaluation of flux control within biochemical pathways. Its foundation is the elasticity coefficients and the flux control coefficients (FCCs). On the basis of a thermokinetic description of reaction rates it is here shown that the elasticity coefficients can be calculated directly from the pool levels of metabolites at steady state. The only requirement is that one thermodynamic parameter be known, namely the reaction affinity at the intercept of the tangent in the inflection point of the curve of reaction rate against reaction affinity. This parameter can often be determined from experiments in vitro. The methodology is applicable only to the analysis of simple two-step pathways, but in many cases larger pathways can be lumped into two overall conversions. In cases where this cannot be done it is necessary to apply an extension of the thermokinetic description of reaction rates to include the influence of effectors. Here the reaction rate is written as a linear function of the logarithm of the metabolite concentrations. With this type of rate function it is shown that the approach of Delgado and Liao [Biochem. J. (1992) 282, 919-927] can be much more widely applied, although it was originally based on linearized kinetics. The methodology of determining elasticity coefficients directly from pool levels is illustrated with an analysis of the first two steps of the biosynthetic pathway of penicillin. The results compare well with previous findings based on a kinetic analysis. PMID:9003411

  20. Trickle-bed reactor for investigating upgrading reactions

    SciTech Connect

    Kottenstette, R.J.; Stephens, H.P.

    1990-01-01

    The catalytic processing of heavy petroleum feeds and many of the heavier synthetic fuels is performed in the liquid phase and quite often in trickle-bed reactors. In this paper we present the basis for the design of a microscale trickle-bed reactor for studying the kinetics of reactions related to coal liquefaction processes. This small (10 cm-long) catalyst bed was used to study the hydrogenation of naphthalene to tetralin at 373 K and the hydrogenation of pyrene to dihydropyrene at 573 K. The hydrogenation of naphthalene to tetralin using a palladium (Pd) catalyst has been shown to be a pseudo-first-order irreversible reaction at 373 K, while the hydrogenation of pyrene to dihydropyrene using a nickel molybdenum on alumina catalyst (NiMo/alumina) has been shown to be a pseudo-first-order reversible reaction at 573 K. First-order kinetic plots for the flow reactor experiments show that plug-flow behavior was achieved for both the hydrogenation of naphthalene and pyrene. In addition, plug flow was not perturbed by increasing the hydrogen gas flow by a factor of four. A reactor of such small scale with achievable plug flow behavior is an important tool for catalyst activity testing since it provides the ability to adjust reaction conditions easily and allows catalyst deactivation to be studied more effectively. In addition, a wide variety of hydrotreating reactions including hydrodesulfurization (HDS), hydrodeoxygenation (HDO), and hydrodenitrogenation (HDN), can be studied using this simple reactor design. 10 refs., 6 figs., 1 tab.

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

    SciTech Connect

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

    2010-08-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  3. Four-Angle Saturation Transfer (FAST) Method for Measuring Creatine Kinase Reaction Rates In Vivo

    E-print Network

    Ouwerkerk, Ronald

    Four-Angle Saturation Transfer (FAST) Method for Measuring Creatine Kinase Reaction Rates In Vivo to the effects of exchange are evaluated for creatine kinase (CK) metab- olism modeled for skeletal and heart rates; creatine kinase; high-energy phosphate; energy metabolism Compromised energy metabolism

  4. 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.

  5. 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.

  6. The Quantum Instanton (QI) Model for Chemical Reaction Rates: The "Simplest" QI with One Dividing Surface

    E-print Network

    Miller, William H.

    The Quantum Instanton (QI) Model for Chemical Reaction Rates: The "Simplest" QI with One Dividing: December 10, 2003 A new version of the quantum instanton (QI) approach to thermal rate constants) is presented, namely, the simplest QI (SQI) approximation with one dividing surface (DS), referred to here

  7. 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.

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

    PubMed

    Baxter; DePaolo

    2000-05-26

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

  9. On the Influence of Uncertainties in Chemical Reaction Rates on Results of the Astrochemical Modelling

    E-print Network

    A. I. Vasyunin; A. M. Sobolev; D. S. Wiebe; D. A. Semenov

    2003-11-19

    With the chemical reaction rate database UMIST95 (Millar et al. 1997) we analyze how uncertainties in rate constants of gas-phase chemical reactions influence the modelling of molecular abundances in the interstellar medium. Random variations are introduced into the rate constants to estimate the scatter in theoretical abundances. Calculations are performed for dark and translucent molecular clouds where gas phase chemistry is adequate. Similar approach was used by Pineau des Forets & Roueff (2000) for the study of chemical bistability. All the species are divided into 6 sensitivity groups according to the value of the scatter in their model abundances computed with varied rate constants. It is shown that the distribution of species within these groups depends on the number of atoms in a molecule and on the adopted physical conditions. The simple method is suggested which allows to single out reactions that are most important for the evolution of a given species.

  10. 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.

  11. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

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

    PubMed

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

    2015-11-01

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

  14. Scale-dependent rates of uranyl surface complexation reaction in sediments

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    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 show that the grain-scale rate constant of U(VI) surface complexation was over 3-10 orders of magnitude smaller than the rate constant calculated using the molecular simulations. 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 that the rate of coupled diffusion and molecular surface complexation reaction in the intragranular porous domains was slower than either individual process alone. The results provide important implications for developing models to scale geochemical/biogeochemical reactions.

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

    NASA Technical Reports Server (NTRS)

    Woon, D. E.; Herbst, E.

    1997-01-01

    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.

  16. Unbound states of 32Cl and the 31S(p,?)32Cl reaction rate

    E-print Network

    M. Matoš; J. C. Blackmon; L. E. Linhardt; D. W. Bardayan; C. D. Nesaraja; J. A. Clark; C. M. Deibel; P. D. O'Malley; P. D. Parker

    2011-11-20

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

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

    SciTech Connect

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

    2011-01-01

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

  18. Astrophysical Rate for 12N(p,g)13O Direct Capture Reactions

    E-print Network

    Li Zhi-Hong

    2009-03-17

    The proton capture on the unstable nuclei plays a very important role for the nucleonsynthesis. The 12N(p,g)13O reaction rates at the energies of astrophysical interests are estimated with the spectroscopic factor and asymptotic normalization coefficient methods. The present results show that the 12N(p,g)13O reaction may play an important role in x-ray bursts.

  19. Quantum mechanical calculation of the rate constant for the reaction Alexandra Viel and Claude Leforestier

    E-print Network

    Miller, William H.

    Quantum mechanical calculation of the rate constant for the reaction H O2~OH O Alexandra Viel reaction1­12 H O2 OH O, 1 and as a realistic prototype for unimolecular dissociation13­18 [HO2]* H O2 I OH evaluation of the CRP N(E). In order to compute N(E), the Manthe and Miller21 expression N E Tr P^ E k pk E 3

  20. Thermonuclear reaction rate of {sup 17}O(p,{gamma}){sup 18}F

    SciTech Connect

    Fox, C.; Iliadis, C.; Champagne, A.E.; Fitzgerald, R.P.; Longland, R.; Newton, J.; Pollanen, J.; Runkle, R.

    2005-05-01

    The {sup 17}O(p,{gamma}){sup 18}F and {sup 17}O(p,{alpha}){sup 14}N reactions have a profound influence on hydrogen-burning nucleosynthesis in a number of stellar sites, including red giants, asymptotic giant branch (AGB) stars, massive stars, and classical novae. Previously evaluated thermonuclear rates for both reactions carry large uncertainties. We investigated the proton-capture reaction on {sup 17}O in the bombarding energy range of E{sub p}{sup lab} = 180-540 keV. We observed a previously undiscovered resonance at E{sub R}{sup lab} = 193.2 {+-} 0.9 keV. The resonance strength amounts to ({omega}{gamma}){sub p{gamma}}(1.2{+-}0.2)x10{sup -6} eV. With this value, the uncertainties of the {sup 17}O(p,{gamma}){sup 18}F reaction rates are reduced by orders of magnitude in the peak temperature range of classical novae (T=0.1-0.4 GK). We also report on a reevaluation of the {sup 17}O(p,{gamma}){sup 18}F reaction rates at lower temperatures that are pertinent to red giants, AGB stars, or massive stars. The present work establishes the {sup 17}O(p,{gamma}){sup 18}F reaction rates over a temperature range of T= 0.01-1.5 GK with statistical uncertainties of 10-50%. The new recommended reaction rates deviate from the previously accepted values by an order of magnitude around T{approx_equal}0.2 GK and by factors of 2-3 at T < 0.1 GK.

  1. Mineral/solution reaction rates in a mixed flow reactor: Wollastonite hydrolysis

    NASA Astrophysics Data System (ADS)

    Rimstidt, J. Donald; Dove, Patricia M.

    1986-11-01

    A newly developed mixed flow reactor was used to measure the rate of hydrolysis of wollastonite over the pH range of 3 to 8. This design avoids abrasion of the solid sample by confining it within a nylon mesh while the reacting solution is circulated over it by a stirrer. The rate of reaction was determined from the difference of the compositions of the input and output solutions following the methods used by chemical engineers for the analysis of mixed flow reactors, also called continuously stirred tank reactors (CSTR). This apparatus, constructed from easily obtainable parts, avoids many of the problems inherent in studying mineral/solution reaction kinetics in batch reactors. The hydrolysis of wollastonite CaSiO3 + 2 H+ + H2O = Ca2+ + H4SiO4 can be fit to a rate law of the form: dnH+/ dt = kadKH+mH+/(1.0 + KH+mH+) where kad = 9.80 × 10 -8molm-2sec-1 and KH+ = 2.08 × 10 5. Over the pH range of 4 to 7, the data also may fit a simple linear form: dnH+/ dt = - Ak+( aH+) 0.40 where k+ = 3.80 × 10 -6 sec -1 at 25°C. The presence of calcium ion in the solution at concentrations up to 1.0 mol kg -1 produces only a minor reduction of the reaction rate. The activation energy for this reaction is 79.2 kJ mol -1. Examination of the surfaces of the reacted grains showed no evidence of incongruent reaction leading to a product layer but did show the extensive development of etch pits leading to a rapid increase in the specific surface area. At large extents of reaction at low pH, diffusion of ions into or from these deep etch pits may limit the reaction rate.

  2. 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.

  3. 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.

  4. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

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

    PubMed

    Hua, Pei; Vasyukova, Ekaterina; Uhl, Wolfgang

    2015-05-15

    A second order kinetic model for simulating chlorine decay in bulk water due to the reaction with dissolved organic matter (DOM) was developed. It takes into account the decreasing reactivity of dissolved organic matter using a variable reaction rate coefficient (VRRC) which decreases with an increasing conversion. The concentration of reducing species is surrogated by the maximum chlorine demand. Temperature dependency, respectively, is described by the Arrhenius-relationship. The accuracy and adequacy of the proposed model to describe chlorine decay in bulk water were evaluated and shown for very different waters and different conditions such as water mixing or rechlorination by applying statistical tests. It is thus very well suited for application in water quality modeling for distribution systems. PMID:25765169

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

    NASA Astrophysics Data System (ADS)

    Yasuda, Keiji; Matsuura, Kazumasa

    2013-07-01

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

  8. Effect of macromolecular crowding on the rate of diffusion-limited enzymatic reaction

    E-print Network

    Manish Agrawal; S. B. Santra; Rajat Anand; Rajaram Swaminathan

    2008-07-19

    The cytoplasm of a living cell is crowded with several macromolecules of different shapes and sizes. Molecular diffusion in such a medium becomes anomalous due to the presence of macromolecules and diffusivity is expected to decrease with increase in macromolecular crowding. Moreover, many cellular processes are dependent on molecular diffusion in the cell cytosol. The enzymatic reaction rate has been shown to be affected by the presence of such macromolecules. A simple numerical model is proposed here based on percolation and diffusion in disordered systems to study the effect of macromolecular crowding on the enzymatic reaction rates. The model explains qualitatively some of the experimental observations.

  9. A combined quantum-classical dynamics method for calculating thermal rate constants of chemical reactions in solution

    E-print Network

    Truong, Thanh N.

    -flux correlation function for calculating the thermal rate constants of chemical reactions in solution in this study would provide a complete tool for studying the quantum dynamics of chemical reactions the thermal chemical reaction rate constants. Furthermore, we also employ an efficient and accurate quantum

  10. Accurate quantum calculations of the reaction rates for H/D+CH4.

    PubMed

    van Harrevelt, Rob; Nyman, Gunnar; Manthe, Uwe

    2007-02-28

    In previous work [T. Wu, H. J. Werner, and U. Manthe, Science 306, 2227 (2004)], accurate quantum reaction rate calculations of the rate constant for the H+CH4-->CH3+H2 reaction have been presented. Both the electronic structure calculations and the nuclear dynamics calculations are converged with respect to the basis sets employed. In this paper, the authors apply the same methodology to an isotopic variant of this reaction: D+CH4-->CH3+HD. Accurate rate constants are presented for temperatures between 250 and 400 K. For temperatures between 400 and 800 K, they use a harmonic extrapolation to obtain approximate rate constants for H/D+CH4. The calculations suggest that the experimentally reported rate constants for D+CH4 are about a factor of 10-20 too high. For H+CH4, more accurate experiments are available and agreement is much better: the difference is less than a factor of 2.6. The kinetic isotope effect for the H/D+CH4 reactions is studied and compared with experiment and transition state theory (TST) calculations. Harmonic TST was found to provide a good description of the kinetic isotope effect. PMID:17343444

  11. Accurate quantum calculations of the reaction rates for H /D+CH4

    NASA Astrophysics Data System (ADS)

    van Harrevelt, Rob; Nyman, Gunnar; Manthe, Uwe

    2007-02-01

    In previous work [T. Wu, H. J. Werner, and U. Manthe, Science 306, 2227 (2004)], accurate quantum reaction rate calculations of the rate constant for the H +CH4?CH3+H2 reaction have been presented. Both the electronic structure calculations and the nuclear dynamics calculations are converged with respect to the basis sets employed. In this paper, the authors apply the same methodology to an isotopic variant of this reaction: D +CH4?CH3+HD. Accurate rate constants are presented for temperatures between 250 and 400K. For temperatures between 400 and 800K, they use a harmonic extrapolation to obtain approximate rate constants for H /D+CH4. The calculations suggest that the experimentally reported rate constants for D +CH4 are about a factor of 10-20 too high. For H +CH4, more accurate experiments are available and agreement is much better: the difference is less than a factor of 2.6. The kinetic isotope effect for the H /D+CH4 reactions is studied and compared with experiment and transition state theory (TST) calculations. Harmonic TST was found to provide a good description of the kinetic isotope effect.

  12. 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.

  13. Rate Constants for H + Cyanoacetylene Reaction for Nitrile Chemistry in Titan's Atmosphere

    NASA Astrophysics Data System (ADS)

    Cody, R. J.; Parker, J. K.; Payne, W. A.; Stief, L. J.

    2002-09-01

    Cyanoacetylene (HC3N) is one of the few nitrile compounds observed by Voyager in the atmosphere of Titan. The three body reaction H + HC3N + M -> products (1) constitutes one of the loss processes for cyanoacetylene in the photochemical models of the Titan atmosphere; e.g. the 1984 model of Yung, Allen and Pinto. The rate constant for this reaction has never been measured. The models use a value equal to that for the reaction H + C2H2 + M. We have measured the rate constant for Reaction 1 at T = 298 K over a pressure range of 0.5 - 2.0 Torr with helium as the bath gas. The experimental technique is discharge fast flow with mass spectrometric detection and monitoring of the first order decay of HC3N. The H atom, which is the excess reactant by a factor of 100-660, is generated via the fast reaction F + H2 -> H + HF. For each pressure, first order rate constants (kfirst) were measured for [H]= 1.2 - 13 x 1013 molecule cm-3. The bimolecular rate constants (kbi) were derived from the slopes of the plots of kfirst versus [H]. Within our experimental uncertainty, we did not see a pressure dependence of the bimolecular rate constant for the limited pressure range of 0.5 - 2 Torr at T = 298K. The results at T=298K are kbi(0.5 Torr)=2.0x10-13, kbi(1.0 Torr)=2.2x10-13 and kbi(2.0 Torr)=1.8x10-13, all in units of cm3 molecule-1 s-1. These measured rate constants are about a factor of 50 faster than those estimated by analogy with the H + C2H2 reaction. These results could render Reaction 1 a more important loss process than previously estimated. Measurements of the rate constants for reaction 1 are continuing at T = 250K and 200K. The Planetary Atmospheres Program of NASA Headquarters is providing the funding for this research.

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

    PubMed Central

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

    2012-01-01

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

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

    SciTech Connect

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

    2015-08-01

    A micromodel system with a pore structure for heterogeneous flow and transport was used to investigate the effect of subgrid transport heterogeneity on redox reaction rates. Hematite reductive dissolution by injecting a reduced form of flavin mononucleotide (FMNH2) at variable flow rates was used as an example to probe the variations of redox reaction rates in different subgrid transport domains. Experiments, pore-scale simulations, and macroscopic modeling were performed to measure and simulate in-situ hematite reduction and to evaluate the scaling behavior of the redox reaction rates from the pore to macroscopic scales. The results indicated that the measured pore-scale rates of hematite reduction were consistent with the predictions from a pore scale reactive transport model. A general trend is that hematite reduction followed reductant transport pathways, starting from the advection-dominated pores toward the interior of diffusion-dominated domains. Two types of diffusion domains were considered in the micromodel: a micropore diffusion domain, which locates inside solid grains or aggregates where reactant transport is limited by diffusion; and a macropore diffusion domain, which locates at wedged, dead-end pore spaces created by the grain-grain contacts. The rate of hematite reduction in the advection-dominated domain was faster than those in the diffusion-controlled domains, and the rate in the macropore diffusion domain was faster than that in the micropore domain. The reduction rates in the advection and macropore diffusion domains increased with increasing flow rate, but were affected by different mechanisms. The rate increase in the advection domain was controlled by the mass action effect as a faster flow supplied more reactants, and the rate increase in the macropore domain was more affected by the rate of mass exchange with the advection domain, which increased with increasing flow rate. The hematite reduction rate in the micropore domain was, however, not affected by the flow rate because molecular diffusion limits reductant supply to the micropore domain interior. Domain-based macroscopic models were evaluated to scale redox reaction rates from the pore to macroscopic scales. A single domain model, which ignores subgrid transport heterogeneity deviated significantly from the pore-scale results. Further analysis revealed that the rate expression for hematite reduction was not scalable from the pore to porous media using the single domain model. A three-domain model, which effectively considers subgrid reactive diffusion in the micropore and macropore domains, significantly improved model description. Overall this study revealed the importance of subgrid transport heterogeneity in the manifestation of redox reaction rates in porous media and in scaling reactions from the pore to porous media. The research also supported that the domain-based scaling approach can be used to directly scale redox reactions in porous media with subgrid transport heterogeneity.

  16. Determination of reaction mechanisms and rates involving SO and NO radicals

    NASA Astrophysics Data System (ADS)

    Wijesingha, Manoj; Nanayakkara, Asiri

    2015-12-01

    Reaction rates and mechanisms involving radicals SO and NO are studied using ab initio electronic structure methods and transition-state theory calculations for the temperature range 200 K-2000 K. The molecules involved in these reactions are optimized at CCSD levels with basis set cc-PVTZ. The potential energy surface is determined computationally by MP2/6-31G(d,p) method. Moreover CCSD/cc-PVTZ levels of theory are employed to locate stationary points, which are then characterized by calculation of vibrational frequencies to locate the transition states. In this investigation, we find that the possible products in the ground state consist of cis-SONO, SNO2, trans-SONO, cis-NOSO, t-NOSO, NSO2, cis-OSNO, trans-OSNO, S + NO2 and N + SO2. All intermediate states of the reaction SO + NO are positive energy of formation relative to the reactants. According to the reaction profiles of SO + NO, the molecular structures of the reactants are shifted to S + NO2 (49.02 kcal/mol) and N + SO2 (25.22 kcal/mol) through four transition structures and shifted to trans-OSNO (13.39 kcal/mol) via three transition structures. The rates calculated with variational transition state theory show that for the temperature range 200 K-2000 K, three parameter Arrhenius equation produces the most accurate reaction rates.

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

    PubMed Central

    Amontov, Sergey; Jäschke, Andres

    2006-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  19. Effect of electric fields on the reaction rates in shock initiating and detonating solid explosives

    NASA Astrophysics Data System (ADS)

    Tarver, Craig M.

    2012-03-01

    The presence of a strong electric field has been demonstrated to effect the shock initiation and detonation wave propagation of solid high explosives. Several mechanisms have been proposed to explain the observed increased shock sensitivity, increased detonation velocity, and decreased failure diameter of certain explosives. The most likely chemical mechanism is postulated to be the excitation of some of the explosive molecules and/or intermediate reaction products to higher energy electronic states, which rapidly transition nonradiatively to the ground electronic state with excited vibrational states. This vibrational excitation increases the reaction rates of the explosive decomposition chain reactions. The resulting shorter duration reaction zone causes faster shock to detonation transition, decreased failure thickness, and increased detonation velocity for a specific charge diameter.

  20. Absolute rate coefficient and mechanism of gas phase reaction of ketenyl radical and SO2.

    PubMed

    Du, Lin; Carl, Shaun A

    2012-10-18

    The kinetics of the gas phase reaction of the ketenyl radical with SO(2) was investigated over the temperature range 296-568 K using a laser-photofragment/laser-induced fluorescence technique (LP/LIF). The reactor pressure was 10 Torr N(2) or He. Pulsed photolysis of ketene (CH(2)CO) at 193 nm was used as the source of HCCO radicals. The rate coefficient for the title reaction was determined to be described by k(T) = (1.05 ± 0.33) × 10(-12) exp[(690 ± 98)K/T] cm(3) s(-1) molecule(-1) (2? error). We applied the coupled cluster and density functional theory to explore the mechanism of the title reaction. The dominant reaction pathway begins with a barrierless association of the C of the CH group of HCCO and the O atom of SO(2). PMID:23020066

  1. 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.

  2. 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.

  3. Extended Reaction Rate Integral as Solutions of Some General Differential Equations

    E-print Network

    D. P. Joseph; H. J. Haubold

    2010-01-13

    Here an extended form of the reaction rate probability integral, in the case of nonresonant thermonuclear reactions with the depleted tail and the right tail cut off, is considered. The reaction rate integral then can be looked upon as the inverse of the convolution of the Mellin transforms of Tsallis type statistics of nonextensive statistical mechanics and stretched exponential as well as that of superstatistics and stretched exponentials. The differential equations satisfied by the extended probability integrals are derived. The idea used is a novel one of evaluating the extended integrals in terms of some special functions and then by invoking the differential equations satisfied by these special functions. Some special cases of limiting situations are also discussed.

  4. The Impact of Nuclear Reaction Rate Uncertainties on Evolutionary Studies of the Nova Outburst

    E-print Network

    W. Raphael Hix; Michael S. Smith; Anthony Mezzacappa; Sumner Starrfield; Donald L. Smith

    2000-01-27

    The observable consequences of a nova outburst depend sensitively on the details of the thermonuclear runaway which initiates the outburst. One of the more important sources of uncertainty is the nuclear reaction data used as input for the evolutionary calculations. A recent paper by Starrfield, Truran, Wiescher, & Sparks (1998) has demonstrated that changes in the reaction rate library used within a nova simulation have significant effects, not just on the production of individual isotopes (which can change by an order of magnitude), but on global observables such as the peak luminosity and the amount of mass ejected. We present preliminary results of systematic analyses of the impact of reaction rate uncertainties on nova nucleosynthesis.

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  6. 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.

  7. 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…

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

    NASA Astrophysics Data System (ADS)

    Brooke, George M., IV

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    We apply Thermostatted Ring Polymer Molecular Dynamics (TRPMD), a recently proposed approximate quantum dynamics method, to the computation of thermal reaction rates. Its short-time transition-state theory limit is identical to rigorous quantum transition-state theory, and we find that its long-time limit is independent of the location of the dividing surface. TRPMD rate theory is then applied to one-dimensional model systems, the atom-diatom bimolecular reactions H + H2, D + MuH, and F + H2, and the prototypical polyatomic reaction H + CH4. Above the crossover temperature, the TRPMD rate is virtually invariant to the strength of the friction applied to the internal ring-polymer normal modes, and beneath the crossover temperature the TRPMD rate generally decreases with increasing friction, in agreement with the predictions of Kramers theory. We therefore find that TRPMD is approximately equal to, or less accurate than, ring polymer molecular dynamics for symmetric reactions, and for certain asymmetric systems and friction parameters closer to the quantum result, providing a basis for further assessment of the accuracy of this method.

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

    SciTech Connect

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

    1980-01-01

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

  11. Metamorphic reaction rates at ˜650-800 °C from diffusion of niobium in rutile

    NASA Astrophysics Data System (ADS)

    Cruz-Uribe, Alicia M.; Feineman, Maureen D.; Zack, Thomas; Barth, Matthias

    2014-04-01

    The ability to quantify the rates at which metamorphic reactions occur is critical to assessing the extent to which equilibrium is achieved and maintained in a variety of dynamic settings. Here we investigate the kinetics of rutile replacement by titanite during amphibolite-facies overprinting of eclogite, garnet amphibolite and anorthosite from Catalina Island, CA, the Tromsø Nappe, Norway, the North Qaidam terrane, China, and the Guichicovi Complex, Mexico. Trace element concentration profiles across rutile rimmed by titanite, as determined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), reveal Nb zoning in rutile that we interpret as the result of Nb back-diffusion from the rutile-titanite boundary. We present new field-based reaction rates calculated from grain boundary velocities, which in turn were calculated using a 1-D diffusion model for Nb back-diffusion into rutile during titanite replacement over the temperature range 670-770 °C. Our data are consistent with or slightly faster than previous estimates of field-based reaction rates for regional metamorphism, and extend the temperature and compositional range over which regional metamorphic reaction rates are known.

  12. Effects of mineral spatial distribution on reaction rates in porous media

    E-print Network

    Peters, Catherine A.

    Effects of mineral spatial distribution on reaction rates in porous media L. Li,1 C. A. Peters,2 January 2007. [1] This study examined the effects of variations in mineral spatial distributions concentrations. With small percentages of reactive minerals the scaling effects are large, and the effect

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

    NASA Astrophysics Data System (ADS)

    Lopez, Evelyn; Simon, Sindee L.

    2015-03-01

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

  14. Electrochemical degradation of sulfonamides at BDD electrode: kinetics, reaction pathway and eco-toxicity evaluation.

    PubMed

    Fabia?ska, Aleksandra; Bia?k-Bieli?ska, Anna; Stepnowski, Piotr; Stolte, Stefan; Siedlecka, Ewa Maria

    2014-09-15

    The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na2SO4. The intermediates identified by LC-MS and GC-MS analysis suggested that the hydroxyl radicals attack mainly the SN bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test. PMID:25215656

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

    NASA Technical Reports Server (NTRS)

    Torr, D. G.

    1979-01-01

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

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

    PubMed

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

    2005-06-01

    We present a quantum-mechanical investigation of the LiH depletion reaction LiH+H-->Li+H2 and of the H exchange reaction LiH+H'-->LiH'+H. We report product distributions, rate constant, and mechanism of the former, and rate constant and mechanism of the latter reaction. We use the potential-energy surface by Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)], the real-wave-packet method by Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)], and the J-shifting approximation. The 1H2 nuclear-spin statistics and progressions of vib-rotational states (v',j') rule both initial-state-resolved and thermal product distributions, which have saw-toothed shapes with odd j' preferred with respect to even j'. At high collision energies and temperatures, we obtain a regular 3-to-1 intensity alternation of rotational states. At low collision energies and temperatures, the degeneracy and density of many H2 levels can, however, give more irregular distributions. During the collision, the energy flows from the reactant translational mode to the product vibration and recoil ones. The rate constants of both reactions are not Arrhenius type because the reactions are barrier-less. The low-temperature, LiH depletion rate constant is larger than the H exchange one, whereas the contrary holds at high temperature. The real-time mechanisms show the nuclear rearrangements of the nonreactive channel and of the reactive ones, and point out that the LiH depletion is preferred over the H exchange at short times. This confirms the rate-constant results. PMID:15974734

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

    USGS Publications Warehouse

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

    2010-01-01

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

  18. 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.

  19. 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.

  20. Test of the quantum instanton approximation for thermal rate constants for some collinear reactions

    NASA Astrophysics Data System (ADS)

    Ceotto, Michele; Miller, William H.

    2004-04-01

    Two variants of the recently developed quantum instanton (QI) model for calculating thermal rate constants of chemical reactions are applied to several collinear atom-diatom reactions with various skew angles. The results show that the original QI version of the model is consistently more accurate than the "simplest" quantum instanton version (both being applied here with one "dividing surface") and thus to be preferred. Also, for these examples (as with other earlier applications) the QI results agree well with the correct quantum rates (to within ˜20% or better) for all temperatures >200 K, except for situations where dynamical corrections to transition state theory (i.e., "re-crossing" dynamics) are evident. (Since re-crossing effects are substantially reduced in higher dimensionality, this is not a cause for serious concern.) A procedure is also described which facilitates use of the METROPOLIS algorithm for evaluating all quantities that appear in the QI rate expression by Monte Carlo path integral methods.

  1. Quantum three-body calculation of nonresonant triple-? reaction rate at low temperatures

    NASA Astrophysics Data System (ADS)

    Ogata, Kazuyuki; Kan, Masataka; Kamimura, Masayasu

    2010-06-01

    Triple-? reaction rate is re-evaluated by directly solving the three-body Schrödinger equation. The resonant and nonresonant processes are treated on the same footing using the continuum-discretized coupled-channels method for three-body scattering. An accurate description of the ?-? nonresonant states significantly quenches the Coulomb barrier between the first two ?-particles and the third ?-particle. Consequently, the ?-? nonresonant continuum states give a markedly larger contribution at low temperatures than that reported in previous studies. We show that Nomoto's method for three-body nonresonant capture processes, which is adopted in the NACRE compilation and many other studies, is a crude approximation of the accurate quantum three-body model calculation. We find an increase in triple-? reaction rate by 26 orders of magnitude around 107 K compared with the rate of NACRE.

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

    PubMed

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

    2014-06-01

    A kinetic model is provided to obtain reaction rate constants in successive enzymatic reactions that are monitored using NMR spectroscopy and hyperpolarized substrates. The model was applied for simulation and analysis of the successive oxidation of choline to betaine aldehyde, and further to betaine, by the enzyme choline oxidase. This enzymatic reaction was investigated under two different sets of conditions: two different choline molecular probes were used, [1,1,2,2-D4 , 1-(13) C]choline chloride and [1,1,2,2-D4 , 2-(13) C]choline chloride, in different MR systems (clinical scanner and high-resolution spectrometer), as well as in different reactors and reaction volumes (4.8 and 0.7 mL). The kinetic analysis according to the model yielded similar results in both set-ups, supporting the robustness of the model. This was achieved despite the complex and negating influences of reaction kinetics and polarization decay, and in the presence of uncontrolled mixing characteristics, which may introduce uncertainties in both effective timing and effective pulses. The ability to quantify rate constants using hyperpolarized MR in the first seconds of consecutive enzyme activity is important for further development of the utilization of dynamic nuclear polarization-MR for biological determinations. PMID:24639024

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

    SciTech Connect

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

    2011-03-01

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

  4. 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.

  5. 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-?SR techniques that follow the disappearance of the spin-polarised Mu atom with time. Reported here is the first measurement of a slow Mu reaction rate in the gas phase by the technique of diamagnetic radio frequency (RF) resonance, where the amplitude of the MuH product formed in the Mu + C3H8 reaction is followed with time. The measured rate constant, kMu = (6.8 ± 0.5) × 10(-16) cm(3) s(-1) at 300 K, is surprisingly only about a factor of three slower than that expected for H + C3H8, indicating a dominant contribution from quantum tunneling in the Mu reaction, consistent with elementary transition state theory calculations of the kMu/kH kinetic isotope effect. PMID:26165545

  6. Pore-scale heterogeneous reaction rates on a dissolving limestone surface

    NASA Astrophysics Data System (ADS)

    Levenson, Yael; Emmanuel, Simon

    2013-10-01

    The rate at which limestone dissolves determines the resistance of buildings and monuments to weathering, the efficiency of carbon capture in deep geological reservoirs, and the processes by which soils, rocks, and landscapes form and evolve. However, the normalized rates of mineral dissolution measured in laboratory experiments are often found to be far greater than those measured in field settings. Here, we use atomic force microscopy (AFM) measurements to demonstrate experimentally that the rate of calcite dissolution within micron-size pores at the surface of a limestone sample is much lower than the rate of dissolution in the surrounding calcite surface. In addition, we use numerical simulations to show that this difference cannot be explained using a simple diffusion-surface reaction model. We suggest that the observed heterogeneous reaction rates could instead be due to the elevated density of reactive high curvature features on the polished surface surrounding the pore. These high curvature features can strongly affect local interfacial free energy, making such surfaces more prone to dissolution. As a result, polished surfaces should be more reactive than pore surfaces that have effectively been smoothed during prolonged contact with natural fluids. As rate experiments routinely use polished and powdered samples, the results may help to explain the widely reported discrepancy between lab and field-based dissolution rates.

  7. Rate increase in chemical reaction and its variance under turbulent equilibrium

    E-print Network

    Shunichi Tsuge

    2000-01-27

    As contrast to the Maxwellian distribution, equilibrium distribution of the second kind or turbulent equilibrium is shown to exist under tertiary molecular chaos hypothesis to replace the classical binary chaos by Boltzmann. It is expressed as bimodal Maxwellians each mode differing by plus/minus root-mean-squares of fluctuations in macroscopic variables. Chemical reaction rates calculated using the turbulent-equilibrium are obtained in a closed form, accounting for discrepancy between experiments and classical theory based on Arrhenius' law that underestimates the burning rate considerably. The key issue is the correct estimation of the high-energy tail of the distribution function that is minor in population, yet playing a major role for reactions with high activation energy. It is extremely sensitive to turbulence level in the temperature, causing slightly subcritical molecules to clear the potential barrier to cause reactions just like quantum particles undergoing tunnelling effect owing to the uncertainty principle. Variance of the fluctuating turbulent chemical reaction rate is also calculated, verifying that relative variance based on the turbulent equilibrium is low, whereas its classical counterpart (Arrhenius) is pathologically high. A closed set of equations governing reactive turbulent gases is presented on this sound basis.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  9. The rate of the F + H2 reaction at very low temperatures.

