Sample records for pseudo-first-order reaction rate

  1. Pseudo-first-order reaction of chemically and biologically formed green rusts with HgII and C??H??N?O?: effects of pH and stabilizing agents (phosphate, silicate, polyacrylic acid, and bacterial cells).

    PubMed

    Remy, P-Ph; Etique, M; Hazotte, A A; Sergent, A-S; Estrade, N; Cloquet, C; Hanna, K; Jorand, F P A

    2015-03-01

    The kinetics of Hg(II) and methyl red (MR) reduction by hydroxycarbonate green rust (GR1) and by hydroxysulfate green rust (GR2) were studied in the presence of naturally occurring organic and inorganic ligands (phosphate, polyacrylic acid, bacterial cells, silicate). The reducing ability of biogenic hydroxycarbonate green rust (GR1bio), obtained after microbial reduction of lepidocrocite by Shewanella putrefaciens, was also investigated and compared to those of chemically synthesized GR1 and GR2 (GR1ab and GR2ab). Pseudo first-order rate constants (kobs) of Hg(II) reduction (at pH 7.0, 8.2, and 9.5) and MR reduction (at pH 7.0) were determined and were normalized to the structural Fe(II) content of GRs (kFeII) and to the estimated concentration of surface Fe(II) sites (kS). The kS values ranged from 0.3 L mmol(-1) min(-1) to 43 L mmol(-1) min(-1) for the Hg reduction, and from 0.007 L mmol(-1) min(-1) to 3.4 L mmol(-1) min(-1) for the MR reduction. No significant discrepancy between GRab and GRbio was observed in term of reactivity. However, the reduction kinetics of MR was generally slower than the Hg(II) reduction kinetics for all tested GRs. While a slight difference in Hg(II) reduction rate was noted whatever the pH values (7.0, 8.2, or 9.5), the reduction of MR was significantly affected in the presence of ligands. A decrease by a factor of 2-200, depending on the type of ligand used, was observed. These data give new insights into the reactivity of GRs in the presence of co-occurring organic and inorganic ligands, and have major implications in the characterization of contaminated systems as well as water treatment processes. PMID:25543237

  2. Four-dimensional polymer collapse: Pseudo-first-order transition in interacting self-avoiding walks

    E-print Network

    Prellberg, Thomas

    Four-dimensional polymer collapse: Pseudo-first-order transition in interacting self-avoiding walks provided the first evidence that the collapse, or coil-globule transition of an isolated polymer, the canonical lattice model of polymer collapse, namely, interacting self-avoiding walks, to show

  3. Rate coefficient measurements for the reaction OH + ClO â products

    Microsoft Academic Search

    Carla S. Kegley-Owen; Mary K. Gilles; James B. Burkholder; A. R. Ravishankara

    1999-01-01

    The rate coefficient for the reaction OH + ClO â products (1) was measured under pseudo-first-order conditions in OH. A discharge flow system was used to produce ClO, and its concentration was measured by UV\\/visible absorption. OH was produced by pulsed laser photolysis of Oâ (or ClO) at 248 nm in the presence of HâO and was monitored by laser-induced

  4. Rate constant for the reaction of ozone with diethyl sulfide

    NASA Astrophysics Data System (ADS)

    Du, Lin; Xu, Yongfu; Ge, Maofa; Jia, Long

    The rate constant for the reaction of diethyl sulfide (DES; C 2H 5SC 2H 5) with ozone was determined for the first time, which was (2.77±0.27)×10 -19 cm 3 molecule -1 s -1 under a room temperature of (289±1) K. Experiments were conducted under supposedly pseudo-first-order decay conditions, keeping [DES] 0>50[O 3] 0, but having different combinations of [DES] 0 and [O 3] 0. Cyclohexane was added into the reactor to eliminate the effect of OH radicals. The wall decay of ozone and the role of cyclohexane were also discussed in the present work.

  5. 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.

  6. Rate coefficient measurements for the reaction OH + ClO {yields} products

    SciTech Connect

    Kegley-Owen, C.S.; Gilles, M.K.; Burkholder, J.B.; Ravishankara, A.R. [National Oceanic and Atmospheric Administration, Boulder, CO (United States). Aeronomy Lab.] [National Oceanic and Atmospheric Administration, Boulder, CO (United States). Aeronomy Lab.; [Univ. of Colorado, Boulder, CO (United States). Cooperative Inst. for Research in Environmental Sciences

    1999-07-01

    The rate coefficient for the reaction OH + ClO {yields} products (1) was measured under pseudo-first-order conditions in OH. A discharge flow system was used to produce ClO, and its concentration was measured by UV/visible absorption. OH was produced by pulsed laser photolysis of O{sub 3} (or ClO) at 248 nm in the presence of H{sub 2}O and was monitored by laser-induced fluorescence. The value of {kappa}{sub 1} between 234 and 356 K is given by {kappa}{sub 1}(T) = (8.9 {+-} 2.7) {times} 10{sup {minus}12} exp[(295 {+-} 95)/T] cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, where uncertainties are 95% confidence limits and include estimated systematic uncertainties. Their value is compared with those from previous investigations.

  7. Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

    1984-01-01

    The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

  8. Polychlorinated ethane reaction with zero-valent zinc: pathways and rate control

    NASA Astrophysics Data System (ADS)

    Arnold, William A.; Ball, William P.; Roberts, A. Lynn

    1999-12-01

    Efficient design of zero-valent metal permeable `barriers' for the reduction of organohalides requires information regarding the pertinent reaction rates as well as an understanding of the resultant distribution of products. In this study, the pathways and kinetics for reaction of polychlorinated ethanes with Zn(0) have been examined in batch reactors. Reductive ?-elimination was the only route through which hexachloroethane (HCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,2-trichloroethane (1,1,2-TCA) and 1,2-dichloroethane (1,2-DCA) reacted. Pentachloroethane (PCA) reacted via concurrent reductive ?-elimination (93%) and hydrolysis (7%). As previously demonstrated, 1,1,1-trichloroethane (1,1,1-TCA) and 1,1-dichloroethane (1,1-DCA) reacted predominantly via reductive ?-elimination. Attempts to correlate BET surface area-normalized rate constants ( kSA-BET) with one-electron reduction potential ( E1) met with limited success, as HCA, PCA, 1,1,1,2-TeCA, and 1,1,1-TCA reacted at nearly identical rates despite substantial differences in E1 values. Comparison of the pseudo-first-order rate constants ( kobs) for these species with rate constants ( kLa) obtained from a correlation for mass transfer to suspended particles revealed that the reaction of these species was mass transfer limited even though reaction rates were unaffected by mixing speed. Calculations suggest that mass transfer limitations may also play a role in the design of treatment systems for highly reactive species, with overall rate constants predicted to increase with flow velocity.

  9. Absolute rate constant for the reaction of O(3P) with CH3SSCH3 from 270 to 329 K

    NASA Astrophysics Data System (ADS)

    Lee, Jai H.; Tang, I. N.

    1980-05-01

    Rate constants for the oxidation reactions of organic sulfur compounds have become increasingly important due to the potential role of these compounds in the formation of tropospheric and stratospheric sulfate aerosols. The present study deals with the reaction of the ground state oxygen atom with dimethyl disulfide (DMDS). The discharge fast flow-resonance fluorescence technique was used to monitor the decay of O(3P) concentration in the presence of excess CH3SSCH3 under pseudo-first-order conditions. Over a temperature range from 270 to 329 K, and a pressure range from 0.52 to 2.60 Torr, no variation of the rate constant with temperature and pressure was observed. The results are best represented by the temperature and pressure independent value of (2.12±0.22)×10-10 cm3 molecule-1 s-1, which is about one-half the theoretical collision frequency. The zero activation energy for this reaction is discussed in terms of the temperature dependence of other sulfur compound-oxygen atom reactions reported in the literature.

  10. Rates of Chemical Reactions

    NSDL National Science Digital Library

    National Science Teachers Association (NSTA)

    1900-01-01

    Science Objects are two hour on-line interactive inquiry-based content modules that help teachers better understand the science content they teach. This Science Object is the third of four Science Objects in the Chemical Reactions SciPack. It demonstrates

  11. 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.

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

    EPA Science Inventory

    Quantitative structure-activity relationships (QSARs) are developed relating initial and final pseudo-first-order disappearance rate constants of 45 halogenated aromatic hydrocarbons in anoxic sediments to four readily available molecular descriptors: the carbon-halogen bond stre...