    PubMed

    Tizniti, Meryem; Le Picard, Sébastien D; Lique, François; Berteloite, Coralie; Canosa, André; Alexander, Millard H; Sims, Ian R

    2014-02-01

    The prototypical F + H2 ? HF + H reaction possesses a substantial energetic barrier (~800 K) and might therefore be expected to slow to a negligible rate at low temperatures. It is, however, the only source of interstellar HF, which has been detected in a wide range of cold (10-100 K) environments. In fact, the reaction does take place efficiently at low temperatures due to quantum-mechanical tunnelling. Rate constant measurements at such temperatures have essentially been limited to fast barrierless reactions, such as those between two radicals. Using uniform supersonic hydrogen flows we can now report direct experimental measurements of the rate of this reaction down to a temperature of 11 K, in remarkable agreement with state-of-the-art quantum reactive scattering calculations. The results will allow a stronger link to be made between observations of interstellar HF and the abundance of the most common interstellar molecule, H2, and hence a more accurate estimation of the total mass of astronomical objects. PMID:24451590

  10. The rate of the F + H2 reaction at very low temperatures

    NASA Astrophysics Data System (ADS)

    Tizniti, Meryem; Le Picard, Sébastien D.; Lique, François; Berteloite, Coralie; Canosa, André; Alexander, Millard H.; Sims, Ian R.

    2014-02-01

    The prototypical F + H2 ? HF + H reaction possesses a substantial energetic barrier (~800 K) and might therefore be expected to slow to a negligible rate at low temperatures. It is, however, the only source of interstellar HF, which has been detected in a wide range of cold (10-100 K) environments. In fact, the reaction does take place efficiently at low temperatures due to quantum-mechanical tunnelling. Rate constant measurements at such temperatures have essentially been limited to fast barrierless reactions, such as those between two radicals. Using uniform supersonic hydrogen flows we can now report direct experimental measurements of the rate of this reaction down to a temperature of 11 K, in remarkable agreement with state-of-the-art quantum reactive scattering calculations. The results will allow a stronger link to be made between observations of interstellar HF and the abundance of the most common interstellar molecule, H2, and hence a more accurate estimation of the total mass of astronomical objects.

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

    PubMed Central

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

    2014-01-01

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

  12. Relativistic equilibrium velocity distribution, nuclear fusion reaction rate and the solar neutrino problem

    E-print Network

    Jian-Miin Liu

    2003-07-07

    In solar interior, it is the equilibrium velocity distribution of few high-energy protons and nuclei that participates in determining nuclear fusion reaction rates. So, it is inappropriate to use the Maxwellian velocity distribution to calculate the rates of solar nuclear fusion reactions. We have to use the relativistic equilibrium velocity distribution for the purpose. The nuclear fusion reaction rate based on the relativistic equilibrium velocity distribution has a reduction factor with respect to that based on the Maxwellian distribution. The reduction factor depends on the temperature, reduced mass and atomic numbers of the studied nuclear fusion reactions, in other words, it varies with the sort of neutrinos. Substituting the relativistic equilibrium velocity distribution for the Maxwellian distribution is not important for the calculation of solar sound speeds. The relativistic equilibrium velocity distribution, if adopted in standard solar models, will lower solar neutrino fluxes and change solar neutrino energy spectra but maintain solar sound speeds. This velocity distribution is possibly a solution to the solar neutrino problem.

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

    SciTech Connect

    Scott C. Brooks; Wenming Dong; Sue Carroll; Jim Fredrickson; Ken Kemner; Shelly Kelly

    2006-06-01

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

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

    SciTech Connect

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

    2006-06-01

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

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

    PubMed Central

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

    2015-01-01

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

  16. Rate constants for the reactions of CN with hydrocarbons at low and ultra-low temperatures

    NASA Astrophysics Data System (ADS)

    Sims, Ian R.; Queffelec, Jean-Louis; Travers, Daniel; Rowe, Bertrand R.; Herbert, Lee B.; Karthäuser, Joachim; Smith, Ian W. M.

    1993-08-01

    The pulsed laser-photolysis (PLP), time-resolved laser-induced fluorescence (LIF) technique has been used to study the reactions of the CN radical with CH4, C2H6, C2H4, C3H6 and C2H2 at low and ultra-low temperatures. Using a cryogenically cooled cell, rate constants have been determined for all five reactions at temperatures down to 160 K. The PLP-LIF method has also been implemented in a CRESU (cinétique de réaction en écoulement supersonique uniforme) apparatus providing rate constants for the reactions of CN with C2H6, C2H4 and C2H2 at temperatures down to 25 K. The rate constants for CN+C2H4 and CN+C2H2 increase monotonically as the temperature is lowered from room temperature to 44 K but the values at 25 K are lower than those at 44 K. Remarkably, the rate constant for CN+C2H6 increases below 75 K, reaching its largest value at 25 K. It is tentatively suggested that this behaviour may reflect the transient formation of an energised van der Waals complex which facilitates the subsequent abstraction of an H atom.

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

    SciTech Connect

    Beste, Ariana; Buchanan III, A C

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Wojnárovits, László; Takács, Erzsébet

    2014-03-01

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

  19. Nitrile Chemistry in Titan's Atmosphere: Low Temperature Rate Constants for H + Cyanoacetylene Reaction

    NASA Astrophysics Data System (ADS)

    Cody, R. J.; Parker, J. K.; Payne, W. A.; Stief, L. J.

    2003-05-01

    Cyanoacetylene (HC3N) is one of the few nitrile compounds observed in the atmosphere of Titan by Voyager and from the ground. The three body reaction H + HC3N + M -> products (1) constitutes one of the important loss processes for cyanoacetylene in the photochemical models of the Titan atmosphere; e.g. the 1984 model of Yung, Allen and Pinto and the 1995 model of Toublanc et al. The models calculate a mixing ratio for HC3N that differs considerably from that derived from the observations. The rate constant for Reaction 1 has never been measured. The models use a value equal to that for the reaction H + C2H2 + M. We have measured the rate constant for Reaction 1 at T = 298 K, 250 K, and 200 K with helium as the bath gas at a pressure of 1 Torr; additionally, measurements of k1 were made at T = 298 K with P = 0.5 and 2.0 Torr. The experimental technique is discharge fast flow with mass spectrometric detection and monitoring of the first order decay of HC3N. The H atom, which is the excess reactant by a factor of 100-660, is generated via the fast reaction F + H2 -> H + HF. For each temperature and pressure, first order rate constants (kobs) were measured for a range of [H] 1 - 13 x 1013 molecule cm-3. The bimolecular rate constants (k1) were derived from the slopes of the plots of kobs versus [H]. Within our experimental uncertainty, we did not see a pressure dependence of the bimolecular rate constant for the limited pressure range of 0.5 - 2 Torr at T = 298K. This indicates that the rate constant has reached its high-pressure limit by 1 Torr for T <= 298 K. The results are k1(298K) = 2.1x10--13, k1(250K) = 1.5x10--13 and k1(200K) = 0.93x10--13, all in units of cm3 molecule-1 s-1. These rate constants can be fit by the Arrhenius expression k1 = 1.1x10-12exp(-500/T) cm3 molecule-1 s-1. These measured rate constants are about a factor of 50 faster than those estimated by analogy with the H + C2H2 reaction and have a much weaker temperature dependence. Theoretical calculations of the rate constant were performed to understand the temperature dependence of Reaction 1. These results could render Reaction 1 a more important loss process in Titan's atmosphere than previously estimated. The Planetary Atmospheres Program of NASA Headquarters supported this research.

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

    E-print Network

    Bertulani, C A

    2015-01-01

    Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean $\\sim$ 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    E-print Network

    C. A. Bertulani

    2015-10-02

    Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean $\\sim$ 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.

  3. Effects of Electric Fields on the Chemical Reaction Rates of Detonating Solid Explosives

    NASA Astrophysics Data System (ADS)

    Tarver, Craig

    2011-06-01

    The presence of a strong electric field has been demonstrated to effect the shock initiation and detonation wave propagation of solid high explosives. Several mechanisms have been proposed to explain the observed increased shock sensitivity, increased detonation velocity, and decreased failure diameter of certain explosives. One chemical mechanism is thought to be the excitation of some of the explosive molecules to higher energy electronic states, which rapidly decay to the ground electronic state while vibrationally exciting the molecules. This process increases the overall reaction rate of the explosive and produces a shorter duration reaction zone. The shorter reaction time results in a more rapid transition to detonation, a decreased failure diameter, and an increased detonation velocity for a specific charge diameter. This work was performed under the auspices of the U. S. Department of Energy by the Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344.

  4. Laboratory Experiments and Investigations on the Reaction Rates of Mg-sulfates Under Mars Relevant Conditions

    NASA Astrophysics Data System (ADS)

    Wang, A.; Freeman, J. J.

    2009-12-01

    Large deposits of hydrous Mg-sulfates was identified on Mars by orbital remote sensing (OMEGA on Mars Express and CRISM on Mars Reconnaissance Orbiter). Kieserite (MgSO4.H2O) and a non-specific “polyhydrated sulfates” are among the most observed and widely distributed sulfates (Bibring et al., 2005, Murchie et al., 2007). They frequently co-exist (Gendrin et al., 2005) and sometimes occur in alternative stratigraphic layers (Roach et al., 2008). Mg-sulfates were suggested, by compositional correlations and mineral models, to exist in Meridiani outcrops (Clark et al., 2005) and in rocks and regolith at Gusev (Squyres et al., 2006, Haskin et al., 2005, Wang et al., 2006, 2008); but no information on the hydration state of these sulfates can be extracted. We have conducted 188 experiments to investigate the stability fields and phase transition pathways of hydrous Mg-sulfates (Wang et al., 2009). In addition, we can extract the information on the reaction rates of five important dehydration and rehydration processes involved in these experiments. Our experiments were done at four temperatures (50°C, 21°C, 5°C, and -10°C) and ten relative humidity levels, with five hydrous Mg-sulfate species as starting phases. The rate information was extracted from the mineral identifications of the intermediate reaction products, measured by non-invasive Raman spectroscopy at regular time intervals during the entire duration of experiments (tens’ thousands hours). The rates for five processes are all strongly controlled by temperatures. We found that the experimental results match Arrhenius equation very well, thus the rate constants for dehydration and rehydration processes of Mg-sulfates at lower temperatures (down to 180K) can be approximately estimated by using the experimentally derived pre-exponential factor(s) and activation energy(s). In this study, only the orders of magnitudes for reaction rate ratios at different temperatures were considered. The estimated reaction rate ratios at different temperatures for five important processes helped us to understand the stable, especially the metastable, Mg-sulfate species that could be seen at Mars surface in non-polar regions during a moderate obliquity period. Therefore in addition to exam the spectral similarity, we now can use the knowledge gained through the laboratory experiments on stability field, phase transition pathway, and reaction rate of Mg-sulfates to evaluate the realistic mineral candidates for “polyhydrated sulfates”, that were so widely observed on Mars by OMEGA and CRISM. Furthermore, we will be able to investigate the formation mechanism of alternative stratigraphic layers of sulfates on Mars and the paleo-climatic conditions that they may imply.

  5. Silicon Isotopes As a New Method of Measuring Silicate Mineral Reaction Rates in the Critical Zone

    NASA Astrophysics Data System (ADS)

    Zhu, C.; Scheafer, A.; Wang, C.; Liu, Z.; Yuan, H.; Georg, R. B.

    2014-12-01

    29Si doped experiments demonstrated that Si isotope doping is a robust new experimental technique for measuring silicate reaction kinetics. Albite dissolution batch experiments were conducted under ambient temperature and pH 3-7.5. In our experiments, initial solutions were doped with artificial 29Si, resulting in a Si isotopic composition highly anomalous to natural Si isotope compositions. The isotopic contrast and analytical precision of ±0.05 (unit in %) allow detection of the dissolution of a minute amount of albite in the aqueous solutions. Results show that the temporal evolution of 28Si and 29Si abundances in batch experiments (3-270 days) tightly bracketed the steady state albite dissolution rates, and the measured rates are consistent with literature data. Because the precipitation of secondary phases consumes silica but leaves the Si isotope ratios unchanged in experimental solutions, dissolution rates were still measurable when secondary phase precipitation took place in experiments. Meanwhile, the combination of Si isotopes and Si elementary concentrations, precisely determined with the Si isotope dilution method, allowed albite dissolution and secondary phase precipitation rates to be determined simultaneously. Experimental data illustrate that this method allows measurements of silicate reaction rates at precisions and conditions never before possible. The high detection sensitivity allows measuring steady state rates extending to longer experimental duration than previously possible at ambient temperatures. Freedom from interferences of secondary phase precipitation means we can now measure rates at circumneutral pH and near equilibrium conditions under which precipitation likely takes place. Particularly, measurements of rates close to equilibrium would help resolve the long-standing problem of field-lab gap in silicate dissolution rates.

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

    SciTech Connect

    Peters, Catherine A

    2013-02-28

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

  7. Temporal and spatial variation of surface reaction rates in porous media: Applications to silicate weathering

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Percolation theory provides a promising framework for modeling transport in heterogeneous porous media, including hydraulic and electrical conductivity, air permeability, gas diffusivity, and solute transport. Using percolation concepts (e.g., critical path analysis, fractal scaling of percolation clusters, and cluster statistics), we developed a physically-based model for predicting solute transport. Our model predicted spatial solute distributions as a function of time, and arrival time distributions as a function of system size. Our solute transport predictions gave good matches to a wide range of experiments. We now apply our solute transport model to silicate weathering. We assume that surface chemical reactions are at equilibrium at the scale of a single pore, but that at larger length scales, reactions are limited by transport of reactants or products. Using results from published field experiments, we find that the temporal and spatial dependence derived from solute velocity successfully predicts the measured time- and length-dependence of reaction rates and weathering of silicate minerals over a wide range of time and length scale. A similar analysis of lab experiments (uranium breakthrough curves measured in two short and long columns from the Hanford site) indicates that normalized reaction rate versus normalized time follow 2D invasion and 3D random percolation.

  8. How fast, realistically: ab initio calculations of low-energy astrophysical reaction rates

    NASA Astrophysics Data System (ADS)

    Nollett, Kenneth

    2004-05-01

    Understanding the production of nuclei and nuclear energy in astrophysical environments requires as input quantities the rates of many nuclear reactions, but only a small fraction of the cross sections required for nuclear astrophysics will ever be measured in the laboratory. Nuclear astrophysics will therefore always depend on nuclear theory to supply rates fundamentally inaccessible in the laboratory, to extrapolate measured cross sections to different energies or mass numbers relevant for astrophysics, and to resolve discrepancies where there are conflicting laboratory data. Recent years have seen the development of the ``realistic'' nucleon-nucleon interactions that provide excellent descriptions of nucleon-nucleon scattering up to the pion production threshold. Computing wave functions and matrix elements based on these interactions is computation-intensive, even for the nuclei of atomic weight twelve or less for which calculations are feasible with present computers. Consequently, development of the interactions and currents has gone hand-in-hand with development of the computational methods to compute nuclear wave functions and interaction matrix elements based on them, particularly the quantum Monte Carlo and correlated hyperspherical harmonic methods. These developments provide an excellent opportunity for nuclear astrophysics, and they have been applied fruitfully to several reactions of astrophysical interest. I will review these advances in the descriptions of light nuclei and their reactions, as well as their application to specific reactions of interest for the astrophysical problems of solar neutrino production and of the synthesis of light nuclei in the early universe.

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

    SciTech Connect

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-12-09

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

  10. Nuclear Reaction Network for Primordial Nucleosynthesis: a detailed analysis of rates, uncertainties and light nuclei yields

    E-print Network

    P. D. Serpico; S. Esposito; F. Iocco; G. Mangano; G. Miele; O. Pisanti

    2004-12-06

    We analyze in details the standard Primordial Nucleosynthesis scenario. In particular we discuss the key theoretical issues which are involved in a detailed prediction of light nuclide abundances, as the weak reaction rates, neutrino decoupling and nuclear rate modeling. We also perform a new analysis of available data on the main nuclear processes entering the nucleosynthesis reaction network, with particular stress on their uncertainties as well as on their role in determining the corresponding uncertainties on light nuclide theoretical estimates. The current status of theoretical versus experimental results for 2H, 3He, 4He and 7Li is then discussed using the determination of the baryon density as obtained from Cosmic Microwave Background anisotropies.

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

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  13. 23Na(?,p)26Mg Reaction Rate at Astrophysically Relevant Energies.

    PubMed

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

    2015-07-31

    The production of 26Al in massive stars is sensitive to the 23Na(?,p)26Mg cross section. Recent experimental data suggest the currently recommended cross sections are underestimated by a factor of ?40. We present here differential cross sections for the 23Na(?,p)26Mg reaction measured in the energy range E(c.m.)=1.7-2.5??MeV. Concurrent measurements of Rutherford scattering provide absolute normalizations that are independent of variations in target properties. Angular distributions are measured for both p0 and p1 permitting the determination of total cross sections. The results show no significant deviation from the statistical model calculations upon which the recommended rates are based. We therefore retain the previous recommendation without the increase in cross section and resulting stellar reaction rates by a factor of 40, impacting the 26Al yield from massive stars by more than a factor of 3. PMID:26274414

  14. The 23Na(?,p) 26Mg reaction rate at astrophysically relevant energies

    E-print Network

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

    2015-06-23

    The production of 26 Al in massive stars is sensitive to the 23 Na(a,p) 26 Mg cross section. Recent experimental data suggest the currently recommended cross sections are underestimated by a factor of 40. We present here differential cross sections for the 23 Na(a,p) 26 Mg reaction measured in the energy range E c.m. = 1.7 - 2.5 MeV. Concurrent measurements of Rutherford scattering provide absolute normalisations which are independent of variations in target properties. Angular distributions were measured for both p 0 and p 1 permitting the determination of total cross sections. The results show no significant deviation from the statistical model calculations upon which the recommended rates are based. We therefore retain the previous recommendation without the increase in cross section and resulting stellar reaction rates of a factor of 40, impacting on the 26 Al yield from massive stars by more than a factor of three.

  15. 23Na (?,p )26Mg Reaction Rate at Astrophysically Relevant Energies

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    SciTech Connect

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

    2000-04-13

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

  17. Reaction rates of ?-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

    ?-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 ?-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 ?-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 ?-tocopheroxyl radical recycling by ascorbate. PMID:24995727

  18. Nuclear reaction rates and energy in stellar plasmas : The effect of highly damped modes

    E-print Network

    Merav Opher; Luis O. Silva; Dean E. Dauger; Viktor K. Decyk; John M. Dawson

    2001-05-09

    The effects of the highly damped modes in the energy and reaction rates in a plasma are discussed. These modes, with wavenumbers $k \\gg k_{D}$, even being only weakly excited, with less than $k_{B}T$ per mode, make a significant contribution to the energy and screening in a plasma. When the de Broglie wavelength is much less than the distance of closest approach of thermal electrons, a classical analysis of the plasma can

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

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  20. Actinide complexation kinetics: rate and mechanism of dioxoneptunium (V) reaction with chlorophosphonazo III

    SciTech Connect

    Fugate, G.; Feil-Jenkins, J.F.; Sullivan, J.C.; Nash, K.L.

    1996-12-01

    Rates of complex formation and dissociation in NpO{sub 2}{sup +}- Chlorophosphonazo III (2,7-bis(4-chloro-2-phosphonobenzeneazo)-1,8- dihydroxynapthalene-3,6-disulfonic acid)(CLIII) were investigated by stopped-flow spectrophotometry. Also, limited studies were made of the rates of reaction of La{sup 3+}, Eu{sup 3+}, Dy{sup 3+}, and Fe{sup 3+} with CLIII. Rate determining step in each system is an intramolecular process, the NpO{sub 2}{sup +}-CLIII reaction proceeding by a first order approach to equilibrium in the acid range from 0.1 to 1.0 M. Complex formation occurs independent of acidity, while both acid dependent and independent dissociation pathways are observed. Activation parameters for the complex formation reaction are {Delta}H=46.2{+-}0.3 kJ/m and {Delta}S=7{+-} J/mK (I=1.0 M); these for the acid dependent and independent dissociation pathways are {Delta}H=38.8{+-}0.6 kJ/m, {Delta}S=-96{+-}18 J/mK, {Delta}H=70.0{+-} kJ/m, and {Delta}S=17{+-}1 J/mK, respectively. An isokinetic relationship is observed between the activation parameters for CLIII complex formation with NpO{sub 2}{sup +}, UO{sub 2}{sup 2+}, Th{sup 4+}, and Zr{sup 4+}. Rates of CLIII complex formation reactions for Fe{sup 3+}, Zr{sup 4+}, NpO{sub 2}{sup +}, UO{sub 2}{sup 2+}, Th{sup 4+}, La{sup 3+}, Eu{sup 3+}, and Dy{sup 3+} correlate with cation radius rather than charge/radius ratio.

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

    NASA Astrophysics Data System (ADS)

    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.

    2013-05-01

    Measurements of aerosol number distributions down to one molecule have provided information that we've used to develop a new approach for modeling atmospheric nucleation rates. Measurements were carried out with the Cluster Chemical Ionization Mass Spectrometer (Cluster CIMS), the scanning mobility spectrometer using a diethylene glycol condensation particle counter as detector (DEG SMPS), and an ambient pressure proton transfer mass spectrometer for ammonia and amines (AmPMS). The model explains nucleation as a result of cluster evolution due to a sequence of acid-base reactions. We conclude that the smallest stable cluster contains four sulfuric acid molecules. The model leads to a simple analytic expression for nucleation rates that is reasonably consistent (i.e., ± 10x) with atmospheric observations. The model predicts that nucleation rates are equal to a prefactor, P<1, times the sulfuric acid vapor collision rate, (i.e., J=P?0.5?k11 *[H2SO4]2).

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

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1992-01-01

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

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

    E-print Network

    Straube, Arthur V.

    Stochastic theory of large-scale enzyme-reaction networks: Finite copy number corrections to rate of enzyme-catalyzed reactions which are confined inside a small subcellular compartment. This is achieved of the rate equations will always underestimate the actual steady-state substrate concentrations for an enzyme

  4. Experimental and theoretical rate coefficients for the gas phase reaction of ?-Pinene with OH radical

    NASA Astrophysics Data System (ADS)

    Dash, Manas Ranjan; Rajakumar, B.

    2013-11-01

    Rate coefficient for the reaction of ?-pinene with OH radicals was determined at 298 K and 800 Torr of N2 using the relative rate technique. Isobutylene was used as a reference compound and the concentrations of the organics were followed by gas chromatographic analysis. The rate coefficient for the reaction of ?-pinene with OH radical was measured to be (9.35 ± 2.79) × 10-11 cm3 molecule-1 s-1. Theoretical kinetic calculations were also performed for the title reaction using canonical variational transition state theory (CVT) with small-curvature tunneling (SCT). The kinetics data obtained over the temperature range of 200-400 K were used to derive the Arrhenius expression: k(T) = 8.24 × 10-23T3.41 exp[2421/T] cm3 molecule-1 s-1. The OH-driven atmospheric lifetime (?) and global warming potential (GWP) for ?-pinene were computed and concluded that ?-pinene is very short lived (2.5 h) in the Earth's atmosphere with a GWP of 1.6 × 10-2 at 20 years horizon of time and which is negligible. The ozone formation potential of ?-pinene was also calculated and reported in this present work.

  5. 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.

  6. 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.

  7. 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 Administration under contract DE-AC04-94AL85000.

  8. Role of Conformational Structures and Torsional Anharmonicity in Controlling Chemical Reaction Rates and Relative Yields: Butanal + HO2 Reactions

    SciTech Connect

    Zheng, Jingjing; Seal, Prasenjit; Truhlar, Donald G.

    2013-01-01

    Aldehyde–radical reactions are important in atmospheric and combustion chemistry, and the reactions studied here also serve more generally to illustrate a fundamental aspect of chemical kinetics that has been relatively unexplored from a quantitative point of view, in particular the roles of multiple structures and torsional anharmonicity in determining the rate constants and branching ratios (product yields). We consider hydrogen abstraction from four carbon sites of butanal (carbonyl-C, a-C, b-C and g-C) by hydroperoxyl radical. We employed multi-structural variational transition state theory for studying the first three channels; this uses a multi-faceted dividing surface and allows us to include the contributions of multiple structures of both reacting species and transition states. Multiconfigurational Shepard interpolation (MCSI) was used to obtain the geometries and energies of the potential energy surface along the minimum-energy paths, with gradients and Hessians calculated by the M08-HX/maug-cc-pVTZ method. We find the numbers of structures obtained for the transition states are 46, 60, 72 and 76respectively for the H abstraction at the carbonyl C, the a position, the b position and the g position. Our results show that neglecting the factors arising from multiple structures and torsional anharmonicity would lead to errors at 300, 1000 and 2400 K of factors of 8, 11 and 10 for abstraction at the carbonyl-O, 2, 11 and 25 at the a-C position, 2, 23 and 47 at the b-C position, and 0.6, 8 and 18 at the g-C position. The errors would be even larger at high temperature for the reverse of the H abstraction at the b-C. Relative yields are changed as much as a factor of 7.0 at 200 K, a factor of 5.0 at 298 K, and a factor of 3.7 in the other direction at 2400 K. The strong dependence of the product ratios on the multi-structural anharmonicity factors shows that such factors play an important role in controlling branching ratios in reaction mechanism networks.

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

    NASA Astrophysics Data System (ADS)

    Zegers, Remco

    2015-04-01

    Weak reaction rates such as electron captures and beta decays play major roles in a variety of astrophysical phenomena, such as core-collapse and thermonuclear supernovae and accreting neutron stars. Consequently, the use of accurate weak reaction rates in astrophysical simulations to understand these phenomena is important. Unfortunately, the number of relevant nuclei is typically very large, and, except for a few special cases, it is impossible to rely on experimental results only: theoretical models must be used to estimate the weak reaction rates. These models can then be benchmarked and improved on the basis of a limited number of experimental data. The most important nuclear structure input that is required for calculating weak reaction rates are Gamow-Teller transition strengths. Although these can be extracted from beta and electron-capture decay data, the energy window accessible by such experiments is limited, if accessible at all. However, at the high temperatures and densities that occur in massive stars prior to the cataclysmic demise, transitions to final states at high excitation energies are important. In addition, to properly test theory, full Gamow-Teller transition strength distributions are very valuable. Fortunately, nature is kind: charge-exchange experiments at intermediate energies can provide the relevant strength distributions over a wide energy window and a variety of charge-exchange probes, such as (p,n), (n,p), (d,2 He) and (t,3 He) have been used to extract strengths of relevance for astrophysics (and for other purposes). This presentation will focus on efforts to validate electron capture rates calculated based on nuclear structure models for nuclei with masses ranging from A ~ 40-65, and on studies aimed at testing astrophysical sensitivities to uncertainties/deviations in the theoretical rates. These efforts include experiments with unstable isotopes, and special gamma-ray coincidence techniques to localize very weak, but astrophysically important, low-lying Gamow-Teller transitions. Future efforts will focus on heavier nuclei (A>65) and nuclei further from stability. For the latter, opportunities provided at the Facility for Rare Isotope Beams (FRIB) will be critically important. In particular, experiments enables by the construction of a High Rigidity Spectrometer will strongly enhance the impact of the data for the validation and improvements of novel theoretical approaches. This work was supported by the US National Science Foundation (under Grants PHY-1102511 and PHY-0822648 [JINA]) and the US Department Of Energy under Grant DE- 334 AC02-05CH11231 (LBNL).

  11. Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Zhou, Yong; Zhang, Dong H.

    2014-11-01

    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+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high 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+CH4 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 H2+CH3 reaction are found to be in good consistency with experimental observations.

  12. Reaction rate uncertainties and 26Al in AGB silicon carbide stardust

    E-print Network

    M. A. van Raai; M. Lugaro; A. I. Karakas; C. Iliadis

    2007-12-21

    Stardust is a class of presolar grains each of which presents an ideally uncontaminated stellar sample. Mainstream silicon carbide (SiC) stardust formed in the extended envelopes of carbon-rich asymptotic giant branch (AGB) stars and incorporated the radioactive nucleus 26Al as a trace element. The aim of this paper is to analyse in detail the effect of nuclear uncertainties, in particular the large uncertainties of up to four orders of magnitude related to the 26Al_g+(p,gamma)27Si reaction rate, on the production of 26Al in AGB stars and compare model predictions to data obtained from laboratory analysis of SiC stardust grains. Stellar uncertainties are also briefly discussed. We use a detailed nucleosynthesis postprocessing code to calculate the 26Al/27Al ratios at the surface of AGB stars of different masses (M = 1.75, 3, and 5 M_sun) and metallicities (Z = 0.02, 0.012, and 0.008). For the lower limit and recommended value of the 26Al_g(p,gamma)27Si reaction rate, the predicted 26Al/27Al ratios replicate the upper values of the range of the 26Al/27Al ratios measured in SiC grains. For the upper limit of the 26Al_g(p,gamma)27Si reaction rate, instead, the predicted 26Al/27Al ratios are approximately 100 times lower and lie below the range observed in SiC grains. When considering models of different masses and metallicities, the spread of more than an order of magnitude in the 26Al/27Al ratios measured in stellar SiC grains is not reproduced. We propose two scenarios to explain the spread of the 26Al/27Al ratios observed in mainstream SiC, depending on the choice of the 26Al_g+p reaction rate. One involves different times of stardust formation, the other involves extra-mixing processes. Stronger conclusions will be possible after more information is available from future nuclear experiments on the 26Al_g+p reaction.

  13. Thermonuclear reaction rate of 18O(p,gamma)19F

    E-print Network

    M. Q. Buckner; C. Iliadis; J. M. Cesaratto; C. Howard; T. B. Clegg; A. E. Champagne; S. Daigle

    2012-12-05

    For stars between 0.8-8.0 solar masses, nucleosynthesis enters its final phase during the asymptotic giant branch (AGB) stage. During this evolutionary period, grain condensation occurs in the stellar atmosphere, and the star experiences significant mass loss. The production of presolar grains can often be attributed to this unique stellar environment. A subset of presolar oxide grains features dramatic 18O depletion that cannot be explained by the standard AGB star burning stages and dredge-up models. An extra mixing process, referred to as "cool bottom processing" (CBP), was proposed for low-mass AGB stars. The 18O depletion observed within certain stellar environments and within presolar grain samples may result from the 18O+p processes during CBP. We report here on a study of the 18O(p,gamma)19F reaction at low energies. Based on our new results, we found that the resonance at Er = 95 keV (lab) has a negligible affect on the reaction rate at the temperatures associated with CBP. We also determined that the direct capture S-factor is almost a factor of 2 lower than the previously recommended value at low energies. An improved thermonuclear reaction rate for 18O(p,gamma)19F is presented.

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

    SciTech Connect

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

    1992-01-01

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

  15. Rates of hydroxyl radical reactions with some HFCs. [HydroFluoroCarbons

    NASA Technical Reports Server (NTRS)

    Demore, William B.

    1993-01-01

    Relative rate constants for OH reactions with some HFCs have been determined at 298 K by a technique which measures the loss of HFC greater than OH. The following ratios were determine: k(152a)/k(CH4) = 5.2 +/- 0.5, k(CH4)/k(125) = 3.9 +/- 0.5, k(CH4)/k(134a) = 2.1 +/- 0.2, k(134a)/k(125) = 2.0 +/- 0.2, and k(C2H6)/k(152a) = 6.2 +/- 1.0. These results are in good agreement with literature values for the absolute rate constants except for HFC 134a, where a slower rate constant is indicated.

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

    SciTech Connect

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

    2010-08-12

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

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  19. Evaluation of electron capture reaction rates in Ni isotopes in stellar environments

    SciTech Connect

    Suzuki, Toshio; Honma, Michio; Mao, Helene; Otsuka, Takaharu; Kajino, Toshitaka

    2011-04-15

    Electron capture rates in Ni isotopes are studied in stellar environments, that is, at high densities and high temperatures during the core-collapse and postbounce explosive nucleosynthesis in supernovae. Reaction rates in {sup 58}Ni and {sup 60}Ni, as well as in {sup 56}Ni, {sup 62}Ni, and {sup 64}Ni, are evaluated by shell-model calculations with the use of a new shell-model Hamiltonian in the fp shell, GXPF1J. While the previous shell-model calculations failed to reproduce the measured peaks of Gamow-Teller strength in {sup 58}Ni and {sup 60}Ni, the present new Hamiltonian is found to reproduce them very well, as well as the capture rates obtained from the observed strengths. Strengths and energies of the Gamow-Teller transitions in {sup 56}Ni, {sup 62}Ni, and {sup 64}Ni are also found to be consistent with the observations.

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

    SciTech Connect

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

    2013-05-20

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

  1. Reaction rates for sulfur fixation with iron at 1100 to 1275 K

    NASA Astrophysics Data System (ADS)

    Shumaker, Craig B.; Schuhmann, R.

    1983-06-01

    The rates of sulfidizing iron in a simulated coal gasification atmosphere were studied. Mixtures of H2S and CO were passed through fixed beds of coal char and prereduced iron ore, and effluent gas compositions were measured as a function of time. These mixtures ranged from 2.5 pct to 10 pct H2S at various flow rates, with temperatures from 1100 K to 1275 K and iron ore sizes from 10 mesh down to 100 mesh. Experimental conditions were established to form a steady state reaction profile in the fixed bed. Analysis of the exit gas provided a measurement of the profile. The slope of the profile was used directly as a measure of the reactivity of the solids in the bed. The development of this experimental technique and its experimental design requirements are discussed. The observed sulfidization rate of the in situ reduced iron ore is characterized by a single rate constant m (minutes-1), which varies primarily with temperature and particle size and is substantially independent of gas flow rate, bed configuration, and H2S content of the incoming gas. Accordingly, the rate constant m can be applied in the design of a combined sulfur fixation, coal gasification reactor to estimate the solids retention time, and the minimum mass of iron required per cross sectional area of reactor.

  2. Estimates of neutron reaction rates in three portable He-3 proportional counters

    SciTech Connect

    Descalle, M; Labov, S

    2007-03-01

    The goal of this study is to obtain Monte Carlo estimates of neutron reaction rates for the {sup 3}He(n,p){sup 3}H reaction in two portable He-3 proportional counters in several configurations to quantify contributions from the environment, and optimize the tube characteristics. The smallest tube (0.5-inch diameter, 2-inch long, P = 10 atm) will not meet requirements. The largest tube (1-inch diameter, 4-inch long, P = 6 or 10 atm) will meet requirements and the tube length could be decreased to 2-inch at 6 atm and 1-inch at 10 atm. The 'medium' tube (3/4-inch diameter, 2-inch long, P = 10 atm) will meet requirements for the parallelepiped body, but will not for the cylindrical body.

  3. Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers

    SciTech Connect

    Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

    1993-08-03

    A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

  4. Rate Equations and Kinetic Parameters of the Reactions Involved in Pyrite Oxidation by Thiobacillus ferrooxidans

    PubMed Central

    Lizama, Hector M.; Suzuki, Isamu

    1989-01-01

    Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 ?M Fe2+ per min per FeS2 percent pulp density for the spontaneous pyrite dissolution, 10 ?M Fe2+ per min per mM Fe3+ for the indirect leaching with Fe3+, 90 ?M O2 per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 ?M O2 per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The Km values for pyrite concentration were similar and were 1.9, 2.5, and 2.75% pulp density for indirect leaching, washed pyrite oxidation by T. ferrooxidans, and unwashed pyrite oxidation by T. ferrooxidans, respectively. The last reaction was competitively inhibited by increasing concentrations of cells, with a Ki value of 0.13 mg of wet cells per ml. T. ferrooxidans cells also increased the rate of Fe2+ production from Fe3+ plus pyrite. PMID:16348054

  5. Quantum three-body calculation of the nonresonant triple-?reaction rate at low temperatures

    E-print Network

    Kazuyuki Ogata; Masataka Kan; Masayasu Kamimura

    2009-07-22

    The triple-\\alpha reaction rate is re-evaluated by directly solving the three-body Schr\\"odinger equation. The resonant and nonresonant processes are treated on the same footing using the continuum-discretized coupled-channels method for three-body scattering. Accurate description of the \\alpha-\\alpha nonresonant states significantly quenches the Coulomb barrier between the two-\\alpha's and the third \\alpha particle. Consequently, the \\alpha-\\alpha nonresonant continuum states below the resonance at 92.04 keV, i.e., the ground state of 8Be, give markedly larger contribution at low temperatures than in foregoing studies. We show that Nomoto's method for three-body nonresonant capture processes, which is adopted in the NACRE compilation and many other studies, is a crude approximation of the accurate quantum three-body model calculation. We find about 20 orders-of-magnitude enhancement of the triple-\\alpha reaction rate around 10^7 K compared to the rate of NACRE.

  6. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    NASA Technical Reports Server (NTRS)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

  7. Rates of reaction and process design data for the Hydrocarb Process

    SciTech Connect

    Steinberg, M.; Kobayashi, Atsushi; Tung, Yuanki

    1992-08-01

    In support of studies for developing the coprocessing of fossil fuels with biomass by the Hydrocarb Process, experimental and process design data are reported. The experimental work includes the hydropryolysis of biomass and the thermal decomposition of methane in a tubular reactor. The rates of reaction and conversion were obtained at temperature and pressure conditions pertaining to a Hydrocarb Process design. A Process Simulation Computer Model was used to design the process and obtain complete energy and mass balances. Multiple feedstocks including biomass with natural gas and biomass with coal were evaluated. Additional feedstocks including green waste, sewage sludge and digester gas were also evaluated for a pilot plant unit.

  8. Microscopic Theory of Protein Folding Rates.II: Local Reaction Coordinates and Chain Dynamics

    E-print Network

    John J. Portman; Shoji Takada; Peter G. Wolynes

    2000-08-30

    The motion involved in barrier crossing for protein folding are investigated in terms of the chain dynamics of the polymer backbone, completing the microscopic description of protein folding presented in the previous paper. Local reaction coordinates are identified as collective growth modes of the unstable fluctuations about the saddle-points in the free energy surface. The description of the chain dynamics incorporates internal friction (independent of the solvent viscosity) arising from the elementary isomerizations of the backbone dihedral angles. We find that the folding rate depends linearly on the solvent friction for high viscosity, but saturates at low viscosity because of internal friction. For $\\lambda$-repressor, the calculated folding rate prefactor, along with the free energy barrier from the variational theory, gives a folding rate that agrees well with the experimentally determined rate under highly stabilizing conditions, but the theory predicts too large a folding rate at the transition midpoint. This discrepancy obtained using a fairly complete quantitative theory inspires a new set of questions about chain dynamics, specifically detailed motions in individual contact formation.

  9. On the theory of the reaction rate of vibrationally excited CO molecules with OH radicals

    NASA Astrophysics Data System (ADS)

    Chen, Wei-Chen; Marcus, R. A.

    2006-01-01

    The dependence of the rate of the reaction CO +OH?H+CO2 on the CO-vibrational excitation is treated here theoretically. Both the Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant kRRKM and a nonstatistical modification knon [W.-C. Chen and R. A. Marcus, J. Chem. Phys. 123, 094307 (2005).] are used in the analysis. The experimentally measured rate constant shows an apparent (large error bars) decrease with increasing CO-vibrational temperature Tv over the range of Tv's studied, 298-1800K. Both kRRKM(Tv) and knon(Tv) show the same trend over the Tv-range studied, but the knon(Tv) vs Tv plot shows a larger effect. The various trends can be understood in simple terms. The calculated rate constant kv decreases with increasing CO vibrational quantum number v, on going from v =0 to v =1, by factors of 1.5 and 3 in the RRKM and nonstatistical calculations, respectively. It then increases when v is increased further. These results can be regarded as a prediction when v state-selected rate constants become available.

  10. Temperature and kinetic energy dependences of the rate constant for the reaction 22Ne++20Ne

    NASA Astrophysics Data System (ADS)

    Morris, Robert A.; Viggiano, A. A.; Paulson, John F.; Su, Timothy

    1990-06-01

    Rate constants for the reaction 22Ne++20Ne-->20Ne++22Ne have been measured as a function of average center-of-mass kinetic energy () at each of three temperatures: 193, 296, and 464 K. The measurements were made in the range of from 0.02 to 1 eV. The temperature dependence of the rate constant was determined for the first time and is of the form T0.29. The rate constants measured as a function of at the different temperatures depend only on and not on experimental temperature for a given , as expected. Measured reduced mobilities are also reported for 22Ne+ drifting in He. Classical trajectory calculations of the rate constants have been performed using the probability function of Rapp and Francis [J. Chem. Phys. 37, 2631 (1962)], and Dewangen [J. Phys. B 6, L20 (1973)] [as corrected by Gerlich (private communication)] as a function of internuclear separation. The theoretical rate constants are 10-30 % higher than the measured values.

  11. Benchmark reaction rates, the stability of biological molecules in water, and the evolution of catalytic power in enzymes.

    PubMed

    Wolfenden, Richard

    2011-01-01

    The rates of enzyme reactions fall within a relatively narrow range. To estimate the rate enhancements produced by enzymes, and their expected affinities for transition state analog inhibitors, it is necessary to measure the rates of the corresponding reactions in water in the absence of a catalyst. This review describes the spontaneous cleavages of C-C, C-H, C-N, C-O, P-O, and S-O bonds in biological molecules, as well as the uncatalyzed reactions that correspond to phosphoryl transfer reactions catalyzed by kinases and to peptidyl transfer in the ribosome. The rates of these reactions, some with half-lives in excess of one million years, span an overall range of 10¹?-fold. Moreover, the slowest reactions tend to be most sensitive to temperature, with rates that increase as much as 10?-fold when the temperature is raised from 25° to 100°C. That tendency collapses, by many orders of magnitude, the time that would have been required for chemical evolution on a warm earth. If the catalytic effect of primitive enzymes, like that of modern enzymes and many nonenzymatic catalysts, were mainly to reduce a reaction's enthalpy of activation, then the resulting rate enhancement would have increased automatically as the surroundings cooled. By reducing the time required for early chemical evolution in a warm environment, these findings counter the view that not enough time has passed for terrestrial life to have evolved to its present level of complexity. PMID:21495848

  12. Absolute rate constants for the reaction of atomic hydrogen with ketene from 298 to 500 K

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

    Rate constants for the reaction of atomic hydrogen with ketene have been measured at room temperature by two techniques, flash photolysis-resonance fluorescence and discharge flow-resonance fluorescence. The measured values are (6.19 + or - 1.68) x 10 to the -14th and (7.3 + or - 1.3) x 10 to the -14th cu cm/molecule/s, respectively. In addition, rate constants as a function of temperature have been measured over the range 298-500 K using the FP-RF technique. The results are best represented by the Arrhenius expression k = (1.88 + or - 1.12) x 10 to the -11th exp(-1725 + or - 190/T) cu cm/molecule/s, where the indicated errors are at the two standard deviation level.

  13. Elementary reaction rate measurements at high temperatures by tunable-laser flash-absorption

    SciTech Connect

    Hessler, J.P.

    1993-12-01

    The major objective of this program is to measure thermal rate coefficients and branching ratios of elementary reactions. To perform these measurements, the authors constructed an ultrahigh-purity shock tube to generate temperatures between 1000 and 5500 K. The tunable-laser flash-absorption technique is used to measure the rate of change of the concentration of species which absorb below 50,000 cm{sup {minus}1} e.g.: OH, CH, and CH{sub 3}. This technique is being extended into the vacuum-ultraviolet spectral region where one can measure atomic species e.g.: H, D, C, O, and N; and diatomic species e.g.: O{sub 2}, CO, and OH.

  14. Fluorometric reaction rate method for determination of hydrogen perioxide at the nanomolar level

    SciTech Connect

    Peinado, J.; Torbio, F.; Perez-Bendito, D.

    1986-07-01

    A kinetic nonenzymatic method is proposed for determination of hydrogen peroxide at the nanomolar level and applied to the analysis of several types of coffee, tea, and milk samples. The method is based on the Mn(II)-catalyzed oxidation of 2-hydroxynaphthaldehyde thiosemicarbazone (HNTS) by H/sub 2/O/sub 2/. The reaction is monitored spectrofluorometrically by measuring the initial rate at the excitation and emission wavelength of the oxidation product. The kinetic study involved obtaining the rate law and evaluating and optimizing the chemical variables. Sallent features of the method are (a) a linear calibration graph is obtained from 50 to 2000 nM; (b) no enzymes are required; and (c) it tolerates moderate amounts of various metal ions.

  15. PH-dependence of the steady-state rate of a two-step enzymic reaction.

    PubMed

    Brocklehurst, K; Dixon, H B

    1976-04-01

    1. The pH-dependence is considered of a reaction between E and S that proceeds through an intermediate ES under "Briggs-Haldane' conditions, i.e. there is a steady state in ES and [S]o greater than [E]T, where [S]o is the initial concentration of S and [E]T is the total concentration of all forms of E. Reactants and intermediates are assumed to interconvert in three protonic states (E equilibrium ES; EH equilibrium EHS; EH2 equilibrium EH2S), but only EHS provides products by an irreversible reaction whose rate constant is kcat. Protonations are assumed to be so fast that they are all at equilibrium. 2. The rate equation for this model is shown to be v = d[P]/dt = (kcat.[E]T[S]o/A)/[(KmBC/DA) + [S]o], where Km is the usual assembly of rate constants around EHS and A-D are functions of the form (1 + [H]/K1 + K2/[H]), in which K1 and K2 are: in A, the molecular ionization constants of ES; in B, the analogous constants of E; in C and D, apparent ionization constants composed of molecular ionization constants (of E or ES) and assemblies of rate constants. 3. As in earlier treatments of this type of reaction which involve either the assumption that the reactants and intermediate are in equilibrium or the assumption of Peller & Alberty [(1959) J. Am. Chem. Soc. 81, 5907-5914] that only EH and EHS interconvert directly, the pH-dependence of kcat. is determined only by A. 4. The pH-dependence of Km is determined in general by B-C/A-D, but when reactants and intermediate are in equilibrium, C identical to D and this expression simplifies to B/A. 5. The pH-dependence of kcat./Km, i.e. of the rate when [S]o less than Km, is not necessarily a simple bell-shaped curve characterized only by the ionization constants of B, but is a complex curve characterized by D/B-C. 6. Various situations are discussed in which the pH-dependence of kcat./Km is determined by assemblies simpler than D/B-C. The special situation in which a kcat./Km-pH profile provides the molecular pKa values of the intermediate ES complex is delineated. PMID:7241

  16. Measurement of (alpha,n) reaction cross sections of erbium isotopes for testing astrophysical rate predictions

    E-print Network

    G. G Kiss; T. Szücs; T. Rauscher; Zs Török; L. Csedreki; Zs Fülöp; Gy Gyürky; Z. Halász

    2015-03-06

    The $\\gamma$-process in core-collapse and/or type Ia supernova explosions is thought to explain the origin of the majority of the so-called $p$ nuclei (the 35 proton-rich isotopes between Se and Hg). Reaction rates for $\\gamma$-process reaction network studies have to be predicted using Hauser-Feshbach statistical model calculations. Recent investigations have shown problems in the prediction of $\\alpha$-widths at astrophysical energies which are an essential input for the statistical model. It has an impact on the reliability of abundance predictions in the upper mass range of the $p$ nuclei. With the measurement of the $^{164,166}$Er($\\alpha$,n)$^{167,169}$Yb reaction cross sections at energies close to the astrophysically relevant energy range we tested the recently suggested low energy modification of the $\\alpha$+nucleus optical potential in a mass region where $\\gamma$-process calculations exhibit an underproduction of the $p$ nuclei. Using the same optical potential for the $\\alpha$-width which was derived from combined $^{162}$Er($\\alpha$,n) and $^{162}$Er($\\alpha$,$\\gamma$) measurement makes it plausible that a low-energy modification of the optical $\\alpha$+nucleus potential is needed.

  17. Measurement of (alpha,n) reaction cross sections of erbium isotopes for testing astrophysical rate predictions

    E-print Network

    Kiss, G G; Rauscher, T; Török, Zs; Csedreki, L; Fülöp, Zs; Gyürky, Gy; Halász, Z

    2015-01-01

    The $\\gamma$-process in core-collapse and/or type Ia supernova explosions is thought to explain the origin of the majority of the so-called $p$ nuclei (the 35 proton-rich isotopes between Se and Hg). Reaction rates for $\\gamma$-process reaction network studies have to be predicted using Hauser-Feshbach statistical model calculations. Recent investigations have shown problems in the prediction of $\\alpha$-widths at astrophysical energies which are an essential input for the statistical model. It has an impact on the reliability of abundance predictions in the upper mass range of the $p$ nuclei. With the measurement of the $^{164,166}$Er($\\alpha$,n)$^{167,169}$Yb reaction cross sections at energies close to the astrophysically relevant energy range we tested the recently suggested low energy modification of the $\\alpha$+nucleus optical potential in a mass region where $\\gamma$-process calculations exhibit an underproduction of the $p$ nuclei. Using the same optical potential for the $\\alpha$-width which was der...

  18. Measurement of (?,n) reaction cross sections of erbium isotopes for testing astrophysical rate predictions

    NASA Astrophysics Data System (ADS)

    Kiss, G. G.; Szücs, T.; Rauscher, T.; Török, Zs; Csedreki, L.; Fülöp, Zs; Gyürky, Gy; Halász, Z.

    2015-05-01

    The ?-process in core-collapse and/or type Ia supernova explosions is thought to explain the origin of the majority of the so-called p nuclei (the 35 proton-rich isotopes between Se and Hg). Reaction rates for ?-process reaction network studies have to be predicted using Hauser-Feshbach statistical model calculations. Recent investigations have shown problems in the prediction of ?-widths at astrophysical energies which are an essential input for the statistical model. It has an impact on the reliability of abundance predictions in the upper mass range of the p nuclei. With the measurement of the 164,166Er(?,n)167,169Yb reaction cross sections at energies close to the astrophysically relevant energy range we tested the recently suggested low energy modification of the ?+nucleus optical potential in a mass region where ?-process calculations exhibit an underproduction of the p nuclei. Using the same optical potential for the ?-width which was derived from combined 162Er(?,n) and 162Er(?,?) measurement makes it plausible that a low-energy modification of the optical ?+nucleus potential is needed.

  19. Rapid gas-phase reactions - The reaction of ammonia and the methylamines with boron trifluoride. III - Pressure dependence of rate constant.

    NASA Technical Reports Server (NTRS)

    Glicker, S.

    1973-01-01

    A steady-state flow apparatus, shown earlier to be suitable for the study of rapid gas reactions, has been used to determine the pressure dependence of the relative quasi-bimolecular rate constants for the reactant pairs ammonia (AM)-trimethylamine (TMA) and dimethylamine (DMA)-trimethylamine in reaction with boron trifluoride. The pressure dependence of the former was determined in the range 0.03-75 torr and that of the latter in the range 0.02-720 torr.

  20. I. Determination of chemical reaction rate constants by numerical nonlinear analysis: differential methods

    E-print Network

    Christopher G. Jesudason

    2011-01-26

    The primary emphasis of this work on kinetics is to illustrate the a posteriori approach to applications, where focus on data leads to novel outcomes, rather than the a priori tendencies of applied analysis which imposes constructs on the nature of the observable. The secondary intention is the development of appropriate methods consonant with experimental definitions. By focusing on gradients, it is possible to determine both the average and instantaneous rate constants that can monitor changes in the rate constant with concentration changes as suggested by this theory. Here, methods are developed and discussed utilizing nonlinear analysis which does not require exact knowledge of initial concentrations. These methods are compared with those derived from standard methodology. These gradient methods are shown to be consistent with the ones from standard methods and could readily serve as alternatives for studies where there are limits or unknowns in the initial conditions, such as in the burgeoning fields of astrophysics and astrochemistry, forensics, archeology and biology . All four reactions studied exhibited semi sinusoidal-like change with reactant concentration change which standard methods cannot detect, which seems to constitute the observation of a new effect that is not predicted by current formulations, where the possibility that the observations are due to artifacts from instrumental errors or the optimization method is reasoned as unlikely since the experiments were conducted by different groups at very different times with different classes of reactions.

  1. Reaction Rate Measurement at the Californium User Facility (CUF) for unfolding the neutron spectrum

    NASA Astrophysics Data System (ADS)

    Hannan, Mohammad; Ortega, Ruben

    2011-03-01

    Neutron Activation Analysis was used to determine Reaction Rate measurement of several activation detectors at the ORNL Californium User Facility (CUF). The irradiations were performed with 34 mg Cf 252 neutron source strength.. Ten source capsules > 34 mgwerepositionedconcentricallyaroundasamplecavity . Wehavedeterminedabsoluteactivityperatomof 9 detectors : Au 197 (n , ?) Au 198 , Al 27 (n , ?) Na 24 , Al 27 (n , p) Mg 27 , Fe 56 (n , p) Mn 5 , Fe 54 (n , p) Mn 54 , In 115 (n , ?) In 116 , Ti 46 (n , p) Sc 46 , Ni 60 (n , p) Co 60 , Fe 58 (n , ?) Fe 59 . Theerrorsarewithin 1.5 - 8 60 and Fe 58 have errors of 46% and 32 %. These high errors may be attributed to the counting statistics. These reaction rate values will be used to unfold the neutron spectrum of the CUF using the MAXED 2000, a computer code for the de convolution of multi sphere neutron spectrometer data and the results are discussed. The authors acknowledge help, advise, and using facility at ORNL-CUF to Dr. Rodger martin and Mr. David C. Galsgow.

  2. Advanced methods comparisons of reaction rates in the Purdue Fast Breeder Blanket Facility

    SciTech Connect

    Hill, R.N.; Ott, K.O.

    1988-01-01

    A review of worldwide results revealed that reaction rates in the blanket region are generally underpredicted with the discrepancy increasing with penetration; however, these results vary widely. Experiments in the large uniform Purdue Fast Breeder Blanket Facility (FBBF) blanket yield an accurate quantification of this discrepancy. Using standard production code methods (diffusion theory with 50 group cross sections), a consistent Calculated/Experimental (C/E) drop-off was observed for various reaction rates. A 50% increase in the calculated results at the outer edge of the blanket is necessary for agreement with experiments. The usefulness of refined group constant generation utilizing specialized weighting spectra and transport theory methods in correcting this discrepancy was analyzed. Refined group constants reduce the discrepancy to half that observed using the standard method. The surprising result was that transport methods had no effect on the blanket deviations; thus, transport theory considerations do not constitute or even contribute to an explanation of the blanket discrepancies. The residual blanket C/E drop-off (about half the standard drop-off) using advanced methods must be caused by some approximations which are applied in all current methods. 27 refs., 3 figs., 1 tab.

  3. The Effects of Changes in Reaction Rates on Simulations of Nova Explosions

    E-print Network

    S. Starrfield; C. Iliadis; W. R. Hix; F. X. Timmes; W. M. Sparks

    2007-06-04

    Classical novae participate in the cycle of Galactic chemical evolution in which grains and metal enriched gas in their ejecta, supplementing those of supernovae, AGB stars, and Wolf-Rayet stars, are a source of heavy elements for the ISM. Once in the diffuse gas, this material is mixed with the existing gases and then incorporated into young stars and planetary systems during star formation. Infrared observations have confirmed the presence of carbon, SiC, hydrocarbons, and oxygen-rich silicate grains in nova ejecta, suggesting that some fraction of the pre-solar grains identified in meteoritic material come from novae. The mean mass returned by a nova outburst to the ISM probably exceeds ~2 x 10^{-4} Solar Masses. Using the observed nova rate of 35 per year in our Galaxy, it follows that novae introduce more than ~7 x 10^{-3} Solar Masses per year of processed matter into the ISM. Novae are expected to be the major source of 15N and 17O in the Galaxy and to contribute to the abundances of other isotopes in this atomic mass range. Here, we report on how changes in the nuclear reaction rates affect the properties of the outburst and alter the predictions of the contributions of novae to Galactic chemical evolution. We also discuss the necessity of including the pep reaction in studies of thermonuclear runaways in material accreted onto white dwarfs.

  4. Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1974-01-01

    Rate constants of two elementary bimolecular reactions involved in the oxidation of methane have been determined by monitoring the exponential growth of CO flame band emission behind incident shocks in three suitably chosen gas mixtures. The data do not support a mechanism which invokes the four center process CH3 + O2 yields CH2O + OH for the reaction of methyl with oxygen.

  5. Rate Constants for Reactions between Iodine-and Chlorine-Containing Species: A Detailed Mechanism of the

    E-print Network

    Epstein, Irving R.

    Rate Constants for Reactions between Iodine- and Chlorine-Containing Species: A Detailed Mechanism of the Chlorine Dioxide/Chlorite-Iodide Reaction Istva´n Lengyel, Jing Li, Kenneth Kustin,* and Irving R. Epstein, consisting of four separable parts. Sequentially, beginning with mixing, these parts are the (a) chlorine

  6. Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes

    SciTech Connect

    Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang

    2014-05-07

    We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula.

  7. The 13N(d,n)14O Reaction and the Astrophysical 13N(p,g)14O Reaction Rate

    E-print Network

    Z. H. Li; B. Guo; S. Q. Yan

    2009-03-18

    $^{13}$N($p,\\gamma$)$^{14}$O is one of the key reactions in the hot CNO cycle which occurs at stellar temperatures around $T_9$ $\\geq$ 0.1. Up to now, some uncertainties still exist for the direct capture component in this reaction, thus an independent measurement is of importance. In present work, the angular distribution of the $^{13}$N($d,n$)$^{14}$O reaction at $E_{\\rm{c.m.}}$ = 8.9 MeV has been measured in inverse kinematics, for the first time. Based on the distorted wave Born approximation (DWBA) analysis, the nuclear asymptotic normalization coefficient (ANC), $C^{^{14}O}_{1,1/2}$, for the ground state of $^{14}$O $\\to$ $^{13}$N + $p$ is derived to be $5.42 \\pm 0.48$ fm$^{-1/2}$. The $^{13}$N($p,\\gamma$)$^{14}$O reaction is analyzed with the R-matrix approach, its astrophysical S-factors and reaction rates at energies of astrophysical relevance are then determined with the ANC. The implications of the present reaction rates on the evolution of novae are then discussed with the reaction network calculations.

  8. Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study

    SciTech Connect

    Vasu, Subith; Huynh, Lam; Davidson, David F.; Hanson, Ronald K.; Golden, David

    2011-03-09

    Reactions of hydroxyl (OH) radicals with 1-butene (k1), trans-2-butene (k2), and cis-2-butene (k3) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH3)3-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C5 oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.

  9. 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.

  10. 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.

  11. Bimolecular reaction rates from ring polymer molecular dynamics: Application to H + CH4? H2 + CH3

    NASA Astrophysics Data System (ADS)

    Suleimanov, Yury V.; Collepardo-Guevara, Rosana; Manolopoulos, David E.

    2011-01-01

    In a recent paper, we have developed an efficient implementation of the ring polymer molecular dynamics (RPMD) method for calculating bimolecular chemical reaction rates in the gas phase, and illustrated it with applications to some benchmark atom-diatom reactions. In this paper, we show that the same methodology can readily be used to treat more complex polyatomic reactions in their full dimensionality, such as the hydrogen abstraction reaction from methane, H + CH_4 rArr H_2 + CH_3. The present calculations were carried out using a modified and recalibrated version of the Jordan-Gilbert potential energy surface. The thermal rate coefficients obtained between 200 and 2000 K are presented and compared with previous results for the same potential energy surface. Throughout the temperature range that is available for comparison, the RPMD approximation gives better agreement with accurate quantum mechanical (multiconfigurational time-dependent Hartree) calculations than do either the centroid density version of quantum transition state theory (QTST) or the quantum instanton (QI) model. The RPMD rate coefficients are within a factor of 2 of the exact quantum mechanical rate coefficients at temperatures in the deep tunneling regime. These results indicate that our previous assessment of the accuracy of the RPMD approximation for atom-diatom reactions remains valid for more complex polyatomic reactions. They also suggest that the sensitivity of the QTST and QI rate coefficients to the choice of the transition state dividing surface becomes more of an issue as the dimensionality of the reaction increases.

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

    NASA Technical Reports Server (NTRS)

    Gupta, A.; Coulbert, C.

    1978-01-01

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

  13. Calculation of the transition state theory rate constant for a general reaction coordinate: Application to hydride transfer in an enzyme

    NASA Astrophysics Data System (ADS)

    Watney, James B.; Soudackov, Alexander V.; Wong, Kim F.; Hammes-Schiffer, Sharon

    2006-01-01

    An expression for the transition state theory rate constant is provided in terms of the potential of mean force for a general reaction coordinate and the mass-weighted gradient of this reaction coordinate. The form of the rate constant enables the straightforward calculation of rates for infrequent events with conventional umbrella sampling and free energy perturbation methods. The approach is illustrated by an application to hydride transfer in the enzyme dihydrofolate reductase using a hybrid quantum/classical molecular dynamics method. Inclusion of the nuclear quantum effects of the transferring hydrogen increases the transition state theory rate constant by a factor of 244.

  14. Type Ia supernovae and the ^{12}C+^{12}C reaction rate

    E-print Network

    E. Bravo; L. Piersanti; I. Domínguez; O. Straniero; J. Isern; J. A. Escartín

    2011-10-10

    The experimental determination of the cross-section of the ^{12}C+^{12}C reaction has never been made at astrophysically relevant energies (Ecurve to the dynamical event. We use one-dimensional hydrostatic and hydrodynamic codes to follow the evolution of accreting white dwarfs until they grow close to the Chandrasekhar mass and explode as SNIa. In our simulations, we account for a low-energy resonance by exploring the parameter space allowed by experimental data. A change in the ^{12}C+^{12}C rate similar to the one explored here would have profound consequences for the physical conditions in the SNIa explosion, namely the central density, neutronization, thermal profile, mass of the convective core, location of the runaway hot spot, or time elapsed since crossing the ignition curve. For instance, with the largest resonance strength we use, the time elapsed since crossing the ignition curve to the supernova event is shorter by a factor ten than for models using the standard rate of ^{12}C+^{12}C, and the runaway temperature is reduced from \\sim8.14\\times10^{8} K to \\sim4.26\\times10^{8} K. On the other hand, a resonance at 1.5 MeV, with a strength ten thousand times smaller than the one measured at 2.14 MeV, but with an {\\alpha}/p yield ratio substantially different from 1 would have a sizeable impact on the degree of neutronization of matter during carbon simmering. We conclude that a robust understanding of the links between SNIa properties and their progenitors will not be attained until the ^{12}C+^{12}C reaction rate is measured at energies \\sim1.5 MeV.

  15. Low temperature rate coefficients for the reaction CN + HC3N.

    PubMed

    Cheikh Sid Ely, Sidaty; Morales, Sébastien B; Guillemin, Jean-Claude; Klippenstein, Stephen J; Sims, Ian R

    2013-11-21

    The reaction of CN radicals with HC3N is of interest for interstellar and circumstellar chemistry as well as for the chemistry of Titan's atmosphere, as part of a general scheme for cyanopolyyne synthesis within these low temperature environments. Here, we present the first experimental measurements of its rate coefficient below room temperature down to 22 K, employing the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) technique coupled with pulsed laser photolysis-laser-induced fluorescence. A novel pulsed version of the CRESU technique employing a new spinning disk valve was used for some of the kinetics measurements. The measurements were in excellent agreement with the only previous determination at room temperature and show a marked increase in the rate coefficient as the temperature is lowered, with the results being well represented by the equation k(T) = 1.79 × 10(-11)(T/300 K)(-0.67) cm(3) molecule(-1) s(-1), with a root-mean-square (statistical) error of 0.61 × 10(-11) cm(3) molecule(-1) s(-1), to which should be added 10% estimated likely systematic error. High accuracy ab initio quantum chemical calculations coupled with variational two-transition state theory calculations were also performed and demonstrate excellent agreement within the combined experimental and predicted theoretical uncertainties. The theoretical rate coefficients, adjusted within expected uncertainties, can be accurately reproduced over the 5 to 400 K temperature range by the expression [(1.97 × 10(-8)) T (-1.51) exp(-3.24/T) + (4.85 × 10(-13)) T (0.563) exp (17.6/T)] cm(3) molecule(-1) s(-1), where T is in K. The new measurements are likely to be of interest to astrochemical and planetary atmospheric modelers. PMID:24047203

  16. The role of advanced reactive surface area characterization in improving predictions of mineral reaction rates

    NASA Astrophysics Data System (ADS)

    Beckingham, L. E.; Zhang, S.; Mitnick, E.; Cole, D. R.; Yang, L.; Anovitz, L. M.; Sheets, J.; Swift, A.; Kneafsey, T. J.; Landrot, G.; Mito, S.; Xue, Z.; Steefel, C. I.; DePaolo, D. J.; Ajo Franklin, J. B.

    2014-12-01

    Geologic sequestration of CO2 in deep sedimentary formations is a promising means of mitigating carbon emissions from coal-fired power plants but the long-term fate of injected CO2 is challenging to predict. Reactive transport models are used to gain insight over long times but rely on laboratory determined mineral reaction rates that have been difficult to extrapolate to field systems. This, in part, is due to a lack of understanding of mineral reactive surface area. Many models use an arbitrary approximation of reactive surface area, applying orders of magnitude scaling factors to measured BET or geometric surface areas. Recently, a few more sophisticated approaches have used 2D and 3D image analyses to determine mineral-specific reactive surface areas that account for the accessibility of minerals. However, the ability of these advanced surface area estimates to improve predictions of mineral reaction rates has yet to be determined. In this study, we fuse X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB analysis to determine mineral-specific accessible reactive surface areas for a core sample from the Nagaoka pilot CO2 injection site (Japan). This sample is primarily quartz, plagioclase, smectite, K-feldspar, and pyroxene. SEM imaging shows abundant smectite cement and grain coatings that decrease the fluid accessibility of other minerals. However, analysis of FIB-SEM images reveals that smectite nano-pores are well connected such that access to underlying minerals is not occluded by smectite coatings. Mineral-specific accessible surfaces are determined, accounting for the connectivity of the pore space with and without connected smectite nano-pores. The large-scale impact of variations in accessibility and dissolution rates are then determined through continuum scale modeling using grid-cell specific information on accessible surface areas. This approach will be compared with a traditional continuum scale model using mineral abundances and common surface area estimates. Ultimately, the effectiveness of advanced surface area characterization to improve mineral dissolution rates will be evaluated by comparison of model results with dissolution rates measured from a flow-through column experiment.

  17. The rate of the reaction between C2H and C2H2 at interstellar temperatures

    NASA Technical Reports Server (NTRS)

    Herbst, E.; Woon, D. E.

    1997-01-01

    The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

  18. The interplay between transport and reaction rates as controls on nitrate attenuation in permeable, streambed sediments

    NASA Astrophysics Data System (ADS)

    Lansdown, K.; Heppell, C. M.; Trimmer, M.; Binley, A.; Heathwaite, A. L.; Byrne, P.; Zhang, H.

    2015-06-01

    Anthropogenic nitrogen fixation and subsequent use of this nitrogen as fertilizer have greatly disturbed the global nitrogen cycle. Rivers are recognized hot spots of nitrogen removal in the landscape as interaction between surface water and sediments creates heterogeneous redox environments conducive for nitrogen transformations. Our understanding of riverbed nitrogen dynamics to date comes mainly from shallow sediments or hyporheic exchange flow pathways with comparatively little attention paid to groundwater-fed, gaining reaches. We have used 15N techniques to quantify in situ rates of nitrate removal to 1 m depth within a groundwater-fed riverbed where subsurface hydrology ranged from strong upwelling to predominantly horizontal water fluxes. We combine these rates with detailed hydrologic measurements to investigate the interplay between biogeochemical activity and water transport in controlling nitrogen attenuation along upwelling flow pathways. Nitrate attenuation occurred via denitrification rather than dissimilatory nitrate reduction to ammonium or anammox (range = 12 to >17,000 nmol 15N L-1 h-1). Overall, nitrate removal within the upwelling groundwater was controlled by water flux rather than reaction rate (i.e., Damköhler numbers <1) with the exception of two hot spots of biogeochemical activity. Deep sediments were as important a nitrate sink as shallow sediments with fast rates of denitrification and short water residence time close to the riverbed surface balanced by slower rates of denitrification and water flux at depth. Within this permeable riverbed >80% of nitrate removal occurs within sediments not exposed to hyporheic exchange flows under base flow conditions, illustrating the importance of deep sediments as nitrate sinks in upwelling systems.