  13. Thermochemical pretreatment of lignocellulose to enhance methane fermentation. I. Monosaccharide and furfurals hydrothermal decomposition and product formation rates

    Microsoft Academic Search

    Kent D. Baugh; Perry L. McCarty

    1988-01-01

    Over a pH range 1-4 and temperatures from 170 to 230°C, the decomposition rates of xylose, galactose, mannose, glucose, 2-furfural, and 5-hydroxymethyl-2-furfural (5-HMF) were pseudo first order. The effect of temperature and pH on the pseudo first-order decomposition rate constants was modeled using the Arrhenius equation and acid-base catalysis, respectively. Decomposition rates of the monosaccharides were minimum at a pH

  14. 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...

  15. The rate constant of the reaction NCN + H2 and its role in NCN and NO modeling in low pressure CH4/O2/N2-flames.

    PubMed

    Faßheber, Nancy; Lamoureux, Nathalie; Friedrichs, Gernot

    2015-06-28

    Bimolecular reactions of the NCN radical play a key role in modeling prompt-NO formation in hydrocarbon flames. The rate constant of the so-far neglected reaction NCN + H2 has been experimentally determined behind shock waves under pseudo-first order conditions with H2 as the excess component. NCN3 thermal decomposition has been used as a quantitative high temperature source of NCN radicals, which have been sensitively detected by difference UV laser absorption spectroscopy at [small nu, Greek, tilde] = 30383.11 cm(-1). The experiments were performed at two different total densities of ?? 4.1 × 10(-6) mol cm(-3) and ?? 7.4 × 10(-6) mol cm(-3) (corresponding to pressures between p = 324 mbar and p = 1665 mbar) and revealed a pressure independent reaction. In the temperature range 1057 K < T < 2475 K, the overall rate constant can be represented by the Arrhenius expression k/(cm(3) mol(-1) s(-1)) = 4.1 × 10(13) exp(-101 kJ mol(-1)/RT) (?log?k = ±0.11). The pressure independent reaction as well as the measured activation energy is consistent with a dominating H abstracting reaction channel yielding the products HNCN + H. The reaction NCN + H2 has been implemented together with a set of reactions for subsequent HNCN and HNC chemistry into the detailed GDFkin3.0_NCN mechanism for NOx flame modeling. Two fuel-rich low-pressure CH4/O2/N2-flames served as examples to quantify the impact of the additional chemical pathways. Although the overall NCN consumption by H2 remains small, significant differences have been observed for NO yields with the updated mechanism. A detailed flux analysis revealed that HNC, mainly arising from HCN/HNC isomerization, plays a decisive role and enhances NO formation through a new HNC ? HNCO ? NH2? NH ? NO pathway. PMID:26017854

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

    PubMed

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

    2011-09-29

    Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-CF(3)CH?CHCF(3) (cis-1,1,1,4,4,4-hexafluoro-2-butene) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis (PLP) to produce OH and laser-induced fluorescence (LIF) to detect it. Rate coefficients were measured over a range of temperatures (212-374 K) and bath gas pressures (20-200 Torr; He, N(2)) and found to be independent of pressure over this range of conditions. The rate coefficient has a non-Arrhenius behavior that is well-described by the expression k(1)(T) = (5.73 ± 0.60) × 10(-19) × T(2) × exp[(678 ± 10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (4.91 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1) and the uncertainties are at the 2? level and include estimated systematic errors. Rate coefficients for the analogous OD radical reaction were determined over a range of temperatures (262-374 K) at 100 Torr (He) to be k(2)(T) = (4.81 ± 0.20) × 10(-19) × T(2) × exp[(776 ± 15)/T], with k(2)(296 K) = (5.73 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1). OH radical rate coefficients were also measured at 296, 345, and 375 K using a relative rate technique and found to be in good agreement with the PLP-LIF results. A room-temperature rate coefficient for the O(3) + (Z)-CF(3)CH?CHCF(3) reaction was measured using an absolute method with O(3) in excess to be <6 × 10(-21) cm(3) molecule(-1) s(-1). The atmospheric lifetime of (Z)-CF(3)CH?CHCF(3) due to loss by OH reaction was estimated to be ~20 days. Infrared absorption spectra of (Z)-CF(3)CH?CHCF(3) measured in this work were used to determine a (Z)-CF(3)CH?CHCF(3) global warming potential (GWP) of ~9 for the 100 year time horizon. A comparison of the OH reactivity of (Z)-CF(3)CH?CHCF(3) with other unsaturated fluorinated compounds is presented. PMID:21879770

  17. 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.

  18. Astrophysical Reaction Rates From Statistical Model Calculations

    Microsoft Academic Search

    Thomas Rauscher; Friedrich-Karl Thielemann

    2000-01-01

    Theoretical reaction rates in the temperature range 0.01×109?T(K)?10.0×109 are calculated in the statistical model (Hauser–Feshbach formalism) for targets with 10?Z?83 (Ne to Bi) and for a mass range reaching the neutron and proton driplines. Reactions considered are (n, ?), (n, p), (n, ?), (p, ?), (p, ?), (?, ?), and their inverse reactions. Reaction rates as a function of temperature

  19. Study of reaction processes by in-line near-infrared spectroscopy in combination with multivariate curve resolution Esterification of myristic acid with isopropanol.

    PubMed

    Blanco, Marcelo; Castillo, Miguel; Beneyto, Rafael

    2007-04-30

    The acid-catalysed esterification of myristic acid with isopropanol was studied by using near-infrared spectroscopy (NIR) in combination with soft-modeling curve resolution (MCR) methodology with a view to establishing the effect of experimental variables on the reaction kinetics. The reaction was conducted at temperatures above the boiling point of the alcohol, with continuous addition of an isopropanol/water mixture to the reactor. Spectral and concentration profiles were determined by applying soft-modeling curve resolution methodology to a column-wise augmented data matrix containing the spectra for the pure components. MCR profiles were compared with reference values and found to depart from then by less than 3% as %RSE for concentrations and to exhibit correlation above 0.999 for spectra. The reaction kinetics as estimated from the concentration profiles was found to be pseudo-first-order. Also, the pseudo-first-order rate constant was found to depend on the flow-rate of the isopropanol/water mixture and its water content; although the constant decreased with increase in the proportion of water, a content of ca. 15% could be used without important retarding effects on the kinetics. The proposed NIR-MCR method allows the rate constant and the influence of the initial water content to be determined with a view to minimizing consumption of the raw materials and optimizing the experimental conditions. PMID:19071649

  20. pH & Rate of Enzymatic Reactions.

    ERIC Educational Resources Information Center

    Clariana, Roy B.

    1991-01-01

    A quantitative and inexpensive way to measure the rate of enzymatic reaction is provided. The effects of different pH levels on the reaction rate of an enzyme from yeast are investigated and the results graphed. Background information, a list of needed materials, directions for preparing solutions, procedure, and results and discussion are…

  1. Thermochemical pretreatment of lignocellulose to enhance methane fermentation. I. Monosaccharide and furfurals hydrothermal decomposition and product formation rates

    SciTech Connect

    Baugh, K.D.; McCarty, P.L.

    1988-01-01

    Over a pH range 1-4 and temperatures from 170 to 230/sup 0/C, the decomposition rates of xylose, galactose, mannose, glucose, 2-furfural, and 5-hydroxymethyl-2-furfural (5-HMF) were pseudo first order. The effect of temperature and pH on the pseudo first-order decomposition rate constants was modeled using the Arrhenius equation and acid-base catalysis, respectively. Decomposition rates of the monosaccharides were minimum at a pH 2-2.5. Above pH 2.5, the monosaccharide decomposition was base catalyzed, with acid catalysis occurring at a pH of less than 2 for glucose. The furfurals were subject to acid catalysis at below ca. pH 3.5. The hydrothermal conversion of glucose to its decomposition products during thermochemical pretreatment can be modeled as a combination of series and parallel reactions. The formation rates of identified soluble products from glucose decomposition, 5-HMF and levulinic acid, were also functions of temperature and pH. The rate of 5-HMF formation relative to glucose decomposition decreased as the pH increased from 2.0 to 4.0, with levulinic acid formation only detected when the pH was 2.5 or less. For glucose decomposition, humic solids accounted for ca. 20% of the decomposition products.

  2. Proton inventory investigations of acyl transfer reactions: transition state structures

    E-print Network

    Patterson, Jacob Floyd

    1978-01-01

    The mechanism of the imidazole-catalyzed hydrolysis of N-acetyl- imidazole has been investigated using the proton inventory technique. The linear proton inventory (a plot of the rate constant versus the atom fraction of deuterium in the solvent mixture... 70 70 71 72 74 75 77 TABLE IV VI VII VIII IX XI XII LIST OF TABLES Pseudo-First Order Rate Constants for the Imidazole- Catalyzed Hydrolysis of N-acetylimidazole at pH 7, 25. 00+0, 05'C and n = 0. 000 Pseudo-First Order Rate...