  19. High-precision {sup 28}Si(p,t){sup 26}Si reaction to determine {sup 22}Mg({alpha},p){sup 25}Al reaction rates

    SciTech Connect

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

    2011-08-15

    The rise time of stellar x-ray bursts is a signature of thermonuclear runaway processes in the atmosphere of neutron stars and is highly sensitive to a series of ({alpha},p) reactions via high-lying resonances in sd-shell nuclei. Lacking data for the relevant resonance levels, the stellar reaction rates have been calculated using statistical, Hauser-Feshbach models, assuming a high-level density. This assumption may not be correct in view of the selectivity of the ({alpha},p) reaction to natural parity states. We measured the {sup 28}Si(p,t){sup 26}Si reaction with a high-resolution spectrometer to identify resonance levels in {sup 26}Si above the {alpha}-emission threshold at 9.164 MeV excitation energy. These resonance levels are used to calculate the stellar reaction rate of the {sup 22}Mg({alpha},p){sup 25}Al reaction and to test the validity of the statistical assumption.

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

    NASA Technical Reports Server (NTRS)

    Sislian, J. P.

    1978-01-01

    The nonequilibrium flow field resulting from the turbulent mixing and combustion of a supersonic axisymmetric hydrogen jet in a supersonic parallel coflowing air stream is analyzed. Effective turbulent transport properties are determined using the (K-epsilon) model. The finite-rate chemistry model considers eight reactions between six chemical species, H, O, H2O, OH, O2, and H2. The governing set of nonlinear partial differential equations is solved by an implicit finite-difference procedure. Radial distributions are obtained at two downstream locations of variables such as turbulent kinetic energy, turbulent dissipation rate, turbulent scale length, and viscosity. The results show that these variables attain peak values at the axis of symmetry. Computed distributions of velocity, temperature, and mass fraction are also given. A direct analytical approach to account for the effect of species concentration fluctuations on the mean production rate of species (the phenomenon of unmixedness) is also presented. However, the use of the method does not seem justified in view of the excessive computer time required to solve the resulting system of equations.

  1. MORATE: a program for direct dynamics calculations of chemical reaction rates by semiempirical molecular orbital theory

    NASA Astrophysics Data System (ADS)

    Truong, Thanh N.; Lu, Da-hong; Lynch, Gillian C.; Liu, Yi-Ping; Melissas, Vasilios S.; Stewart, James J. P.; Steckler, Rozeanne; Garrett, Bruce C.; Isaacson, Alan D.; Gonzalez-Lafont, Angels; Rai, Sachchida N.; Hancock, Gene C.; Joseph, Tomi; Truhlar, Donald G.

    1993-04-01

    We present a computer program, MORATE (Molecular Orbital RATE calculations), for direct dynamics calculations of unimolecular and bimolecular rate constants of gas-phase chemical reactions involving atoms, diatoms, or polyatomic species. The potential energies, gradients, and higher derivatives of the potential are calculated whenever needed by semiempirical molecular orbital theory without the intermediary of a global or semiglobal fit. The dynamical methods used are conventional or variational transition state theory and multidimensional semiclassical approximations for tunneling and nonclassical reflection. The computer program is conveniently interfaced package consisting of the POLYRATE program, version 4.5.1, for dynamical rate calculations, and the MOPAC program, version 5.03, for semiempirical electronic structure computations. All semiempirical methods available in MOPAC, in particular MINDO/3, MNDO, AM1, and PM3, can be called on to calculate the potential and gradient. Higher derivatives of the potential are obtained by numerical derivatives of the gradient. Variational transition states are found by a one-dimensional search of generalized-transition-state dividing surfaces perpendicular to the minimum-energy path, and tunneling probabilities are evaluated by numerical quadrature.

  2. Zero energy resonances in reactive scattering: anomalous temperature dependence of atom--molecule reaction rates

    NASA Astrophysics Data System (ADS)

    Simbotin, I.; Ghosal, S.; Côté, R.

    2010-03-01

    We show that rate coefficients for inelastic processes---reactive, or nonreactive---in the (ultra)cold regime can be greatly affected by the presence of a resonance pole near E=0 in the entrance channel. This problem has been investigated previously [E. Bodo et al., J. Phys. B 37 (2004) 3641] but their analysis was restricted to the energy dependence of the reaction cross section for a particular case. Here, we present the general case, and we emphasize the possibility of a wide intermediate regime of temperatures where the rate coefficient has an anomalous temperature dependence; namely it increases as 1/T when T decreases. Eventually, the temperature dependence reverts back to the standard behavior given by Wigner's law, i.e., the rate coefficient becomes constant, but this may only be recovered at extremely low T (very deep into the ultracold regime). Thus, at least in some exceptional cases, most of the (ultra)cold regime could be dominated by this anomalous behavior.

  3. Relationship of reaction rate to amounts adsorbed for the low-temperature ortho-para hydrogen shift

    SciTech Connect

    Kauffman, D.; Brown, L.F.; Manogue, W.H.

    1981-10-01

    The relationships between the amounts of adsorbed reactant and product and the forward and reverse reaction rates were measured for the ortho-para hydrogen system on a chromia-alumina catalyst at 75.7 K. Total adsorption was measured rapidly; individual species isotherms as functions of pressure and composition were extracted from the total adsorption data. Reaction rates were determined as functions of pressure and composition using an integral, packed-bed reactor. The resulting relationship s between individual surface reaction rates and the amounts of adsorbed reactants are nonlinear. The observed results can be explained by a reaction mecha nism involving mobile adsorbed products and reactants. The reactants in this system primarily are physically adsorbed, so these results may be generalized to other systems only with caution.

  4. An Analogy Using Pennies and Dimes to Explain Chemical Kinetics Concepts

    ERIC Educational Resources Information Center

    Cortes-Figueroa, Jose E.; Perez, Wanda I.; Lopez, Jose R.; Moore-Russo, Deborah A.

    2011-01-01

    In this article, the authors present an analogy that uses coins and graphical analysis to teach kinetics concepts and resolve pseudo-first-order rate constants related to transition-metal complexes ligand-solvent exchange reactions. They describe an activity that is directed to upper-division undergraduate and graduate students. The activity…

  5. Early diagenetic processes, fluxes, and reaction rates in sediments of the South Atlantic

    SciTech Connect

    Schulz, H.D.; Dahmke, A.; Schinzel, U.; Wallmann, K.; Zabel, M. )

    1994-05-01

    Porewaters recovered from sediment cores (gravity corers, box corers, and multicorers) from various subregions of the South Atlantic (Amazon River mouth, equatorial upwelling, Congo River mouth, Benguela coastal upwelling area, and Angola Basin) were investigated geochemically. Objectives included determination of Eh, pH, oxygen, nitrate, sulfate, alkalinity, phosphate, ammonium, fluoride, sulfide, Ca, Mg, Sr, Fe, Mn, and Si, in order to quantify organic matter diagenesis and related mineral precipitation and dissolution processes. Porewater profiles from the eastern upwelling areas of the South Atlantic suggest that sulfate reduction in the deeper parts of the sediment may be attributed mainly to methane oxidation, whereas organic matter degradation by sulfate reduction is restricted to the near-surface sediments. Further, a prominent concentration gradient change of sulfate and related mineralization products occurred typically in the upwelling sediments at a depth of 4 to 8 m, far below the zone of bioturbation or bioirrigation. Because other sedimentological reasons seem to fail as explanations, an early diagenetic sulfide oxidation to sulfate within the anoxic environment is discussed. Porewater profiles from the sediments of the Amazon fan area are mainly influenced by reactions with Fe(III)-phases. The remarkable linearity of the concentration gradients of sulfate supports the idea of distinct reaction layers in these sediments. In contrast to the upwelling sediments, the sulfate gradient develops from the sediment surface to a sulfate reduction zone at a depth of 5.3 m, probably because a reoxidation of sulfide is prevented by the reaction with iron oxides and the formation of iron sulfide minerals. A comparison of organic matter degradation rates from the different areas of the South Atlantic show the expected relationship to primary productivity.

  6. A mm/submm Wave Spectrometer to Quantify Astrochemical Reaction Rates

    NASA Astrophysics Data System (ADS)

    Laas, Jacob C.; Weaver, Susanna L. Widicus

    2013-06-01

    Complex organic molecules (COMs) are being routinely detected at millimeter and submillimeter wavelengths toward a variety of interstellar environments. There is a growing consensus that their formation is dominated by barrierless, diffusion-limited addition reactions of radicals on icy grain surfaces. While astrochemical models have predicted the presence of many of these COMs, discrepancies have arisen between their observed and predicted relative abundances. It is likely that these discrepancies arise from uncertainties in the rates for the dissociation reactions that form the precursor radicals. More complete laboratory information is needed to improve the predictive power of astrochemical models of organic chemistry. We have developed a laboratory experiment that utilizes mm/submm wave direct absorption spectroscopy to probe photodissociation branching ratios that are relevant to astrochemical models of complex organic chemistry. We have benchmarked the performance of this spectrometer by examining the dissociation of methanol using a high-voltage discharge source. We will report on these results, and the progress of utilizing this spectrometer for photodissociation studies of COMs and COM precursors.

  7. Dependence of Substrate Irradiation Reaction Rate Stimulation on Lactic Dehydrogenase Source

    E-print Network

    George Bass; James Chenevey

    2013-04-16

    Stimulation of LDH initial reaction rates by timed pre-irradiation of crystalline sodium pyruvate and lithium lactate is reported for enzymes isolated from rabbit muscle, pig heart, human erythrocytes and chicken heart. The phenomenon investigated is referred to as the Comorosan effect. For the mammalian source enzymes, the pyruvate irradiation stimulations occurred at irradiation times of 5 and 35 sec. and the lactate irradiation times at 15 and 45 seconds. In contrast, for the chicken heart enzyme, the pyruvate irradiation stimulations occurred at 15 and 35 sec., while those for lactate occurred at 5 and 20 sec. Thus, a shift in stimulatory irradiation times is found on going from the mammalian enzymes to the avian enzyme. A similar shift between mammalian and yeast enzymes has been established by Comorosan and co-workers. For the chicken heart LDH, the separation between successive irradiation times is different for the forward and reverse reactions. This is the first reported incidence of the separation not being the same.

  8. Analytical Solution of Steady State Equations for Chemical Reaction Networks with Bilinear Rate Laws

    PubMed Central

    Halász, Ádám M.; Lai, Hong-Jian; McCabe, Meghan M.; Radhakrishnan, Krishnan; Edwards, Jeremy S.

    2014-01-01

    True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher dimensional space. We show that the linearized version of the steady state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1. PMID:24334389

  9. Pressure dependence on the reaction propagation rate of PETN at high pressure

    SciTech Connect

    Foltz, M.F.

    1993-04-01

    The reaction propagation rate (RPR) of the sensitive high explosive pentaerythritol tetranitrate (PETN) was measured in a diamond anvil cell (DAC) over the pressure range of 2--20 GPa. The experimental technique used is the same as that previously reported. The RPR data shows that it burns one to two orders of magnitude faster in the DAC than 1,3,5,-triamino-2,4,6-trinitrobenzene (TATB) and nitromethane (CH{sub 3}NO{sub 2}) respectively. The PETN RPR curve did not show sample pressure-dependent behavior like that of nitromethane, but instead varied abruptly like the RPR curve of TATB. In order to interpret these changes, static-pressure DAC mid-IR FTIR spectra were taken of micro-pellets of PETN embedded in KBr. The relationship between changes in the spectra, the RPR curve, and published single crystal PETN wedge test data are discussed.

  10. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption.

    PubMed

    Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao; Subbaraman, Ram; Danilovic, Nemanja; van der Vliet, Dennis; Paulikas, Arvydas P; Stamenkovic, Vojislav R; Markovic, Nenad M

    2013-04-01

    The development of hydrogen-based energy sources as viable alternatives to fossil-fuel technologies has revolutionized clean energy production using fuel cells. However, to date, the slow rate of the hydrogen oxidation reaction (HOR) in alkaline environments has hindered advances in alkaline fuel cell systems. Here, we address this by studying the trends in the activity of the HOR in alkaline environments. We demonstrate that it can be enhanced more than fivefold compared to state-of-the-art platinum catalysts. The maximum activity is found for materials (Ir and Pt?.?Ru?.?) with an optimal balance between the active sites that are required for the adsorption/dissociation of H? and for the adsorption of hydroxyl species (OHad). We propose that the more oxophilic sites on Ir (defects) and PtRu material (Ru atoms) electrodes facilitate the adsorption of OHad species. Those then react with the hydrogen intermediates (Had) that are adsorbed on more noble surface sites. PMID:23511418

  11. Temperature dependence of the NO + O3 reaction rate from 195 to 369 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Allen, J. E., Jr.; Brobst, W. D.

    1981-01-01

    The temperature dependence of the NO + O3 reaction rate was examined by means of the fast flow technique. Several different experimental conditions and detection schemes were employed. With excess NO or excess O3, NO2 chemiluminescence was monitored. In addition, with excess O3, NO was followed by fluorescence induced by an NO microwave discharge lamp. The results of the three independent sets of data are compared and found to agree within experimental error, indicating the absence of secondary chemistry which might complicate the kinetics. The data exhibit curvature on an Arrhenius plot; however, the simple Arrhenius expression k = (2.6 + or - 0.8) x 10 to the -12th exp(-1435 + or - 64/T) cu cm/molecule s is an adequate description for T between 195 and 369 K. This result is compared to earlier determinations.

  12. Relative rate constants for the reactions of atomic oxygen with HO2 anad OH radicals

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1983-01-01

    Relative rate constants for the reactions O + HO2 - OH + O2 (1) and O + OH - H + O2 (2) were obtained by using the discharge-flow resonance fluorescence technique at 2 torr total pressure and 299 K. HO2 radicals were generated by reacting atomic hydrogen with an excess of O2. Quasi-steady-state concentrations of OH and HO2 were established in the presence of excess atomic oxygen. Observed concentration ratios, namely the ratio of the OH concentration to the HO2 concentration, resulted in a value of 1.7 + or 0.2 for k1/k2. The error limits are twice the standard deviation obtained from the data analysis. Overall experimental error is estimated to be + or - 25 percent. This result confirms earlier direct measurements of k1 and k2 which required knowledge of absolute radical or atomic oxygen concentrations.

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

    PubMed

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

    2015-11-01

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

  14. Absolute Determination of the 22Na(p,g) Reaction Rate in Novae

    E-print Network

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

    2011-02-04

    Gamma-ray telescopes in orbit around the Earth are searching for evidence of the elusive radionuclide 22Na produced in novae. Previously published uncertainties in the dominant destructive reaction, 22Na(p,g)23Mg, indicated new measurements in the proton energy range of 150 to 300 keV were needed to constrain predictions. We have measured the resonance strengths, energies, and branches directly and absolutely by using protons from the University of Washington accelerator with a specially designed beamline, which included beam rastering and cold vacuum protection of the 22Na implanted targets. The targets, fabricated at TRIUMF-ISAC, displayed minimal degradation over a ~ 20 C bombardment as a result of protective layers. We avoided the need to know the stopping power, and hence the target composition, by extracting resonance strengths from excitation functions integrated over proton energy. Our measurements revealed that resonance strengths for E_p = 213, 288, 454, and 610 keV are stronger by factors of 2.4 to 3.2 than previously reported. Upper limits have been placed on proposed resonances at 198-, 209-, and 232-keV. We have re-evaluated the 22Na(p,g) reaction rate, and our measurements indicate the resonance at 213 keV makes the most significant contribution to 22Na destruction in novae. Hydrodynamic simulations including our rate indicate that the expected abundance of 22Na ejecta from a classical nova is reduced by factors between 1.5 and 2, depending on the mass of the white-dwarf star hosting the nova explosion.

  15. Helium effects on microstructural change in RAFM steel under irradiation: Reaction rate theory modeling

    NASA Astrophysics Data System (ADS)

    Watanabe, Y.; Morishita, K.; Nakasuji, T.; Ando, M.; Tanigawa, H.

    2015-06-01

    Reaction rate theory analysis has been conducted to investigate helium effects on the formation kinetics of interstitial type dislocation loops (I-loops) and helium bubbles in reduced-activation-ferritic/martensitic steel during irradiation, by focusing on the nucleation and growth processes of the defect clusters. The rate theory model employs the size and chemical composition dependence of thermal dissociation of point defects from defect clusters. In the calculations, the temperature and the production rate of Frenkel pairs are fixed to be T = 723 K and PV = 10-6 dpa/s, respectively. And then, only the production rate of helium atoms was changed into the following three cases: PHe = 0, 10-7 and 10-5 appm He/s. The calculation results show that helium effect on I-loop formation quite differs from that on bubble formation. As to I-loops, the loop formation hardly depends on the existence of helium, where the number density of I-loops is almost the same for the three cases of PHe. This is because helium atoms trapped in vacancies are easily emitted into the matrix due to the recombination between the vacancies and SIAs, which induces no pronounced increase or decrease of vacancies and SIAs in the matrix, leading to no remarkable impact on the I-loop nucleation. On the other hand, the bubble formation depends much on the existence of helium, in which the number density of bubbles for PHe = 10-7 and 10-5 appm He/s is much higher than that for PHe = 0. This is because helium atoms trapped in a bubble increase the vacancy binding energy, and suppress the vacancy dissociation from the bubble, resulting in a promotion of the bubble nucleation. And then, the helium effect on the promotion of bubble nucleation is very strong, even the number of helium atoms in a bubble is not so large.

  16. Reaction rates, depositional history and sources of indium in sediments from Appalachian and Canadian Shield lakes

    NASA Astrophysics Data System (ADS)

    Tessier, André; Gobeil, Charles; Laforte, Lucie

    2014-07-01

    Sediment cores were collected at the deepest site of twelve headwater lakes from the Province of Québec, Canada that receive contaminants only from atmospheric deposition, either directly to the lake surface or indirectly from the watershed. Several of the lakes are located within relatively short distance (<40 km) and others at more than 200 km from potential sources of contamination. The sediments were dated and analyzed for In and other elements including Fe, Mn, Al and organic C. Fe-rich authigenic material was collected on Teflon sheets inserted vertically into the sediments at the only study site whose hypolimnion remains perennially oxic. Porewater samples collected at the coring site of four of the lakes were also analyzed for In and other solutes including sulfide, sulfate, Fe, Mn, inorganic and organic C and major ions. The porewater In profiles display concentration gradients at or below the sediment-water interface. Modeling these profiles with a one-dimensional transport-reaction equation assuming steady state allows definition of depth intervals (zones) where In is either released to or removed from porewater and quantification of net In reactions rates in each zone. The position of the In consumption zones, the shape of the vertical profiles of dissolved In, sulfide and iron, as well as thermodynamic calculations of saturation states collectively suggest that In(OH)3(s) and In2S3(s) do not precipitate in the sediments and that adsorption of In onto sedimentary FeS(s) does not occur. However, similarities in the In and Fe porewater profiles, and the presence of In in the authigenic Fe-rich solids, reveal that part of the In becomes associated with authigenic Fe oxyhydroxides in the perennially oxic lake and is coupled to the Fe redox cycling. Comparison of the In/Corg and In/Fe molar ratios in the authigenic Fe-rich material and in surface sediments (0-0.5 cm) of this lake suggests that most non-lithogenic In was bound to humic substances. From the magnitude of the net In reaction rates, we infer that the post-depositional redistribution of this element is quantitatively not important and that the In sedimentary record represents accurately In deposition at the sampling sites. Reconstructed chronologies of the anthropogenic In deposition and comparison of In inventories among lakes point to non-ferrous metal smelters as a past significant source of atmospheric In contamination and to a significant reduction of industrial In emissions into the North American atmosphere in recent decades.

  17. Influence of changing particle structure on the rate of gas-solid gasification reactions. Final report, July 1981-March 1984

    SciTech Connect

    Not Available

    1984-04-04

    The objetive of this work is to determine the changes in the particle structure of coal as it undergoes the carbon/carbon dioxide reaction (C + CO/sub 2/ ..-->.. 2CO). Char was produced by heating the coal at a rate of 25/sup 0/C/min to the reaction temperatures of 800/sup 0/C, 900/sup 0/C, 1000/sup 0/C and 1100/sup 0/C. The changes in surface area and effective diffusivity as a result of devolitization were determined. Changes in effective diffusivity and surface area as a function of conversion have been measured for reactions conducted at 800, 900, 1000 and 1100/sup 0/C for Wyodak coal char. The surface areas exhibit a maximum as a function of conversion in all cases. For the reaction at 1000/sup 0/C the maximum in surface area is greater than the maxima determined at all other reaction temperatures. Thermogravimetric rate data were obtained for five coal chars; Wyodak, Wilcox, Cimmeron, Illinois number 6 and Pittsburgh number 6 over the temperature range 800-1100/sup 0/C. All coal chars exhibit a maximum in reaction rate. Five different models for gas-solid reactions were evaluated. The Bhatia/Perlmutter model seems to best represent the data. 129 references, 67 figures, 37 tables.

  18. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

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

  20. Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

    1984-01-01

    Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

  1. 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.

  2. A model to predict the thermal reaction norm for the embryo growth rate from field data.

    PubMed

    Girondot, Marc; Kaska, Yakup

    2014-10-01

    The incubation of eggs is strongly influenced by temperature as observed in all species studied to date. For example, incubation duration, sexual phenotype, growth, and performances in many vertebrate hatchlings are affected by incubation temperature. Yet it is very difficult to predict temperature effect based on the temperature within a field nest, as temperature varies throughout incubation. Previous works used egg incubation at constant temperatures in the laboratory to evaluate the dependency of growtProd. Type: FTPh rate on temperature. However, generating such data is time consuming and not always feasible due to logistical and legislative constraints. This paper therefore presents a methodology to extract the thermal reaction norm for the embryo growth rate directly from a time series of incubation temperatures recorded within natural nests. This methodology was successfully applied to the nests of the marine turtle Caretta caretta incubated on Dalyan Beach in Turkey, although it can also be used for any egg-laying species, with some of its limitations being discussed in the paper. Knowledge about embryo growth patterns is also important when determining the thermosensitive period for species with temperature-dependent sex determination. Indeed, in this case, sexual phenotype is sensitive to temperature only during this window of embryonic development. PMID:25436957

  3. Rate constant for the OH + CO reaction - Pressure dependence and the effect of oxygen

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1984-01-01

    The effect of pressure on the rate constant of the OH + CO reaction has been measured for Ar, N2, and SF6 over the pressure range 200-730 torr. All experiments were at room temperature. The method involved laser-induced fluorescence to measure steady-state OH concentrations in the 184.9 nm photolysis of H2O-CO mixtures in the three carrier gases, combined with supplementary measurements of the CO depletion in these same carrier gases in the presence and absence of competing reference reactants. The effect of O2 on the pressure effect was determined. A pressure enhancement of the rate constant was observed for N2 and SF6, but not for Ar, within an experimental error of about 10 percent. The pressure effect for N2 was somewhat lower than previous literature reports, being about 40 percent at 730 torr. For SF6 a factor of two enhancement was seen at 730 torr. In each case it was found that O2 had no effect on the pressure enhancement. The roles of the radical species HCO and HOCO were evaluated.

  4. Potential chlorofluorocarbon replacements: OH reaction rate constants between 250 and 315 K and infrared absorption spectra

    SciTech Connect

    Garland, N.L.; Medhurst, L.J.; Nelson, H.H.

    1993-12-20

    The authors measured the rate constant for reactions of the OH radical with several potential chlorofluorocarbon replacements over the temperature range 251-314 K using laser photolysis laser-induced fluorescence techniques. The compounds studied and Arrhenius parameters determined from fits to the measured rate constants are as follows: CHF{sub 2}OCHF{sub 2} (E 134), k(T) = (5.4 {+-} 3.5) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}3.1 {+-} 0.4 kcal mol{sup {minus}1})/RT]; CF{sub 3}CH{sub 2}CF{sub 3} (FC 236fa), k(T) = (2.0 {+-} 1.0) x 10{sup {minus}14} cm{sup 3} s{sup {minus}1} exp [({minus}1.8 {+-} 0.3 kcal mol{sup {minus}1})/RT]; CF{sub 3}CHFCHF{sub 2} (FC 236ea), k(T) = (2.0 {+-} 0.9) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.0 {+-} 0.3 kcal mol{sup {minus}1})/RT]; and CF{sub 3}CF{sub 2}CH{sub 2}F (FC 236cb), k(T) = (2.6 {+-} 1.6) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.2 {+-} 0.4 kcal mol{sup {minus}1})/RT]. The measured activation energies (2-3 kcal mol{sup {minus}1}) are consistent with a mechanism of H atom abstraction. The tropospheric lifetimes, estimated from the measured OH reaction rates, and measured integrated infrared absorption cross sections over the range 770 to 1430 cm{sup {minus}1} suggest that E 134 and FC 236fa may have significant global warming potential, while FC 236ea and FC 236cb do not. 17 refs., 4 figs., 3 tabs.

  5. Type Ia supernovae and the 12C+12C reaction rate

    NASA Astrophysics Data System (ADS)

    Bravo, E.; Piersanti, L.; Domínguez, I.; Straniero, O.; Isern, J.; Escartin, J. A.

    2011-11-01

    Context. Even if the 12C+12C reaction plays a central role in the ignition of type Ia supernovae (SNIa), the experimental determination of its cross-section at astrophysically relevant energies (E ? 2 MeV) has never been made. The profusion of resonances throughout the measured energy range has led to speculation that there is an unknown resonance at E0 ~ 1.5 MeV possibly as strong as the one measured for the resonance at 2.14 MeV, i.e. (??)R = 0.13 meV. Aims: We study the implications that such a resonance would have for our knowledge of the physics of SNIa, paying special attention to the phases that go from the crossing of the ignition curve to the dynamical event. Methods: We use one-dimensional hydrostatic and hydrodynamic codes to follow the evolution of accreting white dwarfs until they grow close to the Chandrasekhar mass and explode as SNIa. In our simulations, we account for a low-energy resonance by exploring the parameter space allowed by experimental data. Results: A change in the 12C+12C rate similar to the one explored here would have profound consequences for the physical conditions in the SNIa explosion, namely the central density, neutronization, thermal profile, mass of the convective core, location of the runaway hot spot, or time elapsed since crossing the ignition curve. For instance, with the largest resonance strength we use, the time elapsed since crossing the ignition curve to the supernova event is shorter by a factor ten than for models using the standard rate of 12C+12C, and the runaway temperature is reduced from ~8.14 × 108 K to ~ 4.26 × 108 K. On the other hand, a resonance at 1.5 MeV, with a strength ten thousand times smaller than the one measured at 2.14 MeV, but with an ?/p yield ratio substantially different from 1 would have a sizeable impact on the degree of neutronization of matter during carbon simmering. Conclusions: A robust understanding of the links between SNIa properties and their progenitors will not be attained until the 12C+12C reaction rate is measured at energies ~1.5 MeV.

  6. The 8Li(d,p)9Li Reaction and the Astrophysical 8Li(n,g)9Li Reaction Rate

    E-print Network

    Z. H. Li

    2009-03-18

    The $^8$Li($n,\\gamma$)$^9$Li reaction plays an important role in both the r-process nucleosynthesis and the inhomogeneous big bang models, its direct capture rates can be extracted from the $^8$Li($d, p$)$^9$Li reaction, indirectly. We have measured the angular distribution of the $^8$Li($d, p$)$^9$Li$_{\\textrm{g.s.}}$ reaction at $E_{\\textrm{c.m.}}$ = 7.8 MeV in inverse kinematics using coincidence detection of $^{9}\\textrm{Li}$ and recoil proton, for the first time. Based on Distorted Wave Born Approximation (DWBA) analysis, the $^{8}\\textrm{Li}(d, p)^{9}\\textrm{Li}_{\\textrm{g.s.}}$ cross section was determined to be 7.9 $\\pm$ 2.0 mb. The single particle spectroscopic factor, $S_{1,3/2}$, for the ground state of $^{9}\\textrm{Li}$ = $^{8}\\textrm{Li} \\otimes n$ was derived to be $0.68\\pm 0.14$, and then used to calculate the direct capture cross sections for the $^{8}\\textrm{Li}(n, \\gamma)^{9}\\textrm{Li}_{\\textrm{g.s.}}$ reaction at energies of astrophysical interest. The astrophysical $^{8}\\textrm{Li}(n, \\gamma)^{9}\\textrm{Li}_{\\textrm{g.s.}}$ reaction rate for the direct capture was found to be 3970 $\\pm$ 950 $\\textrm{cm}^{3}\\textrm{mole}^{-1}s^{-1}$ at $T_9$ = 1. This presents the first experimental constraint for the $^{8}\\textrm{Li}(n, \\gamma)^{9}\\textrm{Li}$ reaction rates of astrophysical relevance.

  7. Experimental measurements of low temperature rate coefficients for neutral-neutral reactions of interest for atmospheric chemistry of Titan, Pluto and Triton: reactions of the CN radical.

    PubMed

    Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R

    2010-01-01

    The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere. PMID:21302546

  8. Electron Attachment Reaction Rates in 2D Atomic Hydrogen-Electron Mixed System on Liquid Helium Surface

    SciTech Connect

    Arai, Toshikazu; Mitsui, Tomoyuki; Yayama, Hideki

    2006-09-07

    We have measured the temperature dependence of the electron attachment reaction rate of atomic hydrogen (H) on a liquid 4He surface in applied magnetic fields of 0-5 T at 0.2-0.6 K. The measured surface state electron (SSE) losses are faster at lower temperatures for a given magnetic field. This behavior can be qualitatively understood, since the surface coverage of adsorbed H is large at low temperature and the collisions between H and SSE are frequent. However, the reaction is faster than expected based on the collision frequency argument. The measured reaction rate coefficient Ke is strongly temperature dependent. We observe that, as the temperature is lowered, Ke increases by several orders of magnitude. This indicates that some additional effect enhances electron attachment at low temperature. We discuss a possible reaction mechanism between H and SSE.

  9. New high accuracy measurement of the {sup 17}O(p,{alpha}){sup 14}N reaction rate at astrophysical temperatures

    SciTech Connect

    Sergi, M. L.; Spitaleri, C.; La Cognata, M.; Cherubini, S.; Crucilla, V.; Gulino, M.; Kiss, G. G.; Lamia, L.; Pizzone, R. G.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Tudisco, S.; Tumino, A.; Coc, A.; Burjan, S. V.; Hons, Z.; Kroha, V.; Hammache, F.

    2010-09-15

    The {sup 17}O(p,{alpha}){sup 14}N reaction is of fundamental relevance in several astrophysical scenarios, such as novae, asymptotic giant branch nucleosynthesis, and {gamma}-ray astronomy. We report on the indirect measurement of the {sup 17}O(p,{alpha}){sup 14}N reaction bare-nucleus cross section in the low-energy region. In particular, the two resonances at E{sub R}{sup c.m.}=65 keV and E{sub R}{sup c.m.}=183 keV, which dominate the reaction rate inside the Gamow window, have been observed, and the strength of the 65 keV resonance has been deduced. The reaction rate determination and the comparison with the results of the previous measurements are also discussed.

  10. Width of 27P(1.19 MeV ) and the 26Si(p ,? ) reaction rate

    NASA Astrophysics Data System (ADS)

    Fortune, H. T.

    2015-08-01

    I have used a simple potential model to calculate single-particle widths in 27P. Assuming mirror symmetry, I have combined them with the spectroscopic factor from the reaction 26Mg(d ,p ) to compute proton widths for the 3 /2+ first-excited state. I present results for the resonance strength parameter ? ? and for the (p ,? ) reaction rate for two values of the ? width and two values of the resonance energy.

  11. Absolute Rate Constants for the Reaction of OH with [|#11#|]Cyclopentane and Cycloheptane from 230-350 K

    NASA Astrophysics Data System (ADS)

    Dransfield, T. J.; Gennaco, M. M.; Huang, Y.; Hannun, R. A.

    2011-12-01

    We report absolute measurements of the rate constants of the reaction of hydroxyl radical (OH) with cyclopentane and cycloheptane in 6-8 Torr of nitrogen from 230-350 K using Harvard's High Pressure Flow System. Ethane's reactivity was simultaneously measured as a test of experimental performance. Hydroxyl concentrations were measured using Laser-Induced Fluorescence, and alkane concentrations were measured using Fourier-Transform Infrared Spectroscopy. Recent work on this flow system has suggested that cyclohexane has a significantly higher activation energy to reaction with OH than does cyclo-octane, a result which is not suggested by our understanding of hydrocarbon reactivity nor predicted by structure-activity relationships. This work examines the temperature dependent rates for two other similarly-sized cycloalkanes to determine whether they behave as cyclohexane or as cyclooctane. While several previous experiments have studied the reaction with cyclopentane, there is significant scatter in the room temperature rates, and only four absolute rate measurements are available at non-ambient temperatures. There are only two absolute rate measurements available for the reaction with cycloheptane; only one of these reports a temperature dependence, and that study is limited to temperatures above 298 K. Thus, this work significantly expands the available data set for both reactions. The data for the reactions of OH with ethane, cyclopentane, cyclohexane, and cycloheptane are all modeled using a simple Arrhenius fit, and also with a modified Arrhenius equation based on transition state theory, ignoring tunneling. Results from the latter fit indicate that the activation barriers for both title reactions are greater than that of OH + cyclo-octane. The measured activation energy for OH + cyclopentane actually exceeds that of OH + cyclohexane.

  12. 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. ?fH298o 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

  13. Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

    SciTech Connect

    Koretsky, A.P.

    1984-01-01

    /sup 31/P NMR is a unique tool to study bioenergetics in living cells. The application of magnetization transfer techniques to the measurement of steady-state enzyme reaction rates provides a new approach to understanding the regulation of high energy phosphate metabolism. This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate were compared to whole kidney oxygen consumption and Na/sup +/ reabsorption rates to derive ATP/O values. The problems associated with ATP synthesis rate measurements in kidney, e.g. the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed. In heart, the forward rate through creatine kinase was measured to be larger than the reverse rate. To account for the difference in forward and reverse rates a model is proposed based on the compartmentation of a small pool of ATP.