  3. COMPUTERIZED EXTRAPOLATION OF HYDROLYSIS RATE DATA

    EPA Science Inventory

    The program RATE was developed to aid in the extrapolation and interpretation of hydrolysis rate data to a format that is useful for environmental risk assessment. ydrolysis data typically are reported in the literature as pseudo-first-order rate constants at the temperature and ...

  4. Astrophysical Reaction Rates Obtained By Indirect Techniques

    SciTech Connect

    Tribble, R. E.; Al-Abdullah, T.; Alharbi, A.; Banu, A.; Chen, X.; Clark, H. L.; Fu, C.; Gagliardi, C. A.; Hardy, J. C.; Iacob, V. E.; Lui, Y.-W.; McCleskey, M.; Mukhamedzhanov, A.; Nica, N.; Park, H. I.; Roeder, B.; Simmons, E.; Tabacaru, G.; Tokimoto, Y.; Trache, L. [Cyclotron Institute, Texas A and M University, College Station, TX 77843 (United States)

    2010-08-12

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

  5. Neutron capture reaction rates for stellar nucleosynthesis

    SciTech Connect

    Mengoni, A. [Department of Nuclear Sciences and Applications, Division of Physical and Chemical Sciences, Nuclear Data Section, International Atomic Energy Agency, A-1400 Wagramer Strasse 5, Vienna (Austria)

    2006-03-13

    A short summary of the three fundamental neutron capture reaction processes of interest in stellar nucleosynthesis is presented. Three examples of actual situations in which the capture reaction proceeds through one of these processes are identified and an overview of the experimental data as well as of the model calculations used in the determination of the capture rates are presented.

  6. Rate constant for the Cl + Chloroform reaction

    SciTech Connect

    Brahan, K.M.; Hewitt, A.D.; Boone, G.D. [California State Univ., Fullerton, CA (United States)] [and others

    1995-12-01

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

  7. 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.

  8. How is entropy production rate related to chemical reaction rate?

    E-print Network

    Banerjee, Kinshuk

    2013-01-01

    The entropy production rate is a key quantity in irreversible thermodynamics. In this work, we concentrate on the realization of entropy production rate in chemical reaction systems in terms of the experimentally measurable reaction rate. Both triangular and linear networks have been studied. They attain either thermodynamic equilibrium or a non-equilibrium steady state, under suitable external constraints. We have shown that the entropy production rate is proportional to the square of the reaction velocity only around equilibrium and not any arbitrary non-equilibrium steady state. This feature can act as a guide in revealing the nature of a steady state, very much like the minimum entropy production principle. A discussion on this point has also been presented.

  9. Critical reaction rates in hypersonic combustion chemistry

    SciTech Connect

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

    1989-01-01

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

  10. 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.

  11. 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.

  12. 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.

  13. Rate coefficient for the reaction N + NO

    Microsoft Academic Search

    J. L. Fox

    1994-01-01

    Evidence has been advanced that the rate coefficient for the reaction N + NO â Nâ + O has a small positive temperature dependence at the high temperatures (900-1500 K) that prevail in the terrestrial middle and upper thermosphere by Siskind and Rusch, and at the low temperatures (100-200 K) of the Martian lower thermosphere by Fox. Assuming that the

  14. Thermonuclear reaction rates from statistical model calculations

    Microsoft Academic Search

    Friedrich-Karl Thielemann; James W. Truran; Marcel Arnould

    1986-01-01

    The quality of statistical model predictions for thermonuclear reaction rates is based on the accuracy of theoretical determinations of particle and photon transmission coefficients as well as that of the level densities of excited states in nuclei. The square well potentials for neutrons, protons, and alpha particles, used in previous approaches, have been replaced in this work by realistic optical

  15. Thermonuclear Reaction Rates for Solar Neutrino Processes

    SciTech Connect

    Karathanou, G. I.; Tsikoudi, V.; Kosmas, T. S. [Theoretical Physics Section, University of Ioannina, GR 45110 Ioannina (Greece); Liolios, Th. [Hellenic Army Academy, Department of Physical Sciences and Applications, Vari, GR 16673, Attica (Greece)

    2008-01-24

    Using the formalism for the effective cross-section factor S{sub eff} we calculate the thermonuclear reaction rates and neutrino fluxes for the pp-chain processes. We adopt the recent LUNA experimental data for the nuclear cross-section S-factor and we compute improved and updated solar neutrino fluxes which we compare with those previously obtained.