  14. Investigations of solvent properties and solvent effects on chemical equilibria and reaction rates

    NASA Astrophysics Data System (ADS)

    Defeo, Laura Lynn Thomas

    Thermodynamic and structural properties computed via simulations of pure liquids and dilute solutions are routinely used as a metric of accuracy for condensed-phase force fields and in the development and testing of new methodology. Additionally, reliable modeling of solvent systems is critical to investigations of physical phenomena, such as the elucidation of solvent effects on chemical equilibria and reaction rates. This dissertation highlights a series of studies that span these topics. The Lennard-Jones 12-6 functional form, often invoked to model van der Waals interactions, has been argued to be too repulsive at short internuclear separations. Monte Carlo simulations of organic liquids at various temperatures and pressures show that this function, in conjunction with OPLS parameters, is capable of reproducing experimental densities. In order to address potential cumulative deviations of computed properties and conformational differences between the gas phase and pure liquids, Monte Carlo simulations have been carried out for the homologous n-alkane series C4H10-C12H26 using the OPLS-AA force field. Favorable structural motifs of longer alkanes were also investigated to study self solvation in the gas phase. Next, an overview of the computation of free energy changes in solution using perturbation theory, overlap sampling, and related approximate methods is presented. Results are provided for free energies of hydration of OPLS-AA substituted benzenes in TIP4P water. For comparable amounts of computer time, the double-wide and overlap sampling methods yield very similar results. QM/MM simulations of the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the water-vacuum interface and in the gas phase. The relative free energies of activation and transition structure geometries at the interface were intermediate between those calculated in the gas phase and in bulk water, consistent with estimated experimental rate constants. Energy pair distributions reveal a loss of slightly favorable solute-solvent pair contacts but retention of stronger interactions upon transition from bulk to surface hydration. These strong interactions cause the methyl vinyl ketone transition structure to preferentially orient its carbonyl toward the surface, while the other transition structures prefer orientations parallel to the surface.

  15. A Nonlinear Observer for Semidetectable Chemical Reactions with Application to Kinetic-Rate-Constant Estimation

    E-print Network

    Bernstein, Dennis S.

    A Nonlinear Observer for Semidetectable Chemical Reactions with Application to Kinetic]. For the class of polyno- mial systems that model the concentrations of species of a chemical reaction network that the reactions of chemical networks are semistable, that is, the concentrations converge to nonzero values

  16. Astrophysical Reaction Rate for the Neutron-Generator Reaction {sup 13}C({alpha},n){sup 16}O in Asymptotic Giant Branch Stars

    SciTech Connect

    Johnson, E. D.; Rogachev, G. V.; Baby, L. T.; Cluff, W. T.; Crisp, A. M.; Diffenderfer, E.; Green, B. W.; Hinners, T.; Hoffman, C. R.; Kemper, K. W.; Momotyuk, O.; Peplowski, P.; Pipidis, A.; Reynolds, R.; Roeder, B. T.; Mukhamedzhanov, A. M.; Goldberg, V. Z.; Brown, S.

    2006-11-10

    The reaction {sup 13}C({alpha},n) is considered to be the main source of neutrons for the s process in asymptotic giant branch stars. At low energies, the cross section is dominated by the 1/2{sup +} 6.356 MeV subthreshold resonance in {sup 17}O whose contribution at stellar temperatures is uncertain by a factor of 10. In this work, we performed the most precise determination of the low-energy astrophysical S factor using the indirect asymptotic normalization (ANC) technique. The {alpha}-particle ANC for the subthreshold state has been measured using the sub-Coulomb {alpha}-transfer reaction ({sup 6}Li,d). Using the determined ANC, we calculated S(0), which turns out to be an order of magnitude smaller than in the nuclear astrophysics compilation of reaction rates.

  17. EFFECTS OF PORE STRUCTURE CHANGE AND MULTI-SCALE HETEROGENEITY ON CONTAMINANT TRANSPORT AND REACTION RATE UPSCALING

    SciTech Connect

    Peters, Catherine A

    2013-05-15

    This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE legacy waste problems.

  18. Determination of the astrophysical 12N(p,?)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,?)13O reaction is an important branching point in the rap processes, which are believed to be alternative paths to the slow 3? 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,?)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,?)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,?)13O will only compete successfully with the ?+ decay of 12N at higher (˜2 orders of magnitude) densities than initially predicted.

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

    SciTech Connect

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

    2009-02-25

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

  20. Rate constant measurements for the reaction Cl + CH2O yields HCl + CHO Implications regarding the removal of stratospheric chlorine

    NASA Technical Reports Server (NTRS)

    Anderson, P. C.; Kurylo, M. J.

    1979-01-01

    The flash photolysis resonance fluorescence technique was employed to investigate the rate constant for the reaction Cl + CH2O yields HCl + CHO from 223 to 323 K. An Arrhenius fit of the data gives a rate constant equal to (1.09 + or - 0.40) x 10 to the -10th exp/-(131 + or - 98)/T/ in units of cu cm/molecule per sec. The results are compared to two very recent kinetic studies and are assessed in view of the reaction's role in disrupting the Cl-ClO stratospheric ozone depletion chain.

  1. Quantum reaction rate from higher derivatives of the thermal flux-flux autocorrelation function at time zero

    NASA Astrophysics Data System (ADS)

    Ceotto, Michele; Yang, Sandy; Miller, William H.

    2005-01-01

    A quantum theory of thermal reaction rates is presented which may be viewed as an extension of the recently developed "quantum instanton" (QI) model [W. H. Miller, Y. Zhao, M. Ceotto, and S. Yang, J. Chem. Phys. 119, 1329 (2003)]. It is based on using higher derivatives of the flux-flux autocorrelation function C(t) (as given by Miller, Schwartz, and Tromp) at t=0 to construct a short time approximation for C(t). Tests of this theory on 1d and collinear reactions, both symmetric and asymmetric, show it to be more accurate than the original QI model, giving rate constants to ˜5% for a wide range of temperature.

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

    SciTech Connect

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

    2013-11-07

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

  3. New reaction rates for improved primordial D/H calculation and the cosmic evolution of deuterium

    E-print Network

    Coc, Alain; Uzan, Jean-Philippe; Vangioni, Elisabeth; Descouvemont, Pierre; Illiadis, Christian; Longland, Richard

    2015-01-01

    Primordial or big bang nucleosynthesis (BBN) is one of the three historical strong evidences for the big bang model. Standard BBN is now a parameter free theory, since the baryonic density of the Universe has been deduced with an unprecedented precision from observations of the anisotropies of the cosmic microwave background (CMB) radiation. There is a good agreement between the primordial abundances of 4He, D, 3He and 7Li deduced from observations and from primordial nucleosynthesis calculations. However, the 7Li calculated abundance is significantly higher than the one deduced from spectroscopic observations and remains an open problem. In addition, recent deuterium observations have drastically reduced the uncertainty on D/H, to reach a value of 1.6%. It needs to be matched by BBN predictions whose precision is now limited by thermonuclear reaction rate uncertainties. This is especially important as many attempts to reconcile Li observations with models lead to an increased D prediction. Here, we re-evalua...

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

    SciTech Connect

    Hufnagel, Todd C.

    2014-06-09

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

  5. High-precision (p,t) reaction measurement to determine {sup 18}Ne({alpha},p){sup 21}Na reaction rates

    SciTech Connect

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

    2009-11-15

    x-ray bursts are identified as thermonuclear explosions in the outer atmosphere of accreting neutron stars. The thermonuclear runaway is fueled by the {alpha}p process that describes a sequence of ({alpha},p) reactions triggered by the {sup 18}Ne({alpha},p){sup 21}Na breakout reaction from the hot CNO cycles. We studied the level structure of the compound nucleus {sup 22}Mg by measuring the {sup 24}Mg(p,t){sup 22}Mg reaction at the Grand Raiden spectrometer at Research Center for Nuclear Physics, Osaka. A large number of {alpha}-unbound states was identified and precise excitation energies were determined. Based on shell model and {alpha}-cluster model calculations we predict the level parameters for determining the stellar reaction rate of {sup 18}Ne({alpha},p){sup 21}Na for a wide temperature range. x-ray burst simulations have been performed to study the impact of the reaction on the x-ray burst luminosity.

  6. Modeling kinetic partitioning of secondary organic aerosol and size distribution dynamics: representing effects of volatility, phase state, and particle-phase reaction

    SciTech Connect

    Zaveri, Rahul A.; Easter, Richard C.; Shilling, John E.; Seinfeld, J. H.

    2014-05-27

    Evidence is mounting that the majority of the climatically active aerosols are produced through the growth of smaller particles via secondary organic aerosol (SOA) formation from gas-to-particle conversion of anthropogenic and biogenic volatile organic compounds (VOCs). The timescale of SOA partitioning and the associated size distribution dynamics are expected to depend on the gas-phase oxidation of the precursor VOCs and their products, volatility of these organic solutes, composition and phase state of the pre-existing particles, and diffusivity and reactivity of the solute within the particle phase. This paper describes a new framework for modeling kinetic gas-particle partitioning of SOA, with an analytical treatment for the diffusion-reaction process within the particle phase. The formulation is amenable for eventual use in regional and global climate models, although it currently awaits implementation of the actual particle-phase reactions that are important for SOA formation. In the present work, the model is applied to investigate the competitive growth dynamics of the Aitken and accumulation mode particles while the Kelvin effect and coagulation are neglected for simplicity. The timescale of SOA partitioning and evolution of number and composition size distributions are evaluated for a range of solute volatilities (C*), particle-phase bulk diffusivities (Db), and particle-phase reactivity, as exemplified by a pseudo-first-order rate constant (kc). Results show that irreversible condensation of non-volatile organic vapors (equivalent to ) produces significant narrowing of the size distribution. At the other extreme, non-reactive partitioning of semi-volatile organic vapors is volume-controlled in which the final (equilibrium) size distribution simply shifts to the right on the diameter axis while its shape remains unchanged. However, appreciable narrowing of the size distribution may occur when the pre-existing particles are highly viscous semi-solids such that small particles reach quasi-equilibrium much faster than the large ones. In the case of reactive partitioning (finite ), the size distribution experiences permanent narrowing, which is especially pronounced for Db < 10-13 cm2 s-1 and kc > 0.01 s-1. As a result, both number and composition size distributions are needed to effectively constrain and evaluate the next generation of SOA models that treat phase state thermodynamics, particle-phase diffusion and particle-phase chemical reactions.

  7. Timescales and rates for peridotite-groundwater reactions in the Samail Ophiolite, Sultanate of Oman

    NASA Astrophysics Data System (ADS)

    Paukert, A. N.; Matter, J.; Stute, M.; Kelemen, P. B.

    2014-12-01

    The peridotite section of the Samail Ophiolite, Sultanate of Oman is a site of ongoing low temperature serpentinization and carbonation. We present geochemical data for waters collected from boreholes in the peridotite to help describe subsurface water-rock reactions and rates. We constrained groundwater age using 3H-3He dating, He accumulation, dissolved noble gas thermometry, and stable isotopes (?2H, ?18O). Dissolved gas samples were collected from boreholes and used to estimate ongoing serpentinization rates. Boreholes in peridotite contain two water types: Type I Mg2+-HCO3- water and Type II Ca2+-OH- water. All of our groundwater dating techniques suggest boreholes with Type I water contain modern recharge. Type I boreholes have 3H-3He dates of 0-40 years, 3He/4He ratios similar to the atmosphere, and low levels of He accumulation. Noble gas thermometry shows recharge temperatures of 32oC, the modern mean annual ground temperature. Stable isotopes in Type I waters fall between the northern and southern local meteoric water lines, similar to other modern northern Oman groundwaters (Weyhenmeyer et al., Wat. Resour. Res., 2002). In contrast, Type II hyperalkaline groundwaters from boreholes in peridotite appear to be significantly older. Waters have pre-bomb 3H levels, and significant He accumulation from sources such as crustal production from radioactive decay or mantle He. Noble gas temperatures range from 30oC to 25oC, with the cooler samples potentially having recharged during a glacial period. Stable isotopes for Type II waters plot either between the northern and southern meteoric water lines or are enriched in ?18O. The enrichment may be due to evaporation or a change in the source of local water vapor during glacial periods. Dissolved gases from boreholes with Type I water are primarily N2, while gases from boreholes with Type II water include millimolar concentrations of H2, CH4, or both. These dissolved gases suggest the Type II boreholes are in or near areas of active low temperature serpentinization. Serpentinization rates calculated from dissolved gas concentrations and groundwater flow vary from 4x10-8 to 2x10-6 volume fraction peridotite serpentinized per year.

  8. Effects of a new triple-$\\alpha$ reaction rate on the helium ignition of accreting white dwarfs

    E-print Network

    Saruwatari, Motoaki

    2010-01-01

    Effects of a new triple-alpha reaction rate on the ignition of carbon-oxygen white dwarfs accreting helium in a binary systems have been investigated. The ignition points determine the properties of a thermonuclear explosion of a Type Ia supernova. We examine the cases of different accretion rates of helium and different initial masses of the white dwarf, which was studied in detail by Nomoto. We find that for all cases from slow to intermediate accretion rates, nuclear burnings are ignited at the helium layers. As a consequence, carbon deflagration would be triggered for the lower accretion rate compared to that of $dM/dt\\simeq 4\\times10^{-8} M_{\\odot} \\rm yr^{-1}$ which has been believed to the lower limit of the accretion rate for the deflagration supernova. Furthermore, off-center helium detonation should result for intermediate and slow accretion rates and the region of carbon deflagration for slow accretion rate is disappeared.

  9. Quantum mechanical calculations of state-to-state cross sections and rate constants for the F + DCl ? Cl + DF reaction

    SciTech Connect

    Bulut, Niyazi; K?os, Jacek; Roncero, Octavio

    2015-06-07

    We present accurate state-to-state quantum wave packet calculations of integral cross sections and rate constants for the title reaction. Calculations are carried out on the best available ground 1{sup 2}A? global adiabatic potential energy surface of Deskevich et al. [J. Chem. Phys. 124, 224303 (2006)]. Converged state-to-state reaction cross sections have been calculated for collision energies up to 0.5 eV and different initial rotational and vibrational excitations, DCl(v = 0, j = 0 ? 1; v = 1, j = 0). Also, initial-state resolved rate constants of the title reaction have been calculated in a temperature range of 100-400 K. It is found that the initial rotational excitation of the DCl molecule does not enhance reactivity, in contract to the reaction with the isotopologue HCl in which initial rotational excitation produces an important enhancement. These differences between the isotopologue reactions are analyzed in detail and attributed to the presence of resonances for HCl(v = 0, j), absent in the case of DCl(v = 0, j). For vibrational excited DCl(v = 1, j), however, the reaction cross section increases noticeably, what is also explained by another resonance.

  10. Rate constants for the reactions OH + HOCl. -->. H/sub 2/O + ClO and H + HOCl. -->. products

    SciTech Connect

    Ennis, C.A.; Birks, J.W.

    1988-03-10

    A new laboratory source of gaseous hypochlorous acid (HOCl) has been used in two kinetics investigations in a mass spectrometry-resonance fluorescence discharge flow system. Two potential removal reactions of stratospheric HOCl were studied. The rate constant for the reaction OH + HOCl ..-->.. H/sub 2/O + ClO (1) at 298 K was found to be lower than the NASA estimate by a factor of about 2-12; a value in the range (1.7-9.5) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ s/sup -1/ for k/sub 1/ is reported here. The reaction of Cl/sub 2/O + OH interfered in the study of k/sub 1/ and was the subject of a preliminary investigation. Its rate constant was determined to be (9.4 +/- 1.0) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 298 K. The rate constant for the reaction H + HOCl ..-->.. products (2) was determined to be (5.0 +/- 1.4) x 298 K. Although branching ratios for three possible products channels could not be determined, OH was identified as a product. The results of this work imply that reactions 1 and 2 are not competitive with direct photolysis in the removal of HOCl from the stratosphere.

  11. Absolute rate of the reaction of atomic hydrogen with ethylene from 198 to 320 K at high pressure

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

    The rate constant for the H+C2H4 reaction has been measured as a function of temperature. Experiments were performed with high pressures of Ar heat bath gas at seven temperatures from 198 to 320 K with the flash photolysis-resonance fluorescence (FP-RF) technique. Pressures were chosen so as to isolate the addition rate constant k1. The results are well represented by an Arrhenius expression. The results are compared with other studies and are theoretically discussed.

  12. Rate coefficients for the reaction of OH radicals with cis-3-hexene: an experimental and theoretical study.

    PubMed

    Barbosa, Thaís da Silva; Peirone, Silvina; Barrera, Javier A; Abrate, Juan P A; Lane, Silvia I; Arbilla, Graciela; Bauerfeldt, Glauco Favilla

    2015-04-14

    The kinetics of the cis-3-hexene + OH reaction were investigated by an experimental relative rate method and at the density functional theory level. The experimental set-up consisted of a 200 L Teflon bag, operated at atmospheric pressure and 298 K. OH radicals were produced by the photolysis of H2O2 at 254 nm. Relative rate coefficients were determined by comparing the decays of the cis-3-hexene and reference compounds (cyclohexene, 2-buten-1-ol and allyl ether). The mean second-order rate coefficient value found was (6.27 ± 0.66) × 10(-11) cm(3) molecule(-1) s(-1), the uncertainty being estimated by propagation of errors. Theoretical calculations for the addition reaction of OH to cis-3-hexene have also been performed, at the BHandHLYP/aug-cc-pVDZ level, in order to investigate the reaction mechanism, to clarify the experimental observations and to model the reaction kinetics. Different conformations of the reactants, pre-barrier complexes and saddle points were considered in our calculations. The individual rate coefficients, calculated for each conformer of the reactant, at 298 K, using a microcanonical variational transition state method, are 4.19 × 10(-11) and 1.23 × 10(-10) cm(3) molecule(-1) s(-1). The global rate coefficient was estimated from the Boltzmann distribution of the conformers to be 8.10 × 10(-11) cm(3) molecule(-1) s(-1), which is in agreement with the experimental value. Rate coefficients calculated over the temperature range from 200-500 K are also given. Our results suggest that the complex mechanism, explicitly considering different conformations for the stationary points, must be taken into account for a proper description of the reaction kinetics. PMID:25738192

  13. 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.

  14. Coulomb dissociation of 9Li and the rate of the 8Li(n,g)9Li reaction

    E-print Network

    P. Banerjee; R. Chatterjee; R. Shyam

    2008-09-12

    We calculate the Coulomb dissociation of 9Li on Pb and U targets at 28.5 MeV/A beam energy within a finite range distorted wave Born approximation formalism of the breakup reactions. Invoking the principle of detailed balance, these cross sections are used to determine the excitation function and subsequently the rate of the radiative capture reaction 8Li(n,g)9Li at astrophysical energies. Our method is free from the uncertainties associated with the multipole strength distributions of the 9Li nucleus. The rate of this reaction at a temperature of 10^9K is found to be about 2900 cm^3 mole^{-1} s^{-1}.

  15. Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1975-01-01

    Growth constants, obtained by measuring the blue CO flame band emission behind incident shock waves, were obtained for two elementary bimolecular reactions involved in the oxidation of methane. Gas mixtures containing small amounts of CH4 with varying amounts of CO, O2, and in one case CO2, diluted with argon, were investigated, and exponential growth constants were derived from plots of the logarithm of observed light intensity versus gas time. The rate constant for the reaction O + CH4 yields CH3 + OH was found to be 1.9 times 10 to the 14th exp(-5900/T) cu cm per mole per sec in the range 1300-2000 K; for the reaction CH3 + O2 yields CH3O + O, the rate constant was determined to be 2.4 times 10 to the 13th exp(-14,500/T) cu cm per mole per sec in the range 1200 to 1900 K.

  16. Mapped interpolation scheme for single-point energy corrections in reaction rate calculations and a critical evaluation of dual-level reaction path dynamics methods

    SciTech Connect

    Chuang, Y.Y.; Truhlar, D.G.; Corchado, J.C.

    1999-02-25

    Three procedures for incorporating higher level electronic structure data into reaction path dynamics calculations are tested. In one procedure, variational transition state theory with interpolated single-point energies, which is denoted VTST-ISPE, a few extra energies calculated with a higher level theory along the lower level reaction path are used to correct the classical energetic profile of the reaction. In the second procedure, denoted variational transition state theory with interpolated optimized corrections (VTST-IOC), which the authors introduced earlier, higher level corrections to energies, frequencies, and moments of inertia are based on stationary-point geometries reoptimized at a higher level than the reaction path was calculated. The third procedure, called interpolated optimized energies (IOE), is like IOC except it omits the frequency correction. Three hydrogen-transfer reactions, CH{sub 3} + H{prime}H {r_arrow} CH{sub 3}H{prime} + H (R1), OH + H{prime}H {r_arrow} HOH{prime} + H (R2), and OH + H{prime}CH{sub 3} {r_arrow} HOH{prime} + CH{sub 3} (R3), are used to test and validate the procedures by comparing their predictions to the reaction rate evaluated with a full variational transition state theory calculation including multidimensional tunneling (VTST/MT) at the higher level. The authors present a very efficient scheme for carrying out VTST-ISPE calculations, which are popular due to their lower computational cost. They also show, on the basis of calculations of the reactions R1--R3 with eight pairs of higher and lower levels, that VTST-IOC with higher level data only at stationary points is a more reliable dual-level procedure than VTST-ISPE with higher level energies all along the reaction path. Although the frequencies along the reaction path are not corrected in the IOE scheme, the results are still better than those from VTST-ISPE; this indicates the importance of optimizing the geometry at the highest possible level.

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

    EPA Science Inventory

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

  18. Improved Whitten-Rabinovitch Approximation for the Rice-Ramsperger-Kassel-Marcus Calculation of Unimolecular Reaction Rate Constants for Proteins

    E-print Network

    Kim, Myung Soo

    Improved Whitten-Rabinovitch Approximation for the Rice-Ramsperger-Kassel-Marcus Calculation of Unimolecular Reaction Rate Constants for Proteins Meiling Sun, Jeong Hee Moon, and Myung Soo Kim*, Department-Rabinovitch (WR) approximation used in the semi-classical calculation of the Rice- Ramsperger-Kassel-Marcus (RRKM

  19. Rate constant and mechanism of the reaction between Cl and CH{sub 3}OCl at 295 K

    SciTech Connect

    Carl, S.A.; Roehl, C.M.; Moortgat, G.K.; Crowley, J.N.; Mueller, C.M.

    1996-10-24

    The reaction between Cl atoms and CH{sub 3}OCl was investigated at 295 K in both air and N{sub 2} bath gases at total pressures between 100 and 850 Torr by the relative rate method. The rate constant of the title reaction was found to be a factor 1.07{+-}0.02 (2{sigma}) greater than that of Cl+C{sub 2}H{sub 6} at room temperature and independent of pressure between 100 and 750 Torr. This yields a rate constant of (6.1{+-}0.6)x10{sup -11} cm{sup 3} molecule{sup -1} s{sup -1}. The products of the reaction were detected by FTIR and UV absorption spectroscopy. Analysis of Cl{sub 2} and HCl products allowed branching ratios of 0.2{+-}0.1 for HCl+CH{sub 2}OCl formation and 0.8{+-}0.2 for Cl{sub 2}+CH{sub 3}O formation to be determined. The high rate constant implies that reaction with Cl atoms is an important loss process for CH{sub 3}OCl in the polar stratosphere. 37 refs., 9 figs., 3 tabs.

  20. 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.

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

    SciTech Connect

    McAuliffe, J.J. ); Perry, S.B. ); Brooks, E.E. ); Ingwall, J.S. Harvard Medical School, Boston, MA )

    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 data 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.

  2. Water clusters on graphite: methodology for quantum chemical a priori prediction of reaction rate constants.

    PubMed

    Xu, S; Irle, S; Musaev, D G; Lin, M C

    2005-10-27

    The properties, interactions, and reactions of cyclic water clusters (H(2)O)(n=1-5) on model systems for a graphite surface have been studied using pure B3LYP, dispersion-augmented density functional tight binding (DFTB-D), and integrated ONIOM(B3LYP:DFTB-D) methods. Coronene C(24)H(12) as well as polycircumcoronenes C(96)H(24) and C(216)H(36) in monolayer, bilayer, and trilayer arrangements were used as model systems to simulate ABA bulk graphite. Structures, binding energies, and vibrational frequencies of water clusters on mono- and bilayer graphite models have been calculated, and structural changes and frequency shifts due to the water cluster-graphite interactions are discussed. ONIOM(B3LYP:DFTB-D) with coronene and water in the high level and C(96)H(24) in the low level mimics the effect of extended graphite pi-conjugation on the water-graphite interaction very reasonably and suggests that water clusters only weakly interact with graphite surfaces, as suggested by the fact that water is an excellent graphite lubricant. We use the ONIOM(B3LYP:DFTB-D) method to predict rate constants for model pathways of water dissociative adsorption on graphite. Quantum chemical molecular dynamics (QM/MD) simulations of water clusters and water addition products on the C(96)H(24) graphite model are presented using the DFTB-D method. A three-stage strategy is devised for a priori investigations of high temperature corrosion processes of graphite surfaces due to interaction with water molecules and fragments. PMID:16866408

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

    USGS Publications Warehouse

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

    2009-01-01

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

  4. A note on the quantum-tail effect on fusion reaction rate

    E-print Network

    Alexander L. Zubarev

    2008-05-28

    A study is made of the power-law tail effect in the quantum particle distribution over momentum on the nuclear fusion reactions. Our results do not support the idea of averaging the fusion reaction cross-section over the momentum distribution postulated and used in many publications.

  5. Charting an Alternate Pathway to Reaction Orders and Rate Laws in Introductory Chemistry Courses

    ERIC Educational Resources Information Center

    Rushton, Gregory T.; Criswell, Brett A.; McAllister, Nicole D.; Polizzi, Samuel J.; Moore, Lamesha A.; Pierre, Michelle S.

    2014-01-01

    Reaction kinetics is an axiomatic topic in chemistry that is often addressed as early as the high school course and serves as the foundation for more sophisticated conversations in college-level organic, physical, and biological chemistry courses. Despite the fundamental nature of reaction kinetics, students can struggle with transforming their…

  6. An Interactive Classroom Activity Demonstrating Reaction Mechanisms and Rate-Determining Steps

    ERIC Educational Resources Information Center

    Jennings, Laura D.; Keller, Steven W.

    2005-01-01

    An interactive classroom activity that includes two-step reaction of unwrapping and eating chocolate candies is described which brings not only the reaction intermediate, but also the reactants and products into macroscopic view. The qualitative activation barriers of both steps can be adjusted independently.

  7. Quantum dynamics of the H+CH4-->H2+CH3 reaction in curvilinear coordinates: full-dimensional and reduced dimensional calculations of reaction rates.

    PubMed

    Schiffel, Gerd; Manthe, Uwe

    2010-02-28

    Full-dimensional quantum dynamics calculations for the H+CH(4)-->H(2)+CH(3) reaction using curvilinear coordinates are presented. A curvilinear coordinate system to describe reactions of the type X+YCH(3)-->XY+CH(3) is developed which facilitates efficient calculations using the multiconfigurational time-dependent Hartree (MCTDH) approach. To describe the bending motion of the X and Y atoms relative to the axis defined by the CH(3) fragment, coordinates based on stereographic projection are introduced. These coordinates yield a kinetic energy operator free of singularities within the dynamically relevant region. Employing this curvilinear coordinate system, full-dimensional and reduced dimensional MCTDH calculations study the cumulative reaction probability (for J=0) and the thermal rate constant for the H+CH(4) reaction on the Jordan-Gilbert potential energy surface [J. Chem. Phys. 102, 5669 (1995)]. The full-dimensional results agree very well with previous full-dimensional MCTDH results which used transition state based normal coordinates. The results of our eight-dimensional (8D) calculations are in reasonable agreement with the full-dimensional ones. They deviate significantly from older 8D results of Zhang et al. [J. Chem. Phys. 127, 234213 (2007)] but agree well with more recent results from the same group. PMID:20192286

  8. Quantum dynamics of the H+CH4-->H2+CH3 reaction in curvilinear coordinates: Full-dimensional and reduced dimensional calculations of reaction rates

    NASA Astrophysics Data System (ADS)

    Schiffel, Gerd; Manthe, Uwe

    2010-02-01

    Full-dimensional quantum dynamics calculations for the H+CH4?H2+CH3 reaction using curvilinear coordinates are presented. A curvilinear coordinate system to describe reactions of the type X +YCH3?XY+CH3 is developed which facilitates efficient calculations using the multiconfigurational time-dependent Hartree (MCTDH) approach. To describe the bending motion of the X and Y atoms relative to the axis defined by the CH3 fragment, coordinates based on stereographic projection are introduced. These coordinates yield a kinetic energy operator free of singularities within the dynamically relevant region. Employing this curvilinear coordinate system, full-dimensional and reduced dimensional MCTDH calculations study the cumulative reaction probability (for J =0) and the thermal rate constant for the H+CH4 reaction on the Jordan-Gilbert potential energy surface [J. Chem. Phys. 102, 5669 (1995)]. The full-dimensional results agree very well with previous full-dimensional MCTDH results which used transition state based normal coordinates. The results of our eight-dimensional (8D) calculations are in reasonable agreement with the full-dimensional ones. They deviate significantly from older 8D results of Zhang et al. [J. Chem. Phys. 127, 234213 (2007)] but agree well with more recent results from the same group.

  9. EFFECTS OF REACTION PARAMETERS ON ELECTROCHEMICAL DECHLORINATION OF TRICHLOROETHYLENE RATE AND BY-PRODUCTS

    EPA Science Inventory

    Trichloroethylene (TCE) was electrochemically dechlorinated in aqueous environments using granular graphite cathode in a mixed reactor. Effects of pH, current, electrolyte type, and flow rate on TCE dechlorination rate were evaluated. TCE dechlorination rate constant and gas prod...

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

    PubMed

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

    2015-11-12

    The sensitivity of kinetic observables is analyzed using a newly developed sum over histories representation of chemical kinetics. In the sum over histories representation, the concentrations of the chemical species are decomposed into the sum of probabilities for chemical pathways that follow molecules from reactants to products or intermediates. Unlike static flux methods for reaction path analysis, the sum over histories approach includes the explicit time dependence of the pathway probabilities. Using the sum over histories representation, the sensitivity of an observable with respect to a kinetic parameter such as a rate coefficient is then analyzed in terms of how that parameter affects the chemical pathway probabilities. The method is illustrated for species concentration target functions in H2 combustion where the rate coefficients are allowed to vary over their associated uncertainty ranges. It is found that large sensitivities are often associated with rate limiting steps along important chemical pathways or by reactions that control the branching of reactive flux. PMID:26493932

  11. 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.

  12. Quantum wave-packet dynamics of H+HLi scattering: Reaction cross section and thermal rate constant

    NASA Astrophysics Data System (ADS)

    Padmanaban, R.; Mahapatra, S.

    2004-10-01

    The channel specific and initial state-selected reaction cross section and temperature-dependent rate constant for the title system is calculated with the aid of a time-dependent wave-packet approach and using the ab initio potential energy surface of Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)]. All partial-wave contributions up to the total angular momentum J=74 are explicitly calculated within the coupled states (CS) approximation. Companion calculations are also carried out employing the standard as well as the uniform J-shifting (JS) approximation. The overall variation of reaction cross sections corresponds well to the behavior of a barrierless reaction. The hydrogen exchange channel yielding HLi+H products is seen to be more favored over the HLi depletion channel yielding Li+H2 products at low and moderate collision energies. Sharp resonance features are observed in the cross-section results for the HLi depletion channel at low energies. Resonance features in the reaction cross sections average out with various partial-wave contributions, when compared to the same observed in the individual reaction probability curve. Except near the onset of the reaction, the vibrational and rotational excitation of the reagent HLi, in general, does not dramatically influence the reactivity of either channel. The thermal rate constants calculated up to 4000 K show nearly Arrhenius type behavior. The rate constant decreases with vibrational excitation of the reagent HLi, indicating that the cold HLi molecules are efficiently depleted in the reactive encounter with H at relatively low temperatures. The results obtained from the JS approximation are found to agree well qualitatively with the CS results.

  13. The effect of nuclear reaction rates and convective mixing on the evolution of a 6M{sub ?} star

    SciTech Connect

    Halabi, Ghina M.

    2014-05-09

    We present the evolution of a 6M{sub ?} star, of solar-like initial metallicity, and investigate the effects of key nuclear reaction rates, as well as the treatment of the convective mixing on its evolution along the Cepheid instability strip. In particular, we study the effect of recent estimates of the {sup 14}N(p,?){sup 15}O reaction on the formation and extension of the blue loop during core helium burning. We also investigate the effects induced on this blue loop by the adoption of non-standard convective mixing prescriptions, as well as the implications of modifying the Mixing Length Theory.

  14. A survey of the reaction rate constants for the thermal dissociation and recombination of nitrogen and oxygen

    NASA Technical Reports Server (NTRS)

    Marraffa, Lionel; Dulikravich, George S.; Keeney, Timothy C.; Deiwert, George S.

    1988-01-01

    The objective of the present report is to survey the various values of forward and backward reaction rate constants used by investigators in the field of high-temperature (T greater than 2000 K) gas reactions involving nitrogen and oxygen only. The objective is to find those values that correlate well so that they can be used for the studies of hypersonic flow and supersonic combustion with reasonable confidence. Relatively good agreement among these various values is observed for temperatures lower than 10,000 K.

  15. Measurement of the 17 O(p,?)18F reaction rate at astrophysically relevant energies

    NASA Astrophysics Data System (ADS)

    Hager, U.; Buchmann, L.; Davids, B.; Fallis, J.; Fulton, B. R.; Galinski, N.; Greife, U.; Hutcheon, D. A.; Ottewell, D.; Rojas, A.; Ruiz, C.; Setoodehnia, K.

    2012-03-01

    The 17O(p,?)18F reaction plays an important role in hydrogen-burning nucleosynthesis. Conflicting values for the low-energy behavior of its cross section exist in the literature. We present direct measurements of the astrophysical S factor of the 17O(p,?)18F reaction at center-of-mass energies between 250 and 500 keV. These measurements were conducted in inverse kinematics at the DRAGON recoil separator.

  16. Standard Test Method for Determining Thermal Neutron Reaction Rates and Thermal Neutron Fluence Rates by Radioactivation Techniques

    E-print Network

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 The purpose of this test method is to define a general procedure for determining an unknown thermal-neutron fluence rate by neutron activation techniques. It is not practicable to describe completely a technique applicable to the large number of experimental situations that require the measurement of a thermal-neutron fluence rate. Therefore, this method is presented so that the user may adapt to his particular situation the fundamental procedures of the following techniques. 1.1.1 Radiometric counting technique using pure cobalt, pure gold, pure indium, cobalt-aluminum, alloy, gold-aluminum alloy, or indium-aluminum alloy. 1.1.2 Standard comparison technique using pure gold, or gold-aluminum alloy, and 1.1.3 Secondary standard comparison techniques using pure indium, indium-aluminum alloy, pure dysprosium, or dysprosium-aluminum alloy. 1.2 The techniques presented are limited to measurements at room temperatures. However, special problems when making thermal-neutron fluence rate measurements in high-...