  16. Electric field heating and reaction rate effects

    Microsoft Academic Search

    S. M. A. Ibrahim; D. Bradley

    1986-01-01

    The effects are described of electrical fields upon heating and reaction rates of the reacting gases of methane-air and methane-oxygen in the recirculation zone of a jet-stirred reactor. The effects of thermal and field gas heatings on concentrations of CO and COâ were also studied. The experiments included measurements of gas temperature distribution across the reactor, current-voltage characteristics for dc

  17. Pycnonuclear reaction rates for binary ionic mixtures

    NASA Technical Reports Server (NTRS)

    Ichimaru, S.; Ogata, S.; Van Horn, H. M.

    1992-01-01

    Through a combination of compositional scaling arguments and examinations of Monte Carlo simulation results for the interparticle separations in binary-ionic mixture (BIM) solids, we have derived parameterized expressions for the BIM pycnonuclear rates as generalizations of those in one-component solids obtained previously by Salpeter and Van Horn and by Ogata et al. We have thereby discovered a catalyzing effect of the heavier elements, which enhances the rates of reactions among the lighter elements when the charge ratio exceeds a critical value of approximately 2.3.

  18. Rate coefficient for the reaction N + NO

    NASA Technical Reports Server (NTRS)

    Fox, J. L.

    1994-01-01

    Evidence has been advanced that the rate coefficient for the reaction N + NO right arrow N2 + O has a small positive temperature dependence at the high temperatures (900 to 1500 K) that prevail in the terrestrial middle and upper thermosphere by Siskind and Rusch (1992), and at the low temperatures (100 to 200 K) of the Martian lower thermosphere by Fox (1993). Assuming that the rate coefficient recommended by the Jet Propulsion Laboratory evaluation (DeMore et al., 1992) is accurate at 300 K, we derive here the low temperature value of the activation energy for this reaction and thus the rate coefficient that best fits the Viking 1 measured NO densities. We find that the fit is acceptable for a rate coefficient of about 1.3 x 10(exp -10)(T/300)(exp 0.5)exp(-400/T) and better for a value of about 2.5 x 10(exp -10)(T/300)(exp 0.5)exp(-600/T)cu cm/s.

  19. Physical chemistry of the carbothermic reduction of alumina in the presence of a metallic solvent: Part II. Measurements of kinetics of reaction

    NASA Astrophysics Data System (ADS)

    Frank, Robert A.; Finn, Charles W.; Elliott, John F.

    1989-04-01

    The carbothermic reduction of alumina was studied in the temperature range of 1700°C to 1850°C in the presence of either tin or copper as the metallic solvent. The total pressure in the smelting system was controlled at pressures between 0.08 and 0.20 atm. The overall reaction is Al2O3(s)+3C(s)=2 Al+3CO(g). The rate of reduction of alumina was found to depend strongly on temperature, increasing by three orders of magnitude between 1700°C and 1850°C. Total pressure and activity of aluminum in the solvent bath also affected the rate of reduction. Changes in the alumina particle type and size, in the carbon type, in the carbon-to-oxygen ratio, and in the pellet size had little effect on the rate of reduction of alumina. The kinetics of reduction are shown to follow a pseudo-first order kinetic model.

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

    NASA Technical Reports Server (NTRS)

    Bangert, L. H.

    1975-01-01

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

  1. Fusion Reaction Rate in an Inhomogeneous Plasma

    SciTech Connect

    S. Son; N.J. Fisch

    2004-09-03

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

  2. 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

  3. Photochemical reactions of anthropogenic chemicals in seawater

    SciTech Connect

    Toole, A.P.; Crosby, D.G. (Univ. of California, Davis (USA))