  17. Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth

    DOE PAGESBeta

    Sutter, Eli A.; Sutter, Peter W.

    2014-11-19

    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 Pdmore »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]. In addition, 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 zero-valent metal atoms in solution.« less

  18. Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth

    SciTech Connect

    Sutter, Eli A.; Sutter, Peter W.

    2014-11-19

    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]. In addition, 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 zero-valent metal atoms in solution.

  19. 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 mechanism for ring-retaining product channels is proposed to justify the observed reaction products. The global tropospheric lifetimes estimated from the reported OH- and Cl-rate coefficients show that the main removal path for the investigated methylcyclohexanes is the reaction with OH radicals. But in marine environments, after sunrise, Cl reactions become more important in the tropospheric degradation. Thus, the estimated lifetimes range from 16 to 24 h for the reactions of the OH radical (calculated with [OH]?=?10(6) atoms cm(-3)) and around 7-8 h in the reactions with Cl atoms in marine environments (calculated with [Cl]?=?1.3?×?10(5) atoms cm(-3)). The reaction of Cl atoms and OH radicals and methylcylohexanes can proceed by H abstraction from the different positions. PMID:24788931

  20. Hydrogenation of O and OH on Pt(111): A comparison between the reaction rates of the first and the second hydrogen addition steps

    SciTech Connect

    Näslund, L.-Å.

    2014-03-14

    The formation of water through hydrogenation of oxygen on platinum occurs at a surprisingly low reaction rate. The reaction rate limited process for this catalytic reaction is, however, yet to be settled. In the present work, the reaction rates of the first and the second hydrogen addition steps are compared when hydrogen is obtained through intense synchrotron radiation that induces proton production in a water overlayer on top of the adsorbed oxygen species. A substantial amount of the produced hydrogen diffuses to the platinum surface and promotes water formation at the two starting conditions O/Pt(111) and (H{sub 2}O+OH)/Pt(111). The comparison shows no significant difference in the reaction rate between the first and the second hydrogen addition steps, which indicates that the rate determining process of the water formation from oxygen on Pt(111) is neither the first nor the second H addition step or, alternatively, that both H addition steps exert rate control.

  1. THE EFFECTS OF THERMONUCLEAR REACTION RATE VARIATIONS ON {sup 26}Al PRODUCTION IN MASSIVE STARS: A SENSITIVITY STUDY

    SciTech Connect

    Iliadis, Christian; Champagne, Art; Chieffi, Alessandro; Limongi, Marco E-mail: aec@tunl.duke.edu E-mail: marco@oa-roma.inaf.it

    2011-03-15

    We investigate the effects of thermonuclear reaction rate variations on {sup 26}Al production in massive stars. The dominant production sites in such events were recently investigated by using stellar model calculations: explosive neon-carbon burning, convective shell carbon burning, and convective core hydrogen burning. Post-processing nucleosynthesis calculations are performed for each of these sites by adopting temperature-density-time profiles from recent stellar evolution models. For each profile, we individually multiplied the rates of all relevant reactions by factors of 10, 2, 0.5, and 0.1, and analyzed the resulting abundance changes of {sup 26}Al. In total, we performed {approx}900 nuclear reaction network calculations. Our simulations are based on a next-generation nuclear physics library, called STARLIB, which contains a recent evaluation of Monte Carlo reaction rates. Particular attention is paid to quantifying the rate uncertainties of those reactions that most sensitively influence {sup 26}Al production. For stellar modelers our results indicate to what degree predictions of {sup 26}Al nucleosynthesis depend on currently uncertain nuclear physics input, while for nuclear experimentalists our results represent a guide for future measurements. We also investigate equilibration effects of {sup 26}Al. In all previous massive star investigations, either a single species or two species of {sup 26}Al were taken into account, depending on whether thermal equilibrium was achieved or not. These are two extreme assumptions, and in a hot stellar plasma the ground and isomeric states may communicate via {gamma}-ray transitions involving higher-lying {sup 26}Al levels. We tabulate the results of our reaction rate sensitivity study for each of the three distinct massive star sites referred to above. It is found that several current reaction rate uncertainties influence the production of {sup 26}Al. Particularly important reactions are {sup 26}Al(n,p){sup 26}Mg, {sup 25}Mg({alpha},n){sup 28}Si, {sup 24}Mg(n,{gamma}){sup 25}Mg, and {sup 23}Na({alpha},p){sup 26}Mg. These reactions should be prime targets for future measurements. Overall, we estimate that the nuclear physics uncertainty of the {sup 26}Al yield predicted by the massive star models explored here amounts to about a factor of three. We also find that taking the equilibration of {sup 26}Al levels explicitly into account in any of the massive star sites investigated here has only minor effects on the predicted {sup 26}Al yields. Furthermore, we provide for the interested reader detailed comments regarding the current status of certain reactions, including {sup 12}C({sup 12}C,n){sup 23}Mg, {sup 23}Na({alpha},p){sup 26}Mg, {sup 25}Mg({alpha},n){sup 28}Si, {sup 26}Al {sup m}(p,{gamma}){sup 27}Si, {sup 26}Al(n,p){sup 26}Mg, and {sup 26}Al(n,{alpha}){sup 23}Na.

  2. A year in the life of an aluminous metapelite xenolith--The role of heating rates, reaction overstep, H2O retention and melt loss

    E-print Network

    Zeng, Ning

    by continual prograde reaction and loss to the margins of H2O liberated by subsolidus dehydration reactions temperatures, an effect exacerbated by the effects of melt loss. Whereas corundum growth occurred rates are generally slow, H2O produced by dehydration reactions is generally assumed to be lost

  3. Muonium Addition Reactions and Kinetic Isotope Effects in the Gas Phase: k? Rate Constants for Mu + C2H2.

    PubMed

    Arseneau, Donald J; Garner, David M; Reid, Ivan D; Fleming, Donald G

    2015-07-16

    The kinetics of the addition reaction of muonium (Mu) to acetylene have been studied in the gas phase at N2 moderator pressures mainly from ?800 to 1000 Torr and over the temperature range from 168 to 446 K, but also down to 200 Torr at 168 K and over a much higher range of pressures, from 10 to 44 bar at 295 K, demonstrating pressure-independent rate constants, kMu(T). Even at 200 Torr moderator pressure, the kinetics for Mu + C2H2 addition behave as if effectively in the high-pressure limit, giving k? = kMu due to depolarization of the muon spin in the MuC2H2 radical formed in the addition step. The rate constants kMu(T) exhibit modest Arrhenius curvature over the range of measured temperatures. Comparisons with data and with calculations for the corresponding H(D) + C2H2 addition reactions reveal a much faster rate for the Mu reaction at the lowest temperatures, by 2 orders of magnitude, in accord with the propensity of Mu to undergo quantum tunneling. Moreover, isotopic atom exchange, which contributes in a major way to the analogous D atom reaction, forming C2HD + H, is expected to be unimportant in the case of Mu addition, a consequence of the much higher zero-point energy and hence weaker C-Mu bond that would form, meaning that the present report of the Mu + C2H2 reaction is effectively the only experimental study of kinetic isotope effects in the high-pressure limit for H-atom addition to acetylene. PMID:25664674

  4. 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.

  5. Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

    Absolute rate constants for the reaction OH + H2CO have been measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique. The results were independent of variations in forbidden H2CO, total pressure of forbidden Ar and flash intensity (i.e., initial forbidden OH). The rate constant was found to be invariant with temperature in this range, the best representation being k1 = (1.05 + or - 0.11) x 10 to the -11th cu cm/molecule sec where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k1. The reaction is also discussed from a theoretical point of view.

  6. Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

    Absolute rate constants for the reaction OH ? H2CO measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique are given. The results are independent of variations in H2CO concentration, total pressure Ar concentration, and flash intensity (i.e., initial OH concentration). The rate constant is found to be invariant with temperature in this range, the best representation being k sub 1 = (1.05 ? or - 0.11) x 10 to the 11th power cu cm molecule(-1) s(-1) where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k sub 1. The reaction is also discussed from a theoretical point of view.

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

    NASA Technical Reports Server (NTRS)

    Goldstein, D.; Magnotti, F.; Chinitz, W.

    1983-01-01

    Reaction rates in turbulent, reacting flows are reviewed. Assumed probability density functions (pdf) modeling of reaction rates is being investigated in relation to a three variable pdf employing a 'most likely pdf' model. Chemical kinetic mechanisms treating hydrogen air combustion is studied. Perfectly stirred reactor modeling of flame stabilizing recirculation regions was used to investigate the stable flame regions for silane, hydrogen, methane, and propane, and for certain mixtures thereof. It is concluded that in general, silane can be counted upon to stabilize flames only when the overall fuel air ratio is close to or greater than unity. For lean flames, silane may tend to destabilize the flame. Other factors favoring stable flames are high initial reactant temperatures and system pressure.

  8. Measurement and analysis of the 238U(n, 2n) reaction rate in depleted uranium/polyethylene shells

    NASA Astrophysics Data System (ADS)

    Yan, Xiao-Song; Liu, Rong; Lu, Xin-Xin; Jiang, Li; Wen, Zhong-Wei; Han, Zi-Jie

    2012-07-01

    In order to check the conceptual design of the subcritical blanket in a fusion-fission hybrid reactor, a depleted uranium/polyethylene simulation device with alternate shells has been established. The measurement of the 238U(n, 2n) reaction rate was carried out using an activation technique, by measuring the 208 keV ? rays emitted from 237U. The self-absorption of depleted uranium foils with different thicknesses was experimentally corrected. The distribution of the 238U(n, 2n) reaction rate at 90° to the incident D+ beam was obtained, with uncertainty between 5.3% and 6.0%. The experiment was analyzed using MCNP5 code with the ENDF/BVI library, and the calculated results are all about 5% higher than the measured results.

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

    E-print Network

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

    2011-07-22

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

  10. An extensive study of O(1D) reaction rate coefficients for key ozone depleting substances and greenhouse gases

    NASA Astrophysics Data System (ADS)

    Burkholder, J. B.; Baasandorj, M.; Fleming, E. L.; Jackman, C. H.

    2012-12-01

    A key stratospheric loss process for ozone depleting substances (ODSs) and greenhouse gases (GHGs) is their gas-phase reaction with electronically excited oxygen atoms, O(1D). Although numerous O(1D) reactions have been studied in the past, large uncertainties in the recommended rate coefficients and reactive yields, i.e., loss of ODS or GHG, for use in atmospheric modeling still exist for a number of key compounds. Our understanding of the coupling of atmospheric chemistry and climate-change requires the most accurate reaction rate coefficient data to be used in climate-change model calculations. In this presentation, results from an extensive laboratory study of the total reaction rate coefficient, corresponding to loss of O(1D), and reactive rate coefficients, corresponding to the loss of the reactant compound, will be presented for the ODSs: CFCl3 (CFC-11), CF2Cl2 (CFC-12), CFCl2CF2Cl (CFC-113), CF2ClCF2Cl (CFC-114), CF3CF2Cl (CFC-115), HClCF2 (HCFC-22), CH3CClF2 (HCFC-142b); GHGs: CHF3 (HFC-23), CHF2CF3 (HFC-125), CF3CHCF3 (HFC-227ea), and CF3CH3 (HFC-143a); and the persistent (long-lived) GHGs: NF3, SF5CF3, C2F6, c-C4F8, n-C5F12, and n-C6F14. The results from this work will be compared with results from previous studies and discrepancies discussed along with the atmospheric implications of the improved kinetic dataset on the atmospheric lifetimes of these compounds.

  11. Rates and temperature dependences of the reaction of OH with isoprene, its oxidation products, and selected terpenes

    SciTech Connect

    Kleindienst, T.E.; Harris, G.W.; Pitts, J.N. Jr.

    1982-12-01

    Absolute rate constants determined by using the flash photolysis-resonance fluorescence technique are reported for the reactions of hydroxyl radicals with isoprene, ..cap alpha.., and ..beta..-pinene, methyl vinyl ketone, and methacrolein in the temperature range 297-424 K, and with methylglyoxal at 297 K. These results contribute to a more quantitative understanding of the tropospheric fate of gas-phase biomass-related organics and serve as input to models of the chemistry of the natural troposphere.

  12. Absolute rate parameters for the reaction of ground state atomic oxygen with carbonyl sulfide. [using O(3P) monitoring

    NASA Technical Reports Server (NTRS)

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

    1974-01-01

    The rate parameters for the reaction of O(3P) with carbonyl sulfide, O(3P) + OCS yields CO + SO have been determined directly by monitoring O(3P) using the flash photolysis-resonance fluorescence technique. The value for k sub 1 was measured over a temperature range of 263 - 502 K and the data were fitted to an Arrhenuis expression with good linearity.

  13. Effects of argon flow rate and reaction temperature on synthesizing single-walled carbon nanotubes from ethanol

    NASA Astrophysics Data System (ADS)

    Liu, QiXin; Ouyang, Yu; Zhang, LuYin; Xu, Yan; Fang, Yan

    2009-06-01

    The effects of argon (Ar) flow rate and the reaction temperature on synthesizing single-walled carbon nanotubes (SWCNTs) by means of the catalytic chemical vapor deposition (CCVD) method from ethanol over Fe-Mo/MgO catalyst have been investigated. The fluidized-bed was applied as the reactor. Ethanol vapor was introduced into the fluidized-bed from a temperature-controlled bubbler by the flow of carrier gas (Ar). The as-grown SWCNTs were characterized using Raman spectroscopic and transmission electron microscopy (TEM). The SWCNTs sample, which was synthesized by this equipment at 950 °C with the Ar flow rate 150 sccm, exhibited high quality.

  14. EFFECTS OF PORE STRUCTURE CHANGE AND MULTI-SCALE HETEROGENEITY ON CONTAMINANT TRANSPORT AND REACTION RATE UPSCALING

    SciTech Connect

    Lindquist, W. Brent; Jones, Keith W.; Um, Wooyong; Rockhold, mark; Peters, Catherine A.; Celia, Michael A.

    2013-02-15

    This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site ? specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE’s legacy waste problems. We established three key issues of reactive flow upscaling, and organized this project in three corresponding thrust areas. 1) Reactive flow experiments. The combination of mineral dissolution and precipitation alters pore network structure and the subsequent flow velocities, thereby creating a complex interaction between reaction and transport. To examine this phenomenon, we conducted controlled laboratory experimentation using reactive flow-through columns. ? Results and Key Findings: Four reactive column experiments (S1, S3, S4, S5) have been completed in which simulated tank waste leachage (STWL) was reacted with pure quartz sand, with and without Aluminum. The STWL is a caustic solution that dissolves quartz. Because Al is a necessary element in the formation of secondary mineral precipitates (cancrinite), conducting experiments under conditions with and without Al allowed us to experimentally separate the conditions that lead to quartz dissolution from the conditions that lead to quartz dissolution plus cancrinite precipitation. Consistent with our expectations, in the experiments without Al, there was a substantial reduction in volume of the solid matrix. With Al there was a net increase in the volume of the solid matrix. The rate and extent of reaction was found to increase with temperature. These results demonstrate a successful effort to identify conditions that lead to increases and conditions that lead to decreases in solid matrix volume due to reactions of caustic tank wastes with quartz sands. In addition, we have begun to work with slightly larger, intermediate-scale columns packed with Hanford natural sediments and quartz. Similar dissolution and precipitation were observed in these colums. The measurements are being interpreted with reactive transport modeling using STOMP; preliminary observations are reported here. 2) Multi-Scale Imaging and Analysis. Mineral dissolution and precipitation rates within a porous medium will be different in different pores due to natural heterogeneity and the heterogeneity that is created from the reactions themselves. We used a combination of X-ray computed microtomography, backscattered electron and energy dispersive X-ray spectroscopy combined with computational image analysis to quantify pore structure, mineral distribution, structure changes and fluid-air and fluid-grain interfaces. ? Results and Key Findings: Three of the columns from the reactive flow experiments at PNNL (S1, S3, S4) were imaged using 3D X-ray computed microtomography (XCMT) at BNL and analyzed using 3DMA-rock at SUNY Stony Brook. The imaging results support the mass balance findings reported by Dr. Um’s group, regarding the substantial dissolution of quartz in column S1. An important observation is that of grain movement accompanying dissolution in the unconsolidated media. The resultant movement

  15. Enzymatic hydrolysis of nylons: quantification of the reaction rate of nylon hydrolase for thin-layered nylons.

    PubMed

    Nagai, Keisuke; Iida, Kazuki; Shimizu, Kimiaki; Kinugasa, Ryo; Izumi, Motoki; Kato, Dai-Ichiro; Takeo, Masahiro; Mochiji, Kozo; Negoro, Seiji

    2014-10-01

    Nylon hydrolase degrades various aliphatic nylons, including nylon-6 and nylon-66. We synthesized a nylon-66 copolymer (M w?=?22,900, M n?=?7,400), in which a part of an adipoyl unit (32 % molar ratio) of nylon-66 was replaced with a succinyl unit by interfacial polymerization. To quantify the reaction rate of the enzymatic hydrolysis of nylons at the surface of solid polymers, we prepared a thin layer of nylons on the bottom surface of each well in a polystyrene-based micro-assay plate. The thickness of the nylon layer was monitored by imaging analysis of the photographic data. More than 99 % of the copolymer with thicknesses of 260 nm (approximately 600 layers of polymer strands) were converted to water-soluble oligomers by nylon hydrolase (3 mg enzyme ml(-1)) at 30 °C within 60 h. These results were further confirmed by TLC analysis of the reaction products and by assay of liberated amino groups in the soluble fractions. The degradation rate of the thin-layered nylon-6 was similarly analyzed. We demonstrate that this assay enables a quantitative evaluation of the reaction rate of hydrolysis at the interface between the solid and aqueous phases and a quantitative comparison of the degradability for various polyamides. PMID:24962117

  16. Verification of Radicals Formation in Ethanol-Water Mixture Based Solution Plasma and Their Relation to the Rate of Reaction.

    PubMed

    Sudare, Tomohito; Ueno, Tomonaga; Watthanaphanit, Anyarat; Saito, Nagahiro

    2015-12-01

    Our previous research demonstrated that using ethanol-water mixture as a liquid medium for the synthesis of gold nanoparticles by the solution plasma process (SPP) could lead to an increment of the reaction rate of ?35.2 times faster than that in pure water. This drastic change was observed when a small amount of ethanol, that is, at an ethanol mole fraction (?ethanol) of 0.089, was added in the system. After this composition, the reaction rate decreased continuously. To better understand what happens in the ethanol-water mixture-based SPP, in this study, effect of the ethanol content on the radical formation in the system was verified. We focused on detecting the magnetic resonance of electronic spins using electron spin resonance spectroscopy to determine the type and quantity of the generated radicals at each ?ethanol. Results indicated that ethanol radicals were generated in the ethanol-water mixtures and exhibited maximum quantity at the xethanol of 0.089. Relationship between the ethanol radical yield and the rate of reaction, along with possible mechanism responsible for the observed phenomenon, is discussed in this paper. PMID:26505749

  17. Variations of boundary reaction rate and particle size on the diffusion-induced stress in a phase separating electrode

    SciTech Connect

    Zhang, Lei; He, Linghui; Ni, Yong; Song, Yicheng

    2014-10-14

    In contrast to the case of single-phase delithiation wherein faster discharging leads to higher diffusion-induced stress (DIS), this paper reports nonmonotonous dependency of the boundary reaction rate on the DIS in nanosized spherical electrode accompanying phase separation. It is attributed to a transition from two-phase to single-phase delithiation driven by increase of the boundary reaction rate leading to narrowing and vanishing of the miscibility gap in a range of the particle size. The profiles of lithium concentration and the DIS are identified during the transition based on a continuum model. The resultant maximum DIS first decreases in the region of two-phase delithiation and later returns to increase in the region of single-phase delithiation with the increase of the boundary reaction rate. A map for the failure behavior in the spherical electrode particle is constructed based on the Tresca failure criterion. These results indicate that the failure caused by the DIS can be avoided by appropriate selection of the said parameters in such electrodes.

  18. The Treatment of NonInteger Exponents in Reaction Rate Expressions

    E-print Network

    Bath, University of

    (¸)]; (1) dx 2 d¸ = JH [w(¸) \\Gamma x 2 (¸)]; (2) 0 = JH [x 2 (¸) \\Gamma w(¸)] \\Gamma \\GammaD c expffl c (w as the reaction stops when ff W = 0 and ff W holds this value throughout the remainder of the combustor. JD JH

  19. Aqueous complexation reactions governing the rate and extent of biogeochemical U(VI) reduction

    SciTech Connect

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

    2006-06-01

    The proposed research will elucidate the principal biogeochemical reactions that govern the concentration, chemical speciation, and reactivity of the redox-sensitive contaminant uranium. The results will provide an improved understanding and predictive capability of the mechanisms that govern the biogeochemical reduction of uranium in subsurface environments.

  20. Evaluating effective reaction rates of kinetically driven solutes in large-scale, statistically anisotropic media: Human health risk implications

    NASA Astrophysics Data System (ADS)

    Siirila, Erica R.; Maxwell, Reed M.

    2012-04-01

    The interplay between regions of high and low hydraulic conductivity, degree of aquifer stratification, and rate-dependent geochemical reactions in heterogeneous flow fields is investigated, focusing on impacts of kinetic sorption and local dispersion on plume retardation and channeling. Human health risk is used as an endpoint for comparison via a nested Monte Carlo scheme, explicitly considering joint uncertainty and variability. Kinetic sorption is simulated with finely resolved, large-scale domains to identify hydrogeologic conditions where reactions are either rate limited (nonreactive), in equilibrium (linear equilibrium assumption is appropriate), or are sensitive to time-dependent kinetic reactions. By utilizing stochastic ensembles, effective equilibrium conditions are examined, in addition to parameter interplay. In particular, the effects of preferential flow pathways and solute mixing at the field-scale (marcrodispersion) and subgrid (local dispersion, LD) are examined for varying degrees of stratification and regional groundwater velocities (v). Results show effective reaction rates of kinetic ensembles with the inclusion of LD yield disequilibrium transport, even for averaged (or global) Damköholer numbers associated with equilibrium transport. Solute behavior includes an additive tailing effect, a retarded peak time, and results in an increased cancer risk. The inclusion of LD for nonreactive solutes in highly anisotropic media results in either induced solute retardation or acceleration, a new finding given that LD has previously been shown to affect only the concentration variance. The distribution, magnitude, and associated uncertainty of cancer risk are controlled by the up scaling of these small-scale processes, but are strongly dependent on v and the source term.

  1. The use of carbon monoxide/hydrogen burning velocities to examine the rate of the CO + OH reaction

    SciTech Connect

    McLean, I.C.; Smith, D.B.; Taylor, S.C.

    1994-12-31

    New measurements of burning velocity are reported for selected CO/H{sub 2} mixtures in air, to provide data for examining the rate of the CO + OH reaction. Burning velocities were obtained from measurements on constant-pressure expanding spherical flames. Flame speeds over the first 35 mm of travel were measured by high-speed schlieren cine photography and extrapolated to infinite radius, using a simple phenomenological model, to yield one-dimensional values. Experimental burning velocities were then compared with 1D computed values, obtained using full kinetics. Fuel mixtures of 95% CO + 5% H{sub 2} and 50% CO + 50 % H{sub 2} with air were studied across the stoichiometric range, along with stoichiometric mixtures with varying H{sub 2}/CO ratio. The 95 + 5 % mixture was the prime object of study, since computation revealed that burning velocities for this mixture had the greatest sensitivity to the CO + OH reaction. For the 95 + 5 % mixture, the maximum burning velocity was 0.65 {+-} 0.02 m/s at 51.7 % fuel; the stoichiometric value was 0.34 m/s. For the 50 + 50 % mixture, the corresponding velocities were 1.82 {+-} 0.06 (at 47.2 % fuel) and 1.20 m/s. Computed 1D burning velocities agreed well with experiment when the 1976 recommendation of Baulch et al. for the rate of the CO + OH reaction was used. A more recent recommendation gave values more than 20 % too high. Further computation revealed that the reaction exerts its influence on the burning velocity of these flames at low temperatures, in a relatively narrow region around 1,165 K. Use of different (artificially derived) rate expressions, but having a common value at 1,165 K, produced essentially the same burning velocities. Implications of this for flame chemistry are explored.

  2. Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

    SciTech Connect

    Koretsky, A.P.

    1984-08-01

    This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. Chronically implanted detection coils, employing a balanced matching configuration of capacitors in the tuned circuit, were used to obtain /sup 31/P NMR spectra from heart, kidney, and liver in situ. Gated spectra of heart obtained at systole and diastole and the effects of fructose on kidney and liver were studied. The ability to observe other nuclei using implanted coils is illustrated with /sup 39/K NMR spectra from kidney and muscle. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate (13 ..mu..mol/min/gm tissue) were compared to whole kidney oxygen consumption and Na/sup +/ reabsorption rates to derive ATP/O (0.8 to 1.7) and Na/sup +//ATP (4 to 10) values. The problems associated with ATP synthesis rate measurements in kidney, e.g., the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed.

  3. A Kinetic and Product Study of the Cl + HO2 Reaction

    NASA Technical Reports Server (NTRS)

    Hickson, Kevin M.; Keyser, Leon F.

    2005-01-01

    Absolute rate data and product branching ratios for the reactions Cl + HO2 to HCl + O2 (k1a) and Cl + HO2 to OH + ClO (k1b) have been measured from 226 to 336 K at a total pressure of 1 Torr of helium using the discharge flow resonance fluorescence technique coupled with infrared diode laser spectroscopy. For kinetic measurements, pseudo-first-order conditions were used with both reagents in excess in separate experiments. HO2 was produced by two methods: through the termolecular reaction of H atoms with O2 and also by the reaction of F atoms with H2O2. Cl atoms were produced by a microwave discharge of Cl2 in He. HO2 radicals were converted to OH radicals prior to detection by resonance fluorescence at 308 nm. Cl atoms were detected directly at 138 nm also by resonance fluorescence. Measurement of the consumption of HO2 in excess Cl yielded k1a and measurement of the consumption of Cl in excess HO2 yielded the total rate coefficient, k1. Values of k1a and k1 derived from kinetic experiments expressed in Arrhenius form are (1.6 +/- 0.2) x 10-11 exp[(249 +/- 34)/T] and (2.8 +/- 0.1) x 10-11 exp[(123 +/- 15)/T] cm3 molecule-1 s-1, respectively. As the expression for k1 is only weakly temperature dependent, we report a temperature-independent value of k1 = (4.5 +/- 0.4) x 10-11 cm3 molecule-1 s-1. Additionally, an Arrhenius expression for k1b can also be derived: k1b = (7.7 +/- 0.8) x 10-11 exp[-(708 +/- 29)/T] cm3 molecule-1 s-1. These expressions for k1a and k1b are valid for 226 K T 336 and 256 K T 296 K, respectively. The cited errors are at the level of a single standard deviation. For the product measurements, an excess of Cl was added to known concentrations of HO2 and the reaction was allowed to reach completion. HCl product concentrations were determined by IR absorption yielding the ratio k1a/k1 over the temperature range 236 K T 296 K. OH product concentrations were determined by resonance fluorescence giving rise to the ratio k1b/k1 over the temperature range 226 K T 336 K. Both of these ratios were subsequently converted to absolute numbers. Values of k1a and k1b from the product experiments expressed in Arrhenius form are (1.5 +/- 0.1) x 10-11 exp[(222 +/- 17)/T] and (10.6 +/- 1.5) x 10-11 exp[-(733 +/- 41)/T] cm3 molecule-1 s-1, respectively. These expressions for k1a and k1b are valid for 256 K T 296 and 226 K T 336 K, respectively. A combination of the kinetic and product data results in the following Arrhenius expressions for k1a and k1b of (1.4 +/- 0.3) x 10-11 exp[(269 +/- 58)/T] and (12.7 +/- 4.1) x 10-11 exp[-(801 +/- 94)/T] cm3 molecule-1 s-1, respectively. Numerical simulations were used to check for interferences from secondary chemistry in both the kinetic and product experiments and also to quantify the losses incurred during the conversion process HO2 to OH for detection purposes.

  4. IWTS metal-water reaction rate evaluation (Fauske and Associates report 99-26)

    SciTech Connect

    DUNCAN, D.R.

    1999-07-29

    The report presents a thermal stability analysis of partially metallic particulate in two IWTS components, the knock out pot and settlers. Particulate in the knock out pot is thermally stable for combinations of average particle size and metal mass fraction which appear realistic. Particulate in the settlers is thermally stable when a realistic account of particle reactions over time, metal fraction, and size distribution is considered.

  5. Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L. J.

    1985-01-01

    In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.

  6. New Constraints on the 18F(p,alpha) 15O Rate in Novae from the (d,p) Reaction

    E-print Network

    R. L. Kozub; D. W. Bardayan; J. C. Batchelder; J. C. Blackmon; C. R. Brune; A. E. Champagne; J. A. Cizewski; T. Davinson; U. Greife; C. J. Gross; C. C. Jewett; R. J. Livesay; Z. Ma; B. H. Moazen; C. D. Nesaraja; L. Sahin; J. P. Scott; D. Shapira; M. S. Smith; J. S. Thomas; P. J. Woods

    2005-01-11

    The degree to which the (p,gamma) and (p,alpha) reactions destroy 18F at temperatures 1-4x10^8 K is important for understanding the synthesis of nuclei in nova explosions and for using the long-lived radionuclide 18F, a target of gamma-ray astronomy, as a diagnostic of nova mechanisms. The reactions are dominated by low-lying proton resonances near the 18F+p threshold (E_x=6.411 MeV in 19Ne). To gain further information about these resonances, we have used a radioactive 18F beam from the Holifield Radioactive Ion Beam Facility to selectively populate corresponding mirror states in 19F via the inverse d(18F,p)19F neutron transfer reaction. Neutron spectroscopic factors were measured for states in 19F in the excitation energy range 0-9 MeV. Widths for corresponding proton resonances in 19Ne were calculated using a Woods-Saxon potential. The results imply significantly lower 18F(p,gamma)19Ne and 18F(p,alpha)15O reaction rates than reported previously, thereby increasing the prospect of observing the 511-keV annihilation radiation associated with the decay of 18F in the ashes ejected from novae.

  7. Analysis of progress curves for enzyme-catalysed reactions. Automatic construction of computer programs for fitting integrated rate equations.

    PubMed Central

    Duggleby, R G; Wood, C

    1989-01-01

    The computer analysis of progress curves for enzyme-catalysed reactions involves a series of mathematical and computational tasks. The three most daunting of these are the derivation of an integrated rate equation, solving this equation so that the amount of product formed by the reaction at any time can be calculated, and incorporating this solution into a non-linear-regression computer program. This paper describes the basis of a computer program that greatly simplifies the problem. The proposed mechanism is specified in the familiar kinetic constant form, which is automatically translated into a program capable of fitting this mechanism to a series of experimental progress curves. The approach is illustrated for a reversible reaction with one substrate and one product, and tested with some data obtained for the fumarase reaction. A copy of the program has been deposited as Supplementary Publication SUP 50148 (13 pages) at the British Library Document Supply Centre, Boston Spa, Wetherby, West Yorkshire LS23 7BQ, U.K., from whom copies can be obtained on the terms indicated in Biochem. J. (1989) 257, 5. PMID:2705990

  8. An investigation of the effect of pore scale flow on average geochemical reaction rates using direct numerical simulation

    SciTech Connect

    Molins, Sergi; Trebotich, David; Steefel, Carl; Shen, Chaopeng

    2012-03-30

    The scale-dependence of geochemical reaction rates hinders their use in continuum scale models intended for the interpretation and prediction of chemical fate and transport in subsurface environments such as those considered for geologic sequestration of CO{sub 2}. Processes that take place at the pore scale, especially those involving mass transport limitations to reactive surfaces, may contribute to the discrepancy commonly observed between laboratory-determined and continuum-scale or field rates. Here, the dependence of mineral dissolution rates on the pore structure of the porous media is investigated by means of pore scale modeling of flow and multicomponent reactive transport. The pore scale model is composed of high-performance simulation tools and algorithms for incompressible flow and conservative transport combined with a general-purpose multicomponent geochemical reaction code. The model performs direct numerical simulation of reactive transport based on an operator-splitting approach to coupling transport and reactions. The approach is validated with a Poiseuille flow single-pore experiment and verified with an equivalent 1-D continuum-scale model of a capillary tube packed with calcite spheres. Using the case of calcite dissolution as an example, the high-resolution model is used to demonstrate that nonuniformity in the flow field at the pore scale has the effect of decreasing the overall reactivity of the system, even when systems with identical reactive surface area are considered. The effect becomes more pronounced as the heterogeneity of the reactive grain packing increases, particularly where the flow slows sufficiently such that the solution approaches equilibrium locally and the average rate becomes transport-limited.

  9. An investigation of the effect of pore scale flow on average geochemical reaction rates using direct numerical simulation

    SciTech Connect

    Rafa, S. Molins; Trebotich, D.; Steefel, C. I.; Shen, C.

    2012-02-01

    The scale-dependence of geochemical reaction rates hinders their use in continuum scale models intended for the interpretation and prediction of chemical fate and transport in subsurface environments such as those considered for geologic sequestration of CO{sub 2}. Processes that take place at the pore scale, especially those involving mass transport limitations to reactive surfaces, may contribute to the discrepancy commonly observed between laboratory-determined and continuum-scale or field rates. Here, the dependence of mineral dissolution rates on the pore structure of the porous media is investigated by means of pore scale modeling of flow and multicomponent reactive transport. The pore scale model is comprised of high performance simulation tools and algorithms for incompressible flow and conservative transport combined with a general-purpose multicomponent geochemical reaction code. The model performs direct numerical simulation of reactive transport based on an operator-splitting approach to coupling transport and reactions. The approach is validated with a Poiseuille flow single-pore experiment and verified with an equivalent 1D continuum-scale model of a capillary tube packed with calcite spheres. Using the case of calcite dissolution as an example, the high resolution model is used to demonstrate that non-uniformity in the flow field at the pore scale has the effect of decreasing the overall reactivity of the system, even when systems with identical reactive surface area are considered. The effect becomes more pronounced as the heterogeneity of the reactive grain packing increases, particularly where the flow slows sufficiently such that the solution approaches equilibrium locally and the average rate becomes transport-limited.