    1988-09-01

    Sunlight-driven, photochemical reactions can be a major degradative force for anthropogenic organic compounds in the aquatic environment. Chlorinated phenols, various classes of pesticides, and polycyclic aromatic hydrocarbons are among some examples of the compounds shown to be degraded by sunlight. Most environmental photochemistry has been studied in fresh water, despite the fact that the oceans cover more than 70% of the earths surface and receive large inputs of anthropogenic chemicals via atmospheric transport, runoff, and coastal outfalls. This fact, along with increasing pressure for ocean waste disposal as land options dwindle, present a need for information on the photochemical reactions of anthropogenic organic chemicals in seawater. Several probable seawater pollutants were selected as probes for studying photochemical reactions including, 2-nitrotoluene, 4-nitrotoluene, styrene, 4,5-dichloroguaiacol, 4,5,6-trichloroguaiacol and tetrachloroguaiacol. Dilute solutions of each probe were prepared in buffered (pH 8), distilled water (DW), synthetic seawater (SSW) and natural seawater (NSW), then irradiated in a temperature-controlled photoreactor fitted with a General Electric F40BL fluorescent lamp to simulate sunlight. Samples were taken at regular intervals, concentrated using solid phase extraction techniques and analyzed by gas chromatography. Photolysis rates were determined assuming first, or pseudo-first, order kinetics. Photoproducts were identified by gas chromatography;mass spectrometry and confirmed by comparison to standards when available. By determining rates in DW containing selected components of SSW, at SSW concentrations, the inorganic compounds mediating the photochemical reactions in seawater could be determined.

  4. 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…

  5. Conjugate mass transfer to a spherical drop accompanied by a second-order chemical reaction inside the drop

    Microsoft Academic Search

    Gh Juncu

    2002-01-01

    Conjugate mass transfer between a drop and a surrounding fluid flow with second-order (inclusive the particular case – pseudo-first-order), irreversible chemical reaction in the dispersed phase has been analyzed. The dispersed phase reactant is insoluble in the continuous phase and its complete depletion is allowed. Two sphere models were considered: the rigid sphere and the fluid sphere with internal circulation.

  6. Nuclear Reaction Rates in a Plasma

    E-print Network

    Lowell S. Brown; R. F. Sawyer

    1997-02-26

    The problem of determining the effects of the surrounding plasma on nuclear reaction rates in stars is formulated ab initio, using the techniques of quantum statistical mechanics. We derive a result that expresses the complete effects of Coulomb barrier penetration and of the influence of the surrounding plasma in terms of matrix elements of well defined operators. We find that possible "dynamical screening" effects that have been discussed in the literature are absent. The form of our results suggests that an approach that relies on numerical calculations of the correlation functions in a classical Coulomb gas, followed by construction of an effective two body potential and a quantum barrier penetration calculation, will miss physics that is as important as the physics that it includes.

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

    PubMed

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

    2010-04-01

    Rate coefficients, k, for the gas-phase reaction of the OH radical with CH(2)=CHF (k(1)) and CH(2)=CF(2) (k(2)) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH and laser-induced fluorescence (PLP-LIF) to detect it. Rate coefficients were measured over a range of temperature (220-373 K) and bath gas pressure (20-600 Torr; He, N(2)). The rate coefficients were found to be independent of pressure. The measured rate coefficient for reaction 1 at room temperature was k(1)(296 K) = (5.18 +/- 0.50) x 10(-12) cm(3) molecule(-1) s(-1), independent of pressure, and the temperature dependence is given by the Arrhenius expression k(1)(T) = (1.75 +/- 0.20) x 10(-12) exp[(316 +/- 25)/T] cm(3) molecule(-1) s(-1); the rate coefficients for reaction 2 were k(2)(296 K) = (2.79 +/- 0.25) x 10(-12) cm(3) molecule(-1) s(-1) and k(2)(T) = (1.75 +/- 0.20) x 10(-12) exp[(140 +/- 20)/T] cm(3) molecule(-1) s(-1). The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors. The fall-off parameters for reaction 2 of k(infinity) = 3 x 10(-12) cm(3) molecule(-1) s(-1) and k(0)(296 K) = 1.8 x 10(-28) cm(6) molecule(-2) s(-1) with F(c) = 0.6 reproduce the room temperature data obtained in this study combined with the low pressure rate coefficient data from Howard (J. Chem. Phys. 1976, 65, 4771). OH radical formation was observed for reactions 1 and 2 in the presence of O(2), and the mechanism was investigated using (18)OH and OD rate coefficient measurements with CH(2)=CHF and CH(2)=CF(2) over a range of temperature (260-373 K) and pressure (20-100 Torr, He). Quantum chemical calculations using density functional theory (DFT) were used to determine the geometries and energies of the reactants and adducts formed in reactions 1 and 2 and the peroxy radicals formed following the addition of O(2). The atmospheric lifetimes of CH(2)=CHF and CH(2)=CF(2) due to loss by reaction with OH are approximately 2 and 4 days, respectively. Infrared absorption spectra of CH(2)=CHF and CH(2)=CF(2) were measured, and global warming potentials (GWP) values of 0.7 for CH(2)=CHF and 0.9 for CH(2)=CF(2) were obtained for the 100 year time horizon. PMID:20225809