  10. Averaged collision and reaction rates in a two-species gas of ultracold fermions

    NASA Astrophysics Data System (ADS)

    Pikovski, Alexander

    2013-01-01

    Reactive or elastic two-body collisions in an ultracold gas are affected by quantum statistics. In this paper, we study ensemble-averaged collision rates for a two-species fermionic gas. The two species may have different masses, densities, and temperatures. We investigate how averaged collision rates are affected by the presence of Fermi spheres in the initial states; Pauli blocking of final states is not considered. It is shown that, independently on the details of the collision, Fermi-averaged collision rates deviate from Boltzmann-averaged ones, particularly for a gas with strong imbalance of masses or densities.

  11. Solubility and Reaction Rates of Aluminum Solid Phases Under Geothermal Conditions

    SciTech Connect

    Benezeth, P.; Palmer, D.A.; Wesolowski, D.J.; Anovitz, L.M.

    2000-05-28

    Experimental studies involving equilibrium solubility and dissolution/precipitation rates were initiated on aluminum hydroxide phases prevalent under geothermal reservoir conditions. A large capacity, hydrogen-electrode concentration cell (HECC) was constructed specifically for this purpose.

  12. Averaged collision and reaction rates in a two-species gas of ultracold fermions

    NASA Astrophysics Data System (ADS)

    Pikovski, Alexander

    2014-03-01

    Reactive or elastic two-body collisions in an ultracold gas are affected by quantum statistics. We study ensemble-averaged collision rates for a two-species fermionic gas, where the two species may have different masses, densities, and temperatures. It is shown in what way Fermi-averaged collision rates deviate from Boltzmann-averaged ones, particularly for a gas with strong imbalance of masses or densities. The results are independent of the details of the collision process.

  13. 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.

  14. 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.

  15. Application of chemometrics methods with kinetic constraints for estimation of rate constants of second order consecutive reactions.

    PubMed

    Kompany-Zareh, Mohsen; Khoshkam, Maryam

    2008-05-01

    To determine the rate constants for the second order consecutive reactions of the form U + V -(k1)--> W -(k2)--> P, a number of chemometrics and hard modeling-based methods are described. The absorption spectroscopic data from the reaction were utilized for performing the analysis. Concentrations and extinctions of components were comparable, and all of them were absorbing species. The number of steps in the reaction was less than the number of absorbing species, which resulted in a rank-deficient response matrix. This can cause difficulties for some of the methods described in the literature. The standard MATLAB functions were used for determining the solutions of the differential equations as well as for finding the optimal rate constants to describe the kinetic profiles. The available knowledge about the system determines the approaches described in this paper. The knowledge includes the spectra of reactants and products, the initial concentrations, and the exact kinetics. Some of this information is sometimes not available or is hard to estimate. Multiple linear regression for fitting the kinetic parameters to the obtained concentration profiles, rank augmentation using multiple batch runs, a mixed spectral approach which treats the reaction using a pseudo species concept, and principal components regression are the four groups of methods discussed in this study. In one of the simulated datasets the spectra are quite different, and in the other one the spectra of one reactant and of the product share a high degree of overlap. Instrumental noise, sampling error are the sources of error considered. Our aim was the investigation of the relative merits of each method. PMID:18469471

  16. Kinetics of gas-phase tropospheric reactions of organic solvents and hydroxyl radical by laser photolysis laser-induced fluorescence

    NASA Astrophysics Data System (ADS)

    Kompitsas, Michael; Mellouki, A.; Le Bras, Georges; Roubani-Kalantzopoulou, F.; Mavropoulos, A.; Bassiotis, I.

    1998-07-01

    Hydroxyl gas-phase reactions play a very important role in air pollution. For the majority of chemical compounds of the atmosphere, the reaction with OH radical s is an intermediate one, part of a long chain reaction. A laser photolysis-laser induced fluorescence technique has been sued to study OH reaction kinetics with dioxane. The apparatus consists of two synchronized pulsed laser systems, a six cross flow/steady gas reactor, a photomultiplier for LIF detection and control electronics. The first laser is used for the production of OH radicals by photolysis. The second laser provides a probe-beam which excites the OH radical electronically. Then, the relative population of OH radicals is monitored time-resolved by laser induced fluorescence. All experiments are performed under pseudo- first order kinetic conditions. The major advantages of this technique are: (1) Capability to measure OH reaction kinetics over an extended temperature range, with different reactants using the same apparatus. (2) Generation of a clean source of OH radicals. (3) Capability of atmospheric pressure measurements. (4) Micro-scale simulation of atmospheric reactions.

  17. Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction

    NASA Technical Reports Server (NTRS)

    Hwang, S. M.; Cooke, J. A.; De Witt, K. J.; Rabinowitz, M. J.

    2010-01-01

    Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).

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

    SciTech Connect

    Ji, Y.; Shen, C.

    2014-03-15

    With consideration of magnetic field line curvature (FLC) pitch angle scattering and charge exchange reactions, the O{sup +} (>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{sup +} 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{sup +} 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.

  19. Determination of Rate Constants for Ouabain Inhibition of Adenosine Triphosphatase: An Undergraduate Biological Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Sall, Eri; And Others

    1978-01-01

    Describes an undergraduate biological chemistry laboratory experiment which provides students with an example of pseudo-first-order kinetics with the cardiac glycoside inhibition of mammalism sodium and potassium transport. (SL)

  20. Absolute determination of the {sup 22}Na(p,{gamma}){sup 23}Mg reaction rate in novae

    SciTech Connect

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

    2011-03-15

    Gamma-ray telescopes in orbit around the earth are searching for evidence of the elusive radionuclide {sup 22}Na produced in novae. Previously published uncertainties in the dominant destructive reaction, {sup 22}Na(p,{gamma}){sup 23}Mg, indicated new measurements in the proton energy range of 150 to 300 keV were needed to constrain predictions. We have measured the resonance strengths, energies, and branches directly and absolutely by using protons from the University of Washington accelerator with a specially designed beam line, which included beam rastering and cold vacuum protection of the {sup 22}Na implanted targets. The targets, fabricated at TRIUMF-ISAC, displayed minimal degradation over a {approx}20 C bombardment as a result of protective layers. We avoided the need to know the absolute stopping power, and hence the target composition, by extracting resonance strengths from excitation functions integrated over proton energy. Our measurements revealed that resonance strengths for E{sub p}=213, 288, 454, and 610 keV are stronger by factors of 2.4-3.2 than previously reported. Upper limits have been placed on proposed resonances at 198, 209, and 232 keV. These substantially reduce the uncertainty in the reaction rate. We have re-evaluated the {sup 22}Na(p,{gamma}) reaction rate, and our measurements indicate the resonance at 213 keV makes the most significant contribution to {sup 22}Na destruction in novae. Hydrodynamic simulations including our rate indicate that the expected abundance of {sup 22}Na ejecta from a classical nova is reduced by factors between 1.5 and 2, depending on the mass of the white-dwarf star hosting the nova explosion.

  1. On the introduction of {sup 17}O+p reaction rates evaluated through the THM in AGB nucleosynthesis calculations

    SciTech Connect

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

    2014-05-09

    The rates for the {sup 17}O(p,??{sup 14}N, {sup 17}O(p,?){sup 18}F and {sup 18}O(p,?){sup 15}N reactions deduced trough the Trojan Horse Method (THM) have been introduced into a state-of-the-art asymptotic giant branch (AGB) models for proton-capture nucleosynthesis and cool bottom process. The predicted abundances have been compared with isotopic compositions provided by geochemical analysis of presolar grains. As a result, an improved agreement is found between the models and the isotopic mix of oxide grains of AGB origins, whose composition is the signature of low-temperature proton-capture nucleosynthesis.

  2. Direct measurement of neon production rates by (?,n) reactions in minerals

    NASA Astrophysics Data System (ADS)

    Cox, Stephen E.; Farley, Kenneth A.; Cherniak, Daniele J.

    2015-01-01

    The production of nucleogenic neon from alpha particle capture by 18O and 19F offers a potential chronometer sensitive to temperatures higher than the more widely used (U-Th)/He chronometer. The accuracy depends on the cross sections and the calculated stopping power for alpha particles in the mineral being studied. Published 18O(?,n)21Ne production rates are in poor agreement and were calculated from contradictory cross sections, and therefore demand experimental verification. Similarly, the stopping powers for alpha particles are calculated from SRIM (Stopping Range of Ions in Matter software) based on a limited experimental dataset. To address these issues we used a particle accelerator to implant alpha particles at precisely known energies into slabs of synthetic quartz (SiO2) and barium tungstate (BaWO4) to measure 21Ne production from capture by 18O. Within experimental uncertainties the observed 21Ne production rates compare favorably to our predictions using published cross sections and stopping powers, indicating that ages calculated using these quantities are accurate at the ?3% level. In addition, we measured the 22Ne/21Ne ratio and (U-Th)/He and (U-Th)/Ne ages of Durango fluorapatite, which is an important model system for this work because it contains both oxygen and fluorine. Finally, we present 21Ne/4He production rate ratios for a variety of minerals of geochemical interest along with software for calculating neon production rates and (U-Th)/Ne ages.

  3. Fundamental Kinetic Modeling: ab initio rate constant calculations of elementary reactions 

    E-print Network

    Jenks, Richard Lee

    1998-01-01

    at different theory levels and basis sets. Even a small difference wi 'II result in large changes to the rate constant due to the exponential energy dependence of the Arrhenius equation. Therefore, a standardized theory level and basis set is currently...

  4. The radiative capture reaction rate from $??$ to H dibaryon in the imaginary time method

    E-print Network

    E. Hikota; Y. Funaki; E. Hiyama; M. Oka

    2015-05-08

    Radiative capture rates of thermal $\\Lambda\\Lambda + \\Xi$N states into H dibaryon are calculated in the novel imaginary time method. The H dibaryon is assumed to be a bound state of $\\Xi $N with spin $J^{\\pi}= 0^+$, isospin $I=0$ and strangeness $-2$. We consider $E1$ transition to H from $\\Xi$N $(L=1)$ scattering states which mix with $\\Lambda\\Lambda (L=1)$. In order to calculate the transition rates, we formulate a coupled-channel imaginary time method by extending the one-channel formula originally proposed by Yabana and Funaki. The imaginary time method allows us to avoid the sum over all the excited thermal initial states, and thus to save computational time significantly. The transition rates are given as a function of temperature and the unknown binding energy of the H dibaryon, which we take as a parameter. It is found that the transition rate is not sensitive to the choices of the H binding energy or the strengths of the channel coupling for temperatures 3 MeV or higher.

  5. Radiative capture reaction rate from ? ? to H dibaryon in the imaginary time method

    NASA Astrophysics Data System (ADS)

    Hikota, Eri; Funaki, Yasuro; Hiyama, Emiko; Oka, Makoto

    2015-07-01

    Radiative capture rates of thermal ? ? +? N states into a H dibaryon are calculated in the novel imaginary time method. The H dibaryon is assumed to be a bound state of ? N with spin J?=0+ , isospin I =0 and strangeness -2 . We consider the E 1 transition to H from ? N (L =1 ) scattering states which mix with ? ? (L =1 ) . In order to calculate the transition rates, we formulate a coupled-channel imaginary time method by extending the one-channel formula originally proposed by Yabana and Funaki. The imaginary time method allows us to avoid the sum over all the excited thermal initial states, and thus to save computational time significantly. The transition rates are given as a function of temperature and the unknown binding energy of the H dibaryon, which we take as a parameter. It is found that the transition rate is not sensitive to the choices of the H binding energy or the strengths of the channel coupling for temperatures 3 MeV or higher.

  6. The radiative capture reaction rate from $\\Lambda \\Lambda$ to H dibaryon in the imaginary time method

    E-print Network

    Hikota, E; Hiyama, E; Oka, M

    2015-01-01

    Radiative capture rates of thermal $\\Lambda\\Lambda + \\Xi$N states into H dibaryon are calculated in the novel imaginary time method. The H dibaryon is assumed to be a bound state of $\\Xi $N with spin $J^{\\pi}= 0^+$, isospin $I=0$ and strangeness $-2$. We consider $E1$ transition to H from $\\Xi$N $(L=1)$ scattering states which mix with $\\Lambda\\Lambda (L=1)$. In order to calculate the transition rates, we formulate a coupled-channel imaginary time method by extending the one-channel formula originally proposed by Yabana and Funaki. The imaginary time method allows us to avoid the sum over all the excited thermal initial states, and thus to save computational time significantly. The transition rates are given as a function of temperature and the unknown binding energy of the H dibaryon, which we take as a parameter. It is found that the transition rate is not sensitive to the choices of the H binding energy or the strengths of the channel coupling for temperatures 3 MeV or higher.

  7. USE OF ROUGH SETS AND SPECTRAL DATA FOR BUILDING PREDICTIVE MODELS OF REACTION RATE CONSTANTS

    EPA Science Inventory

    A model for predicting the log of the rate constants for alkaline hydrolysis of organic esters has been developed with the use of gas-phase min-infrared library spectra and a rule-building software system based on the mathematical theory of rough sets. A diverse set of 41 esters ...

  8. Reproducible Preparation of Au/TS-1 with High Reaction Rate for Gas Phase Epoxidation of Propylene

    SciTech Connect

    Lee W. S.; Stach E.; Akatay, M.C.; Ribeiro, F.H.; Delgass, N.

    2012-03-01

    A refined and reliable synthesis procedure for Au/TS-1(Si/Ti molar ratio {approx}100) with high reaction rate for the direct gas phase epoxidation of propylene has been developed by studying the effects of pH of the gold slurry solution, mixing time, and preparation temperature for deposition precipitation (DP) of Au on TS-1 supports. Au/TS-1 catalysts prepared at optimal DP conditions (pH {approx} 7.3, mixing for 9.5 h, room temperature) showed an average PO rate {approx} 160 g{sub PO} h{sup -1} kg{sub Cat}{sup -1} at 200 C at 1 atm. A reproducibility better than {+-}10% was demonstrated by nine independent samples prepared at the same conditions. These are the highest rates yet reported at 200 C. No visible gold particles were observed by the HRTEM analysis in the fresh Au/TS-1 with gold loading up to {approx}0.1 wt%, indicating that the gold species were smaller than 1 nm. Additionally, the rate per gram of Au and the catalyst stability increased as the Au loading decreased, giving a maximum value of 500 g{sub PO} h{sup -1} g{sub Au}{sup -1}, and Si/Ti molar ratios of {approx}100 gave the highest rates.

  9. Reaction time changes with the hazard rate for a behaviorally relevant event when monkeys perform a delayed wrist movement task.

    PubMed

    Tsunoda, Yoshiaki; Kakei, Shinji

    2008-03-12

    Anticipating the timing of behaviorally relevant events is crucial for organizing movement. The time to initiate actions based on events (i.e., reaction time (RT)) is a useful measure to quantify states of anticipation. Few studies have examined how anticipation affects the timing of limb movements. We addressed this question behaviorally with two macaque monkeys performing delayed wrist movement tasks. The interval between target onset and go signal (i.e., foreperiod) varied randomly from 1 to 2 s. The probability that the go signal was about to occur (i.e., hazard rate) increased as the foreperiod increased. The kinematics of wrist movements was not influenced by foreperiod duration. Analyzing RT data with the LATER model indicated that RT distributions swiveled on reciprobit plots as foreperiods increased, suggesting that changes in RT distributions were due to changes in anticipation. RT was inversely related to hazard rate. To better understand the general implications of anticipatory states, we introduced an additional rectangular foreperiod distribution that ranged from 0.9 to 1.5 s. For that distribution, the hazard rate peaks were higher than those of the 1-2 s distribution. Changes in RT were clearly explained by quantitative differences in hazard rate. The decrease in RT in the 0.9-1.5 s foreperiod distribution was greater than that in the 1-2 s foreperiod. Thus, monkeys learned the temporal structure of foreperiod distributions and anticipated the onset of the go signal, based on hazard rates. PMID:18243554

  10. 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.

  11. Rates of dissolved oxygen-induced polymerization reactions of phenol and o-cresol on activated carbon

    SciTech Connect

    Abuzaid, N.S.; Nakhla, G.F.

    1995-12-31

    The effect of different dissolved oxygen (DO) levels on the kinetics of phenol and o-cresol uptake by granular activated carbon (GAC) was investigated in batch reactors. The equilibrium batch capacities matched the corresponding isotherm capacities within a maximum deviation of 6 percent. Equilibrium was attained in the anoxic batches only after 2 days while taking about 14 days for the oxic batches. The homogeneous surface diffusion model (HSDM) accurately predicted the uptake in the anoxic batches but deviated substantially from that of the oxic batches. The diffusivity coefficients for phenol and o-cresol on GAC were highly affected by the DO concentration. The higher the DO content in the sorbate solution the lower the diffusivity coefficient. Three distinct stages were observed in the kinetics of the polymerization reactions; the lag time stage, followed by a stage in which DO was not limiting reactions, and finally, the limiting DO stage. A kinetic model was developed for the polymerization reactions relating the rate constant to the DO levels using a nonlinear relationship. 20 refs., 7 figs., 4 tabs.

  12. UV and solar photo-degradation of naproxen: TiO2 catalyst effect, reaction kinetics, products identification and toxicity assessment.

    PubMed

    Jallouli, Nabil; Elghniji, Kais; Hentati, Olfa; Ribeiro, Ana R; Silva, Adrián M T; Ksibi, Mohamed

    2016-03-01

    Direct photolysis and TiO2-photocatalytic degradation of naproxen (NPX) in aqueous solution were studied using a UV lamp and solar irradiation. The degradation of NPX was found to be in accordance with pseudo-first order kinetics, the photocatalytic process being more efficient than photolysis. The NPX removal by photolysis (pHinitial 6.5) was 83% after 3h, with 11% of chemical oxygen demand (COD) reduction, whereas the TiO2-UV process led to higher removals of both NPX (98%) and COD (25%). The apparent pseudo-first-order rate constant (kapp) for NPX degradation by photolysis ranged from 0.0050min(-1) at pH 3.5 to 0.0095min(-1) at pH 6.5, while it was estimated to be 0.0063min(-1) under acidic conditions in photocatalysis, increasing by 4-fold at pH 6.5. Ultra High Performance Liquid chromatography (UHPLC) coupled with a triple quadrupole detector and also a hybrid mass spectrometer which combines the linear ion trap triple quadrupole (LTQ) and OrbiTrap mass analyser, were used to identify NPX degradation products. The main intermediates detected were 1-(6-methoxynaphtalene-2-yl) ethylhydroperoxide, 2-ethyl-6-methoxynaphthalene, 1-(6-methoxynaphtalen-2-yl) ethanol, 1-(6-methoxynaphtalen-2-yl) ethanone and malic acid. Solar photocatalysis of NPX showed COD removals of 33% and 65% after 3 and 4h of treatment, respectively, and some reduction of acute toxicity, evaluated by the exposure of Eisenia andrei to OECD soils spiked with NPX-treated solutions. PMID:26571001

  13. Reaction of lymphoid organs to laser radiation with different pulsation rates

    NASA Astrophysics Data System (ADS)

    Kapinosov, Ivan K.; Bugaeva, Irine O.; Kolokolov, George R.; Provozina, Helen J.

    1996-05-01

    Experimental studies were performed on 220 male rats of Wistar line to reveal optimal parameters of laser radiation causing positive changes in biotissues and to select methods of laser therapy. Irradiation of the ventral abdominal wall performed by arsenide-gallium injector (710 - 890 nm, exposure - 128 sec) in pulse rate: 3000 Hz, 1500 Hz, 80 Hz. Content of lymphoblasts, medium and small lymphocytes, plasmocytes, T-lymphocytes and T-helpers as well as the activity of chromatin and lysosomal enzymes were determined in the dynamics of thymus, spleen and lymph nodes. During irradiation with the rate of 3000 Hz prevailing inhibiting influence on the immumocytopoesis and functional activity of lymphocytes in all organs studied was state, the effect being manifested by the decrease in the number of all forms of lymphocytes particular on the 3rd-5th-7th day followed by normalization on the 15th- 21st-30th day. Irradiation with the rate of 1500 Hz produced stimulating effect on the immune organs accompanied by reliable excess of control indices of lymphocyte content particularly of poorly differentiated forms (blasts and medium ones), as well as by the increase of the number of plasmocytes, T-lymphocytes, T-helpers with maximum manifestation on the 7th day. On the 15th day there is a decrease, and on the 21st-30th day--there is normalization. Irradiation with the rate of 80 Hz produced the smallest but most marked effect, particularly on the number of lymphoblasts. Peculiarities in kinetics of cellular elements studied were revealed in different lymphoid organs and in different functional zones of these organs.

  14. Reaction Between Thin Gold Wires and Pb-Sn-In Solder (37.5%, 37.5%, 25%), Part A: The Radial Reaction Inside The Solder Mounds, Its Linear Reaction Model, Statistical Variation of Reaction Rate, and Induced Structural Changes In The Solder Mounds.

    SciTech Connect

    Siekhaus, W J

    2011-01-19

    Thermodynamics favors the reaction between indium and gold, since the heat of formation of AuIn{sub 2} is 6 kcal/mole, substantially larger than the heat of formation of any other possible reaction product. Thermodynamic equilibrium between gold and the elements in the solder mound is reached only when ALL gold is converted to AuIn{sub 2}. There are two aspects to this conversion: (A) the reaction WITHIN the solder mound (called here 'radial reaction') and (B) the reaction OUTSIDE the solder mound (called here 'axial reaction') and the transition from (A) to (B). The reaction between thin gold detonator wires and the In/Pb/Sn solder mound in older detonators has been looked at repeatedly. There are, in addition, two studies which look at the reaction between indium and gold in planar geometry. All data are shown in tables I to V. It is the objective of this section dealing with aspect (A), to combine all of these results into a reaction model and to use this reaction model to reliably and conservatively predict the gold-solder reaction rate of soldered gold bridge-wires as a function of storage temperature and time.

  15. 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

    2015-12-01

    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. PMID:26567633

  16. Investigation of the rates of surface and bulk ROS-generating reactions using indigo dye as an indicator

    NASA Astrophysics Data System (ADS)

    Anderson, Carly; Clark, Douglas; Graves, David

    2014-10-01

    We present evidence for the existence of two distinct processes that contribute to the generation of reactive oxygen and nitrogen species (RONS) in liquids exposed to cold atmospheric plasma (CAP) in air. At the plasma-liquid interface, there exists a fast surface reaction zone where RONS from the gas phase interact with species in the liquid. RONS can also be produced by ``slow'' chemical reactions in the bulk liquid, even long after plasma exposure. To separate the effects of these processes, we used indigo dye as an indicator of ROS production; specifically generation of hydroxyl radical. The rate of indigo decolorization while in direct contact with CAP is compared with the expected rate of hydroxyl radical generation at the liquid surface. When added to aqueous solutions after CAP exposure, indigo dye reacts on a time scale consistent with the production of peroxynitrous acid, ONOOH, which is known to decompose to hydroxyl radical below a pH of 6.8. In this study, the CAP used was a air corona discharge plasma run in a positive streamer mode.

  17. Reactivity and reaction rate ratio changes with moderator voidage in a light water high converter reactor lattice

    SciTech Connect

    Chawla, R.; Gmur, K.; Hager, H.; Seiler, R.

    1984-12-01

    Integral reaction rate ratios and other kinfinity-related parameters have been measured in the first three cores of the experimental program on light water high converter reactor (LWHCR) test lattices in the PROTEUS reactor. The reference tight-pitch lattice consisted of two rod types, with an average fissile-plutonium enrichment of 6% and a fuel/moderator ratio of 2.0. The moderators were H/sub 2/O, Dowtherm (simulating an H/sub 2/O voidage of 42.5%), and air (100% void). Comparisons of the measured parameters have been made with calculational results based mainly on the use of two separate codes and their associated data libraries, namely, WIMS-D and EPRI-CPM. A reconstruction of individual components of the kinfinity void coefficient has been carried out on the basis of the measured changes with voidage of the various reaction rate ratios, as well as of kinfinity itself. The subsequent more detailed comparisons between experiment and calculation should provide a useful basis for resolving the conflicting calculational results that have been reported in the past for the void coefficient characteristics of LWHCRs.

  18. Spectroscopy of 19Ne for the thermonuclear 15O(? ,? )19Ne and 18F(p ,? )15O reaction rates

    NASA Astrophysics Data System (ADS)

    Parikh, A.; Laird, A. M.; de Séréville, N.; Wimmer, K.; Faestermann, T.; Hertenberger, R.; Seiler, D.; Wirth, H.-F.; Adsley, P.; Fulton, B. R.; Hammache, F.; Kiener, J.; Stefan, I.

    2015-11-01

    Uncertainties in the thermonuclear rates of the 15O (? ,? ) 19 Ne and 18 F(p ,? ) 15 O reactions affect model predictions of light curves from type I x-ray bursts and the amount of the observable radioisotope 18F produced in classical novae, respectively. To address these uncertainties, we have studied the nuclear structure of 19Ne over Ex=4.0 -5.1 and 6.1-7.3 MeV using the (3He19F,t )19Ne reaction. We find the J? values of the 4.14- and 4.20-MeV levels to be consistent with 9 /2- and 7 /2- , respectively, in contrast to previous assumptions. We confirm the recently observed triplet of states around 6.4 MeV and find evidence that the state at 6.29 MeV, just below the proton threshold, is either broad or a doublet. Our data also suggest that predicted but yet unobserved levels may exist near the 6.86-MeV state. Higher resolution experiments are urgently needed to further clarify the structure of 19Ne around the proton threshold before a reliable 18 F(p ,? ) 15 O rate for nova models can be determined.

  19. An "Aufbau" Approach to Understanding How the King-Altman Method of Deriving Rate Equations for Enzyme-Catalyzed Reactions Works

    ERIC Educational Resources Information Center

    Sims, Paul A.

    2009-01-01

    The King-Altman method of deriving rate equations for enzymatic reactions is applied to the derivation of the Michaelis-Menten equation, along with an explanation for how (or why) the King-Altman method works in this case. The slightly more complicated cases of competitive inhibition and a two-substrate enzyme-catalyzed reaction are then treated…

  20. Combining direct residence time measurements and biogeochemistry to calculate in-situ reaction rates in the hyporheic zone

    NASA Astrophysics Data System (ADS)

    Pittroff, Marco; Gilfedder, Benjamin

    2015-04-01

    The hyporheic zone is an active interface between groundwater, riparian and surface water systems. Exchange and reaction of water, nutrients, and organic matter occur due to variations in surface and groundwater flow regimes, bed topography and active biogeochemistry fuelled by bioavailable carbon. There has been an increasing focus on coupling the residence time of surface water in the hyporheic zone with biogeochemical reactions. However, there are very few tracers that can be used to measure residence times in-situ, especially in complex groundwater-surface water settings. In this work we have used the natural radioisotope Radon (222Rn) as an in-situ tracer for river water residence time in a riffle-pool sequence (Rote Main River), and combined this information with biogeochemical parameters (DOC and C quality, O3, NO3, CO2). We can clearly observe a dependence of reaction progress on the water residence times, with oxygen and nitrate reduction following inverse logarithmic trends as a function of time. By comparing with initial concentrations (the river end member) with riverbed levels we have estimated first-order in-situ reduction rates for nitrate and oxygen. Nitrate reduction rates are at the higher end of published values, which is likely due to the continual supply of bioavailable carbon from the river system. This work helps to better understand the function and efficiency of the hyporheic zone as a natural filter for redox sensitive species such as nitrate at the groundwater - steam interface. It also provides a useful method for estimating residence times in complex, higher order river systems.

  1. On the “direct” calculation of thermal rate constants. II. The flux-flux autocorrelation function with absorbing potentials, with application to the O+HCl?OH+Cl reaction

    E-print Network

    Thompson, Ward H.; Miller, William H.

    1997-01-01

    results of this method applied to the O+HCl reaction using the J-shifting and helicity conserving approximations to include nonzero total angular momentum. The calculated rate constants are compared to experimental and previous theoretical results. Finally...

  2. Rate coefficients for the endothermic reactions C+(^2P)+H2(D2)?CH^+(CD^+)+H(D) as functions of temperature from 400–1300 K

    E-print Network

    Hierl, Peter M.; Morris, Robert A.; Viggiano, A. A.

    1997-03-20

    We have measured the bimolecular rate coefficients for the reactions of C+(2P) with H2 and D2 as functions of temperature from 400 to 1300 K using a high temperatureflowing afterglow apparatus. The temperature dependences ...

  3. 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.

  4. Comment on "Properties of (26)Mg and (26)Si in the sd shell model and the determination of the (25)Al(p,gamma) (26) Si reaction rate"

    SciTech Connect

    Chipps, K.; Bardayan, Daniel W; Liang, J Felix; Pain, Steven D; Smith, Michael Scott; Chae, K. Y.; Pittman, S. T.; Cizewski, J. A.; O'Malley, Patrick; Peters, W. A.; Kozub, R. L.; Matei, Catalin

    2011-01-01

    A recent discussion of theoretical work on the {sup 25}Al(p,{gamma}){sup 26}Si astrophysical reaction rate [W.A. Richter, B. Alex Brown, A. Signoracci and M. Wiescher Phys. Rev. C 83 065803 (2011)] omits some current and relevant experimental information in forming its scientific conclusions. Accounting for this new information has the potential to significantly alter the reaction rate derived in the paper.

  5. Evaluation of Risk Minimisation Measures for Blood Components – Based on Reporting Rates of Transfusion-Transmitted Reactions (1997-2013)

    PubMed Central

    Funk, Markus B.; Heiden, Margarethe; Volkers, Peter; Lohmann, Annette; Keller-Stanislawski, Brigitte

    2015-01-01

    Summary Background To assess the impact of safety measures, we compared reporting rates of transfusion-related reactions before and after the implementation of six measures in 1999, 2004, 2006, 2008 and 2009. Methods Reporting rates of transfusion-transmitted bacterial infection (TTBI), viral infection (TTVI) and immune-mediated transfusion-related acute lung injury (TRALI) were calculated on the basis of confirmed annual reports and distributed blood components. Results The introduction of HCV NAT testing caused a significant reduction of HCV reporting rate from 1:0.6 to 1:83.16 million administered blood components (p < 0.0001), donor screening for antibodies to hepatitis B core antigen caused a reduction of HBV reporting rate from 1:2.90 to 1:10.70 million units (p = 0.0168). A significant reduction from 1:0.094 to 1:2.42 million fresh frozen plasma (FFP) units could also be achieved by risk minimisation TRALI measures (p < 0.0001). Implementation of pre-donation sampling did not result in a significant decrease in TTBI, whereas limitation of shelf life for platelet concentrate (PC) minimised the TTBI reporting rate from 1:0.088 to 1:0.19 million PC units (p = 0.041). For HIV NAT pool testing, no significant reduction in HIV transmission was found due to very low reporting rates (1:10 million versus 1:27 million blood components, p = 0.422). Conclusion On the basis of haemovigilance data, a significant benefit could be demonstrated for four of six implemented safety measures. PMID:26557816

  6. Metabolic Rate and Ground Reaction Force During Motorized and Non-Motorized Treadmill Exercise

    NASA Technical Reports Server (NTRS)

    Everett, Meghan E.; Loehr, James A.; DeWitt, John K.; Laughlin, Mitzi; Lee, Stuart M. C.

    2010-01-01

    PURPOSE: To measure vertical ground reaction force (vGRF) and oxygen consumption (VO2) at several velocities during exercise using a ground-based version of the ISS treadmill in the M and NM modes. METHODS: Subjects (n = 20) walked or ran at 0.89, 1.34, 1.79, 2.24, 2.68, and 3.12 m/s while VO2 and vGRF data were collected. VO2 was measured using open-circuit spirometry (TrueOne 2400, Parvo-Medics). Data were averaged over the last 2 min of each 5-min stage. vGRF was measured in separate 15-s bouts at 125 Hz using custom-fitted pressure-sensing insoles (F-Scan Sport Sensors, Tekscan, Inc). A repeated-measures ANOVA was used to test for differences in VO2 and vGRF between M and NM and across speeds. Significance was set at P < 0.05. RESULTS: Most subjects were unable to exercise for 5 min at treadmill speeds above 1.79 m/s in the NM mode; however, vGRF data were obtained for all subjects at each speed in both modes. VO2 was approx.40% higher during NM than M exercise across treadmill speeds. vGRF increased with treadmill speed but was not different between modes. CONCLUSION: Higher VO2 with no change in vGRF suggests that the additional metabolic cost associated with NM treadmill exercise is accounted for in the horizontal forces required to move the treadmill belt. Although this may limit the exercise duration at faster speeds, high-intensity NM exercise activates the hamstrings and plantarflexors, which are not specifically targeted or well protected by other in-flight countermeasures.

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

    SciTech Connect

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

    2010-02-16

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

  8. Reaction Rate Sensitivity of 44Ti Production in Massive Stars and Implications of a Thick Target Yield Measurement of 40Ca(?, ?)44Ti

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

  9. Encounters of H and D atoms with O{sub 2} in water: Relative diffusion and reaction rates

    SciTech Connect

    Han, P.; Bartels, D.M.

    1993-08-01

    Diffusive encounters of H and D atoms with O{sub 2} in water are investigated with the time-domain EPR free induction decay attenuation technique. Given the paramagnetic triplet ground state of the O{sub 2} molecule, it is expected that all H-O{sub 2} encounters will contribute to spin dephasing, regardless of whether reaction to form HO{sub 2} occurs. In H{sub 2}O the second-order spin-spin dephasing rate of H in the presence of O{sub 2} is 1.94 {times} 10{sup 10} M{sup {minus}1} sec{sup {minus}1} at 25{degrees}C, with an activation energy of 11.22 {+-} 0.33 kJ/mole between 8 and 60{degrees}C. In a mixture of 90% D{sub 2}O and 10% H{sub 2}O, H atom dephasing is marginally slower in the same temperature range. Dephasing of D atoms in 90% D{sub 2}O is ca. 5--10% slower than H, indicating that diffusion of D is slower than H. The results are analyzed in terms of other available data concerning H and O{sub 2} diffusion and the reaction rate in water. It seems clear that neither the Stokes Einstein hydrodynamic theory nor classical activated rate theory applies to the diffusion of light hydrophobic gases in water. The authors tentatively conclude that H-O{sub 2} spin exchange is slightly less efficient than can be predicted in the theoretical diffusion limit.

  10. Predicting the reaction rate constants of micropollutants with hydroxyl radicals in water using QSPR modeling.

    PubMed

    Jin, Xiaohui; Peldszus, Sigrid; Huck, Peter M

    2015-11-01

    Quantitative structure-property relationship (QSPR) models which predict hydroxyl radical rate constants (kOH) for a wide range of emerging micropollutants are a cost effective approach to assess the susceptibility of these contaminants to advanced oxidation processes (AOPs). A QSPR model for the prediction of kOH of emerging micropollutants from their physico-chemical properties was developed with special attention to model validation, applicability domain and mechanistic interpretation. In this study, 118 emerging micropollutants including those experimentally determined by the author and data collected from the literature, were randomly divided into the training set (n=89) and validation set (n=29). 951 DRAGON molecular descriptors were calculated for model development. The QSPR model was calibrated by applying forward multiple linear regression to the training set. As a result, 7 DRAGON descriptors were found to be important in predicting the kOH values which related to the electronegativity, polarizability, and double bonds, etc. of the compounds. With outliers identified and removed, the final model fits the training set very well and shows good robustness and internal predictivity. The model was then externally validated with the validation set showing good predictive power. The applicability domain of the model was also assessed using the Williams plot approach. Overall, the developed QSPR model provides a valuable tool for an initial assessment of the susceptibility of micropollutants to AOPs. PMID:26005810

  11. Theoretical study of thermodynamic properties and reaction rates of importance in the high-speed research program

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen; Bauschlicher, Charles; Jaffe, Richard

    1992-01-01

    One of the primary goals of NASA's high-speed research program is to determine the feasibility of designing an environmentally safe commercial supersonic transport airplane. The largest environmental concern is focused on the amount of ozone destroying nitrogen oxides (NO(x)) that would be injected into the lower stratosphere during the cruise portion of the flight. The limitations placed on NO(x) emission require more than an order of magnitude reduction over current engine designs. To develop strategies to meet this goal requires first gaining a fundamental understanding of the combustion chemistry. To accurately model the combustor requires a computational fluid dynamics approach that includes both turbulence and chemistry. Since many of the important chemical processes in this regime involve highly reactive radicals, an experimental determination of the required thermodynamic data and rate constants is often very difficult. Unlike experimental approaches, theoretical methods are as applicable to highly reactive species as stable ones. Also our approximation of treating the dynamics classically becomes more accurate with increasing temperature. In this article we review recent progress in generating thermodynamic properties and rate constants that are required to understand NO(x) formation in the combustion process. We also describe our one-dimensional modeling efforts to validate an NH3 combustion reaction mechanism. We have been working in collaboration with researchers at LeRC, to ensure that our theoretical work is focused on the most important thermodynamic quantities and rate constants required in the chemical data base.

  12. 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.

  13. How does thermal motion of atoms influence rates of bridge-mediated electron transfer reactions? 1. Dynamical modulation of the effective tunneling coupling.

    NASA Astrophysics Data System (ADS)

    Balabin, Ilya; Skourtis, Spyros; Kawatsu, Tsutomu

    2005-03-01

    Understanding how thermal nuclear motion affects the electron transfer (ET) reaction rates is essential for describing a broad range of vital biological redox reactions as well as designing molecular electronic devices. Theoretical studies of biological ET reaction rates usually assume a) the superexchange ET regime (virtual bridge electronic states), and b) the Franck-Condon approximation (electronic dephasing slower than the time-dependent Franck-Condon factor decay time). We present the first investigation of the electronic dephasing effects and the first quantitative analysis of the modulation of effective tunneling coupling by nuclear dynamics. Molecular dynamics simulations coupled with extended Huckel-level quantum chemical calculations of the effective electronic coupling were performed for the blue copper ET protein azurin. We discuss effects of the donor-to-acceptor distance, tunneling pathway structure, tunneling energy, temperature, and protein motion on the dynamics of the effective tunneling coupling and the ET reaction rate.

  14. Kinetics of the C3H7O2 + NO Reaction: Temperature Dependence of the Overall Rate Constant and the i-C3H7ONO2 Branching Channel

    E-print Network

    Elrod, Matthew J.

    species such as the alkyl nitrates Because reaction 3b removes the radical chain carrier RO2 fromKinetics of the C3H7O2 + NO Reaction: Temperature Dependence of the Overall Rate Constant and the i The temperature dependence of the overall rate constant for the C3H7O2 + NO reaction and the rate constant

  15. Upscaling Reaction Rate Laws In Geochemical Reactive Transport Using Pore-Scale Network Models Dmitri Kavetski1,2,#, Catherine A. Peters1,$, Michael A. Celia1 and Brent Lindquist3

    E-print Network

    Peters, Catherine A.

    Upscaling Reaction Rate Laws In Geochemical Reactive Transport Using Pore-Scale Network Models, Steefel et al, 2005). This work focuses on reaction rate laws describing acid-driven mineral dissolution and examines whether reaction rates applicable at the pore-scale, O(10-100m), are realistic at larger continuum

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

    E-print Network

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

    2008-03-19

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

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

    SciTech Connect

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

    2008-04-15

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

  18. Astrophysical reaction rates for Ni-58,Ni-60(n,gamma) from new neutron capture cross section measurements

    SciTech Connect

    Guber, Klaus H; Derrien, Herve; Leal, Luiz C; Arbanas, Goran; Wiarda, Dorothea; Koehler, Paul; Harvey, John A

    2010-01-01

    New neutron capture cross section of 58,60Ni were measured in the energy range from 100 eV to 600 keV using the Oak Ridge Electron Linear Accelerator (ORELA). The combination of these new neutron capture data with previous transmission data allowed a resonance analysis up to 900 keV using R-matrix theory. The theoretically determined direct capture (DC) cross sections were included in the analyses. From these resonance parameters and the DC contribution, new (n,y) astrophysical reaction rates were determined over the entire energy range needed by the lastest stellar models describing the so-called weak s process. PACS numbers: 25.40.Lw, 26.20Kn, 27.40.+z, 27.50.+e, 97.10.Cv

  19. LWR-PROTEUS Verification of Reaction Rate Distributions in Modern 10 x 10 Boiling Water Reactor Fuel

    SciTech Connect

    Jatuff, F.; Grimm, P.; Joneja, O.; Murphy, M.; Luethi, A.; Seiler, R.; Brogli, R.; Jacot-Guillarmod, R.; Williams, T.; Helmersson, S.; Chawla, R.

    2001-11-15

    HELIOS, CASMO-4, and MCNP4B calculations of reaction rate distributions in a modern, fresh 10 x 10 boiling water reactor fuel element have been validated using the experimental results of the LWR-PROTEUS Phase I project corresponding to full-density water moderation conditions (core 1B). The reaction rate distributions measured with a special gamma-scanning machine employing twin germanium detectors consisted of total fission F{sub tot} and {sup 238}U-capture C{sub 8}. The average statistical errors for the gamma scans were better than 0.5% for F{sub tot} and 0.9% for C{sub 8}. The rod-by-rod measurements were performed on 60 different fuel rods selected from the central part of a test zone consisting of actual, fresh SVEA-96+ fuel elements, thus gaining in realism by departing from conventional fuel rod mockups. In the case of F{sub tot}, the root-mean-square (rms) of the rod-by-rod distribution of differences between calculational and experimental (C-E) values has been found to be 1.1% for HELIOS and for CASMO-4, and 1.3% for MCNP4B. For C{sub 8}, the rms values of the (C-E) distributions are 1.0, 1.3, and 1.4% as obtained with HELIOS, CASMO-4, and MCNP4B, respectively. The effects of using different data libraries (ENDF/B-V, ENDF/B-VI, and JEF-2.2) with MCNP4B were also studied and have been found to be small.

  20. Geometric scaling for a detonation wave governed by a pressure-dependent reaction rate and yielding confinement

    NASA Astrophysics Data System (ADS)

    Li, J.; Mi, X.; Higgins, A. J.

    2015-02-01

    The propagation of detonation waves in reactive media bounded by an inert, compressible layer is examined via computational simulations in two different geometries, axisymmetric cylinders, and two dimensional, planar slabs. For simplicity, an ideal gas equation of state is used with a pressure-dependent reaction rate that results in a detonation wave structure that does not exhibit cellular instability. The detonation is initiated as an ideal Chapman-Jouguet (CJ) detonation with a one-dimensional structure, and then allowed to propagate into a finite diameter or thickness layer of explosive surrounded by an inert layer. The yielding confinement of the inert layer results in the detonation wave decaying to a sub-CJ steady state velocity or failing entirely. Simulations are performed with different values of the reaction rate pressure exponent (n = 2 and 3) and different impedance confinement (greater than, less than, and equal to that of the explosive). The velocity decrement and critical dimension (critical diameter or thickness) are determined, and a 2:1 scaling between the cylinder diameter and slab thickness results is confirmed, in good agreement with curvature-based models of detonation propagation. The measured shock front curvature and detonation velocity relation (DN-?) agrees with the classic model of Wood and Kirkwood. The computational simulations are compared to a simple, analytic model that treats the interaction of the confinement with the detonation products via Newtonian theory and a model that assumes a continuous variation in shock front curvature with the shock angle at the interface with the confinement matching the angle determined by shock polar analysis. The Newtonian model works very well for the case of high impedance confinement, while the shock front curvature model agrees with the simulations for the case of low impedance confinement.

  1. CH(+) Destruction by Reaction with H: Computing Quantum Rates To Model Different Molecular Regions in the Interstellar Medium.

    PubMed

    Bovino, S; Grassi, T; Gianturco, F A

    2015-12-17

    A detailed analysis of an ionic reaction that plays a crucial role in the carbon chemistry of the interstellar medium (ISM) is carried out by computing ab initio reactive cross sections with a quantum method and by further obtaining the corresponding CH(+) destruction rates over a range of temperatures that shows good overall agreement with existing experiments. The differences found between all existing calculations and the very-low-T experiments are discussed and explored via a simple numerical model that links these cross section reductions to collinear approaches where nonadiabatic crossing is expected to dominate. The new rates are further linked to a complex chemical network that models the evolution of the CH(+) abundance in the photodissociation region (PDR) and molecular cloud (MC) environments of the ISM. The abundances of CH(+) are given by numerical solutions of a large set of coupled, first-order kinetics equations that employs our new chemical package krome. The analysis that we carry out reveals that the important region for CH(+) destruction is that above 100 K, hence showing that, at least for this reaction, the differences with the existing laboratory low-T experiments are of essentially no importance within the astrochemical environments discussed here because, at those temperatures, other chemical processes involving the title molecule are taking over. A detailed analysis of the chemical network involving CH(+) also shows that a slight decrease in the initial oxygen abundance might lead to higher CH(+) abundances because the main chemical carbon ion destruction channel is reduced in efficiency. This might provide an alternative chemical route to understand the reason why general astrochemical models fail when the observed CH(+) abundances are matched with the outcomes of their calculations. PMID:26061287

  2. Linking Groundwater Age and Chemistry Data to Determine Redox Reaction Rates and Trends in Nitrate Concentrations in Agricultural Areas. (Invited)

    NASA Astrophysics Data System (ADS)

    Tesoriero, A. J.; Puckett, L.

    2009-12-01

    Use of industrially fixed nitrogen (N) fertilizer for agricultural purposes has increased dramatically, both in the United States (U.S.) and globally, since 1945. As a result, there has been growing concern about the consequences of increases in the amounts of anthropogenic N circulating in the atmosphere, hydrosphere, and biosphere. The U.S. Geological Survey’s National Water-Quality Assessment Program has collected groundwater samples along flow paths in more than 20 agricultural areas covering a range in hydrogeologic settings to evaluate the trends and transformations of agricultural chemicals. Historical trends in nitrogen fluxes to groundwater were evaluated by relating the recharge dates of groundwater samples, estimated using tracer (e.g., chlorofluorocarbon) concentrations, with concentrations of nitrate at the time of recharge, estimated by summing the molar concentrations of the parent compound (nitrate) and its transformation product (excess N2) in the age-dated sample. Results from this analysis indicate that median nitrate (NO3-) concentrations in recharge have increased markedly over the last 50 years: increasing from 4 mg/L (as N) in samples that recharged prior to 1983 to 7.5 mg/L (as N) in samples that recharged since 1983. Trends in nitrate concentrations in recharging groundwater were related to increases in the amount of fertilizer applied. Estimates of the portion of applied N reaching the water table ranged from 4 to 49% among the sites, with a median value of 14%. The fate of NO3- and many other groundwater contaminants is dependent on aquifer redox conditions. The reduction of oxygen is the most energetically favorable reaction that microorganisms use to oxidize organic material or other electron donors (e.g., pyrite). As a result, other reduction reactions (e.g., denitrification) affecting contaminant transport typically do not occur until most dissolved oxygen (DO) has been consumed. To improve assessments of contaminant transformations, first-order oxygen reduction rates were determined in each of 20 study areas by relating measured DO concentrations to groundwater age. First-order rate constants for these aquifers ranged from 0.03 to 0.18 yr-1 and were only weakly correlated with recharge temperature. DO reduction rates varied markedly within some sites, likely the result of changes in the supply of electron donors. The range in oxygen reduction rates both within and between sites is an important consideration when assessing the transport of redox-active contaminants.

  3. CO2 sequestration in feldspar-rich sandstone: Coupled evolution of fluid chemistry, mineral reaction rates, and hydrogeochemical properties

    NASA Astrophysics Data System (ADS)

    Tutolo, Benjamin M.; Luhmann, Andrew J.; Kong, Xiang-Zhao; Saar, Martin O.; Seyfried, William E.

    2015-07-01

    To investigate CO2 Capture, Utilization, and Storage (CCUS) in sandstones, we performed three 150 °C flow-through experiments on K-feldspar-rich cores from the Eau Claire formation. By characterizing fluid and solid samples from these experiments using a suite of analytical techniques, we explored the coupled evolution of fluid chemistry, mineral reaction rates, and hydrogeochemical properties during CO2 sequestration in feldspar-rich sandstone. Overall, our results confirm predictions that the heightened acidity resulting from supercritical CO2 injection into feldspar-rich sandstone will dissolve primary feldspars and precipitate secondary aluminum minerals. A core through which CO2-rich deionized water was recycled for 52 days decreased in bulk permeability, exhibited generally low porosity associated with high surface area in post-experiment core sub-samples, and produced an Al hydroxide secondary mineral, such as boehmite. However, two samples subjected to ?3 day single-pass experiments run with CO2-rich, 0.94 mol/kg NaCl brines decreased in bulk permeability, showed generally elevated porosity associated with elevated surface area in post-experiment core sub-samples, and produced a phase with kaolinite-like stoichiometry. CO2-induced metal mobilization during the experiments was relatively minor and likely related to Ca mineral dissolution. Based on the relatively rapid approach to equilibrium, the relatively slow near-equilibrium reaction rates, and the minor magnitudes of permeability changes in these experiments, we conclude that CCUS systems with projected lifetimes of several decades are geochemically feasible in the feldspar-rich sandstone end-member examined here. Additionally, the observation that K-feldspar dissolution rates calculated from our whole-rock experiments are in good agreement with literature parameterizations suggests that the latter can be utilized to model CCUS in K-feldspar-rich sandstone. Finally, by performing a number of reactive transport modeling experiments to explore processes occurring during the flow-through experiments, we have found that the overall progress of feldspar hydrolysis is negligibly affected by quartz dissolution, but significantly impacted by the rates of secondary mineral precipitation and their effect on feldspar saturation state. The observations produced here are critical to the development of models of CCUS operations, yet more work, particularly in the quantification of coupled dissolution and precipitation processes, will be required in order to produce models that can accurately predict the behavior of these systems.

  4. Evaluation of Reaction Rate Theory and Monte Carlo Methods for Application to Radiation-Induced Microstructural Characterization

    SciTech Connect

    Stoller, Roger E; Golubov, Stanislav I; Becquart, C. S.; Domain, C.

    2007-08-01

    The multiscale modeling scheme encompasses models from the atomistic to the continuum scale. Phenomena at the mesoscale are typically simulated using reaction rate theory, Monte Carlo, or phase field models. These mesoscale models are appropriate for application to problems that involve intermediate length scales, and timescales from those characteristic of diffusion to long-term microstructural evolution (~?s to years). Although the rate theory and Monte Carlo models can be used simulate the same phenomena, some of the details are handled quite differently in the two approaches. Models employing the rate theory have been extensively used to describe radiation-induced phenomena such as void swelling and irradiation creep. The primary approximations in such models are time- and spatial averaging of the radiation damage source term, and spatial averaging of the microstructure into an effective medium. Kinetic Monte Carlo models can account for these spatial and temporal correlations; their primary limitation is the computational burden which is related to the size of the simulation cell. A direct comparison of RT and object kinetic MC simulations has been made in the domain of point defect cluster dynamics modeling, which is relevant to the evolution (both nucleation and growth) of radiation-induced defect structures. The primary limitations of the OKMC model are related to computational issues. Even with modern computers, the maximum simulation cell size and the maximum dose (typically much less than 1 dpa) that can be simulated are limited. In contrast, even very detailed RT models can simulate microstructural evolution for doses up 100 dpa or greater in clock times that are relatively short. Within the context of the effective medium, essentially any defect density can be simulated. Overall, the agreement between the two methods is best for irradiation conditions which produce a high density of defects (lower temperature and higher displacement rate), and for materials that have a relatively high density of fixed sinks such as dislocations.

  5. Rate equation for creatine kinase predicts the in vivo reaction velocity: /sup 31/P NMR surface coil studies in brain, heart, and skeletal muscle of the living rat

    SciTech Connect

    Bittl, J.A.; DeLayre, J.; Ingwall, J.S.

    1987-09-22

    Brain, heart, and skeletal muscle contain four different creatine kinase isozymes and various concentrations of substrates for the creatine kinase reaction. To identify if the velocity of the creatine kinase reaction under cellular conditions is regulated by enzyme activity and substrate concentrations as predicted by the rate equation, the authors used /sup 31/P NMR and spectrophotometric techniques to measure reaction velocity, enzyme content, isozyme distribution, and concentrations of substrates in brain, heart, and skeletal muscle of living rat under basal or resting conditions. The total tissue activity of creatine kinase in the direction of MgATP synthesis provided an estimate for V/sub max/ and exceeded the NMR-determined in vivo reaction velocities by an order of magnitude. The isozyme composition varied among the three tissues: >99% BB for brain; 14% MB, 61% MM, and 25% mitochondrial for heart; and 98% MM and 2% mitochondrial for skeletal muscle. The NMR-determined reaction velocities agreed with predicted values from the creatine kinase rate equation. The concentrations of free creatine and cytosolic MgADP, being less than or equal to the dissociation constants for each isozyme, were dominant terms in the creatine kinase rate equation for predicting the in vivo reaction velocity. Thus, they observed that the velocity of the creatine kinase reaction is regulated by total tissue enzyme activity and by the concentrations of creatine and MgADP in a manner that is independent of isozyme distribution.

  6. Studies on adsorption, reaction mechanisms and kinetics for photocatalytic degradation of CHD, a pharmaceutical waste.

    PubMed

    Sarkar, Santanu; Bhattacharjee, Chiranjib; Curcio, Stefano

    2015-11-01

    The photocatalytic degradation of chlorhexidine digluconate (CHD), a disinfectant and topical antiseptic and adsorption of CHD catalyst surface in dark condition has been studied. Moreover, the value of kinetic parameters has been measured and the effect of adsorption on photocatalysis has been investigated here. Substantial removal was observed during the photocatalysis process, whereas 40% removal was possible through the adsorption route on TiO2 surface. The parametric variation has shown that alkaline pH, ambient temperature, low initial substrate concentration, high TiO2 loading were favourable, though at a certain concentration of TiO2 loading, photocatalytic degradation efficiency was found to be maximum. The adsorption study has shown good confirmation with Langmuir isotherm and during the reaction at initial stage, it followed pseudo-first-order reaction, after that Langmuir Hinshelwood model was found to be appropriate in describing the system. The present study also confirmed that there is a significant effect of adsorption on photocatalytic degradation. The possible mechanism for adsorption and photocatalysis has been shown here and process controlling step has been identified. The influences of pH and temperature have been explained with the help of surface charge distribution of reacting particles and thermodynamic point of view respectively. PMID:25956186

  7. Direct rate constant measurements for the reaction of ground-state atomic oxygen with ethylene, 244-1052 K

    SciTech Connect

    Klemm, R.B.; Nesbitt, F.L.; Skolnik, E.G.; Lee, J.H.; Smalley, J.F.

    1987-03-12

    The rate constant for the reaction of ground-state atomic oxygen with ethylene was determined by using two techniques: flash photolysis-resonance fluorescence (FP-RF, 244-1052 K) and discharge flow-resonance fluorescence (DF-RF, 298-1017 K). Kinetic complications due to the presence of molecular oxygen in the FP-RF experiments at high temperatures (T > 800 K) were overcome by using NO as the photolytic source of the O atoms. The rate constant, k/sub 1/ (T), derived in this study exhibits extreme non-Arrhenius behavior, but it can be successfully fit to the sum of exponentials expression, 244-1052 K, k/sub 1/(T) = (1.02 +/- 0.06) x 10/sup -11/ exp(-753 +/- 17 K/T) + (2.75 +/- 0.26) x 10/sup -10/ exp(-4220 +/- 550 K/T), in units of cm/sup 3/ molecule/sup -1/ s/sup -1/. Additionally, a fit of the results of this work to a simple transition-state theory expression and the comparison of these results with those of other workers are discussed.

  8. 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.

  9. Within-Pin Reaction Rate Distributions: CASMO-4 and HELIOS Compared Against Tomographic Measurements at the PROTEUS Reactor

    SciTech Connect

    Fauchere, C. Pralong; Murphy, M.; Jatuff, F.; Chawla, R.

    2005-05-15

    In the framework of the LWR-PROTEUS project - an extended validation program for advanced light water reactor core analysis tools conducted at the Paul Scherrer Institute - the radial, internal variations of the total fission rate (F{sub tot}) and the capture rate in {sup 238}U (C{sub 8}) have been calculated for zero-burnup pins of a Westinghouse SVEA-96+ boiling water reactor fuel assembly using two codes, namely, CASMO-4 and HELIOS. While F{sub tot} distributions predicted by CASMO-4 and HELIOS are in good agreement, C{sub 8} distributions show significant inconsistencies (20 to 30%). The calculations are compared with experimental results obtained using single photon emission computerized tomography for several SVEA-96+ pins irradiated in the zero-power reactor PROTEUS. The comparisons confirm the predicted shape of the F{sub tot} distributions within UO{sub 2} pins and clearly indicate that HELIOS within-pin predictions for C{sub 8} are more reliable than CASMO-4 results. This is important for the derivation of gamma-ray self-absorption corrections when pin-integrated reaction rates are to be determined using the gamma-scanning technique. Thus, the use of CASMO-4-type within-pin distributions would lead to 3 to 4% discrepancies in the absolute, self-absorption-corrected pin-integrated values deduced for C{sub 8} and hence for C{sub 8}/F{sub tot}. For relative C{sub 8} distributions, the discrepancy would be much smaller, namely, up to {approx}1% if pins containing a burnable absorber are involved.

  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. Ring-polymer molecular dynamics: Rate coefficient calculations for energetically symmetric (near thermoneutral) insertion reactions (X + H2) ? HX + H(X = C(1D), S(1D))

    NASA Astrophysics Data System (ADS)

    Suleimanov, Yury V.; Kong, Wendi J.; Guo, Hua; Green, William H.

    2014-12-01

    Following our previous study of prototypical insertion reactions of energetically asymmetric type with the RPMD (Ring-Polymer Molecular Dynamics) method [Y. Li, Y. Suleimanov, and H. Guo, J. Phys. Chem. Lett. 5, 700 (2014)], we extend it to two other prototypical insertion reactions with much less exothermicity (near thermoneutral), namely, X + H2 ? HX + H where X = C(1D), S(1D), in order to assess the accuracy of this method for calculating thermal rate coefficients for this class of reactions. For both chemical reactions, RPMD displays remarkable accuracy and agreement with the previous quantum dynamic results that make it encouraging for the future application of the RPMD to other barrier-less, complex-forming reactions involving polyatomic reactants with any exothermicity.

  12. 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

    SciTech Connect

    Zhou, Yong; Zhang, Dong H.

    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 high 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.

  13. Level structure of 30S and its importance in the 26Si(?,p)29P and 29P(p,?)30S reaction rates

    NASA Astrophysics Data System (ADS)

    Almaraz-Calderon, S.; Tan, W. P.; Aprahamian, A.; Beard, M.; Berg, G. P. A.; Bucher, B.; Couder, M.; Görres, J.; O'Brien, S.; Patel, D.; Roberts, A.; Sault, K.; Wiescher, M.; Brune, C. R.; Massey, T. N.; Fujita, K.; Hatanaka, K.; Ishiwaka, D.; Matsubara, H.; Okamura, H.; Ong, H. J.; Sakemi, Y.; Shimizu, Y.; Suzuki, T.; Tameshige, Y.; Tamii, A.; Zenihiro, J.; Kubo, T.; Namiki, Y.; Ohkuma, Y.; Shimbara, Y.; Suzuki, S.; Watanabe, R.; Yamada, R.; Adachi, T.; Fujita, Y.; Fujita, H.; Dozono, M.; Wakasa, T.

    2012-12-01

    The level structure of 30S was studied via the 28Si(3He,n) and 32S(p,t) reactions at the Nuclear Science Laboratory of the University of Notre Dame and the Research Center for Nuclear Physics of the University of Osaka, Japan. Important experimental information on the energy levels, decay branching ratios, and tentative spin assignments is extracted to calculate the reaction rates for 29P(p,?)30S and 26Si(?,p)29P, which play a critical role in the reaction flow in explosive hydrogen burning.

  14. Ring-Polymer Molecular Dynamics for the Prediction of Low-Temperature Rates: An Investigation of the C((1)D) + H2 Reaction.

    PubMed

    Hickson, Kevin M; Loison, Jean-Christophe; Guo, Hua; Suleimanov, Yury V

    2015-11-01

    Quantum mechanical calculations are important tools for predicting the rates of elementary reactions, particularly for those involving hydrogen and at low temperatures where quantum effects become increasingly important. These approaches are computationally expensive, however, particularly when applied to complex polyatomic systems or processes characterized by deep potential wells. While several approximate techniques exist, many of these have issues with reliability. The ring-polymer molecular dynamics method was recently proposed as an accurate and efficient alternative. Here, we test this technique at low temperatures (300-50 K) by analyzing the behavior of the barrierless C((1)D) + H2 reaction over the two lowest singlet potential energy surfaces. To validate the theory, rate coefficients were measured using a supersonic flow reactor down to 50 K. The experimental and theoretical rates are in excellent agreement, supporting the future application of this method for determining the kinetics and dynamics of a wide range of low-temperature reactions. PMID:26538033

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

    E-print Network

    Ismagilov, Rustem F.

    experiments with chemical reactions and blood coagulation Biophysical Journal Authors: Rebecca R. Pompano equation for clotting. Fig. S6. Determination of clot time in a simulated clotting reaction. Fig. S7. In a simulated straight channel with Vel = 1 mm/s, "clotting" (convergence to upper steady state) occurred only

  16. The reactions of N-methylformamide and N,N-dimethylformamide with OH and their photo-oxidation under atmospheric conditions: experimental and theoretical studies.

    PubMed

    Bunkan, Arne Joakim C; Hetzler, Jens; Mikoviny, Tomáš; Wisthaler, Armin; Nielsen, Claus J; Olzmann, Matthias

    2015-03-14

    The reactions of OH radicals with CH3NHCHO (N-methylformamide, MF) and (CH3)2NCHO (N,N-dimethylformamide, DMF) have been studied by experimental and computational methods. Rate coefficients were determined as a function of temperature (T = 260-295 K) and pressure (P = 30-600 mbar) by the flash photolysis/laser-induced fluorescence technique. OH radicals were produced by laser flash photolysis of 2,4-pentanedione or tert-butyl hydroperoxide under pseudo-first order conditions in an excess of the corresponding amide. The rate coefficients obtained show negative temperature dependences that can be parameterized as follows: kOH+MF = (1.3 ± 0.4) × 10(-12) exp(3.7 kJ mol(-1)/(RT)) cm(3) s(-1) and kOH+DMF = (5.5 ± 1.7) × 10(-13) exp(6.6 kJ mol(-1)/(RT)) cm(3) s(-1). The rate coefficient kOH+MF shows very weak positive pressure dependence whereas kOH+DMF was found to be independent of pressure. The Arrhenius equations given, within their uncertainty, are valid for the entire pressure range of our experiments. Furthermore, MF and DMF smog-chamber photo-oxidation experiments were monitored by proton-transfer-reaction time-of-flight mass spectrometry. Atmospheric MF photo-oxidation results in 65% CH3NCO (methylisocyanate), 16% (CHO)2NH, and NOx-dependent amounts of CH2[double bond, length as m-dash]NH and CH3NHNO2 as primary products, while DMF photo-oxidation results in around 35% CH3N(CHO)2 as primary product and 65% meta-stable (CH3)2NC(O)OONO2 degrading to NOx-dependent amounts of CH3N[double bond, length as m-dash]CH2 (N-methylmethanimine), (CH3)2NNO (N-nitroso dimethylamine) and (CH3)2NNO2 (N-nitro dimethylamine). The potential for nitramine formation in MF photo-oxidation is comparable to that of methylamine whereas the potential to form nitrosamine and nitramine in DMF photo-oxidation is larger than for dimethylamine. Quantum chemistry supported atmospheric degradation mechanisms for MF and DMF are presented. Rate coefficients and initial branching ratios calculated with statistical rate theory based on molecular data from quantum chemical calculations at the CCSD(T*)-F12a/aug-cc-pVTZ//MP2/aug-cc-pVTZ level of theory show satisfactory agreement with the experimental results. It turned out that adjustment of calculated threshold energies by 0.2 to 8.8 kJ mol(-1) lead to agreement between experimental and predicted results. PMID:25687949

  17. Measurement of the cross section and reaction rate of lithium-8(deuterium,helium-4)helium-6 reaction at the energies of astrophysical interest

    NASA Astrophysics Data System (ADS)

    Sahin, Latife

    The baryon density of the universe is constrained by comparing the light-element nucleosynthesis yields with observationally determined primordial abundances. Two nucleosynthesis models: Inhomogeneous and Standard, are used to predict the abundances of D, 3He, 4He, and 7Li. However, the constraints on baryon density are not very certain due to the uncertainties on observed or predicted abundances. Thus, the 6Li nuclei may provide an additional constraint on the baryon density since it is observed in metal poor stars. So, we report measuring an upper limit for the cross section of 8Li(d, ?)6He reaction in the energy range Ec.m. = 2.3 to 3.5 MeV using a 8Li-radioactive beam on a CD2 foil. The 6He nuclei produced in the reaction were detected in solid-state detectors. The 8Li(d, ?)6He nuclear reaction may affect the primordial abundance of 6Li in Inhomogeneous Big Bang Nucleosynthesis, since 6Li could be synthesized in IBBN via 6He beta decay to 6Li. However, several Big Bang Nucleosynthesis network calculations were found to be insensitive to this reaction, suggesting that the 8Li(d, ?) 6He reaction does not affect 6Li production.

  18. Comparison of computed reaction rates using different methods and data for the STARFIRE and TMHR benchmark blankets

    SciTech Connect

    Scott, A.J.; Takata, M.L.

    1981-12-01

    RAFFLE Monte Carlo calculations using ENDF/B V5 data have been performed for the TMHR suppressed fission benchmark blanket and the STARFIRE Reference Design blanket. One-dimensional cylindrical geometry was employed. ANISN S/sub N/ calculations were also done for both blankets using the DLC37F, FLUNG, and MACKLIB IV data sets. Reaction rates from RAFFLE and ANISN are compared with each other and with results obtained by the blanket designers (ANL, TRW, GA). The purposes of this study are to: (1) partially validate the new RAFFLE libraries for fusion neutronics and, (2) lend confidence to the results of previous ANISN calculations that were done to investigate the feasibility of fusion blanket testing in the Engineering Test Reactor. For both blankets, the tritium breeding ratio (TBR) predicted by RAFFLE and ANISN agree within 3%. For TMHR, our TBR results lie in between those obtained by TRW and GA, which disagree by 10 to 15%. For STARFIRE, our TBR results are 7 to 10% lower than ANL's values. The reason for the large discrepancies is unknown. However, it is concluded that modeling errors are unlikely so that data sources and processing differences used to generate cross section libraries are implied. Additional investigation is needed to resolve the differences.

  19. Preliminary Comparison of Reaction Rate theory and Object Kinetic Monte Carlo Simulations of Defect Cluster Dynamics under Irradiation

    SciTech Connect

    Stoller, Roger E; Golubov, Stanislav I; Becquart, C. S.; Domain, C.

    2006-09-01

    The multiscale modeling scheme encompasses models from the atomistic to the continuum scale. Phenomena at the mesoscale are typically simulated using reaction rate theory (RT), Monte Carlo (MC), or phase field models. These mesoscale models are appropriate for application to problems that involve intermediate length scales ( m to >mm), and timescales from diffusion (~ s) to long-term microstructural evolution (~years). Phenomena at this scale have the most direct impact on mechanical properties in structural materials of interest to nuclear energy systems, and are also the most accessible to direct comparison between the results of simulations and experiments. Recent advances in computational power have substantially expanded the range of application for MC models. Although the RT and MC models can be used simulate the same phenomena, many of the details are handled quite differently in the two approaches. A direct comparison of the RT and MC descriptions has been made in the domain of point defect cluster dynamics modeling, which is relevant to both the nucleation and evolution of radiation-induced defect structures. The relative merits and limitations of the two approaches are discussed, and the predictions of the two approaches are compared for specific irradiation conditions.

  20. Investigation of heating rate effect on solid-phase interaction in Li2CO3 - Fe2O3 reaction mixture

    NASA Astrophysics Data System (ADS)

    Lysenko, E. N.; Nikolaev, E. V.; Vasendina, E. A.

    2015-04-01

    The influence of heating rate on solid-phase interaction in Li2CO3 - Fe2O3 reaction mixture was investigated by thermal analysis method. The powder mixture components were in the ratio corresponding to LiFe5O8 ferrite. The ferrite synthesis was performed by thermal heating of mixture reagents in thermal analyzer up to 800 °C in air at various heating rates in the ranges (5-50) °C/min. The results showed that the heating rate affects the solid-phase interaction in Li2CO3 - Fe2O3 reaction mixture. The reaction phase formation is accompanied by heat endothermic effect, which was observed in the DSC curve in the form of a complex broad peak. For all samples, this complex peaks were decomposed into simpler peaks, and thereby, the enthalpies of the individual phase transitions were determined. It was shown that the heating rate affects the values of enthalpy and temperatures of heat endothermic effects, so that the high heating rate shifts the proceeding of reaction to higher temperatures.