  8. Dependence of Up-scaled Reaction Rate on Flow Rate in Porous Media

    E-print Network

    New York at Stoney Brook, State University of

    model simulations of anorthite and kaolinite reactions in two sandstone pore networks under acidic and investigate the dependence of the observed reaction rates on flow rate. For the anorthite reaction which-scaling of reactive flow, employing it to study up-scaling of anorthite and kaolinite reaction rates in the context

  9. Temporal Scaling of Biogeochemical Reaction Rates

    NASA Astrophysics Data System (ADS)

    Rothman, D. H.; Forney, D. C.

    2007-12-01

    In at least two disparate areas of organic and inorganic geochemistry---the microbial degradation of detritus and the dissolution of minerals in sediments and soils---apparent rate constants k have been observed to diminish with the "age" t of the substrate like k(t) ~eq a t-b, where a ~eq 0.2 and b ~eq 1.0. Published reports display up to ten orders of magnitude in time [1,2]. Because the accuracy of biogeochemical models typically depends crucially on the specification of such rates, an understanding of this scaling law has important implications for predicting the evolution of biogeochemical cycles, especially the cycles of carbon and oxygen. The power-law decay of rates likely derives from a combination of chemical and physical heterogeneity. In a purely chemical scenario, an intrinsically heterogeneous substrate (e.g., a mixture of organic matter ranging from "labile" to "recalcitrant") is assumed to produce the observed slowdown of k(t). In contrast, a physical model assumes a homogeneous substrate in which rates nevertheless vary microscopically due to spatially varying physical constraints. Here we consider the extreme case of a purely physical origin and test its consistency with observations [3]. We first show how a diffusion-limited reaction-diffusion system leads to a logarithmic decay of the substrate. We then show how the power-law for k(t) derives from this logarithmic decay. We obtain not only the correct exponent b=1 but also a good approximation of the prefactor a. By constructing an extensive database of previously published measurements, we show that observations compare well to predictions. The particular way in which diffusion-limitation manifests itself varies from problem to problem. In the case of detrital decay in sediments, we suggest that rates are limited by contact of substrate with extracellular enzymes [3]. Mechanisms in soils are likely similar. For mineral dissolution is sediments, we suggest that rates are limited by diffusion of reactants from the seafloor. [1] J.~J.~Middelburg, Geochim.~Cosmochim.~Acta 53, 1577 (1989). [2] K.~Maher, D.~J.~DePaolo, J.~C.-F.~Lin, Geochim.~Cosmochim.~Acta 68, 4629. [3] D.~H.~Rothman and D.~C.~Forney, Science 316, 1325 (2004).

  10. Micellar Effects on the Reaction S2 O8 2- + Fe(CN)4 (bpy)2-

    PubMed

    Rodriguez; Graciani; Moya

    1997-07-01

    The reaction Fe(CN)4 (bpy)2- + S2 O8 2- has been studied in aqueous solutions of hexadecyltrimethylammonium chloride (CTAC) and bromide (CTAB), sodium dodecyl sulfate (SDS), dodecyl tricosaoxyethylene glycol ether (Brij35 ), and octylphenol(ethyleneoxide)9.5 ether (Triton X-100). The influence of changes in surfactant concentration on the reaction rate has been investigated. Experimental kinetic data show that the reaction rate is not affected by the presence of SDS, Brij35 , and Triton X-100 in the reaction medium within the surfactant concentration range studied. In CTAC and CTAB solutions the observed first order rate constant is much higher than that obtained in pure water, which can be explained by considering that the two anionic reactants are localized at the positively charged micellar surface. This is also in agreement with the observed decrease in the reaction rate when [cationic surfactant] increases. An increase in the surfactant concentration would provoke a decrease in the local concentration of the reagent in excess, S2 O8 2- ions, at the micellar surface, that is, at the reaction site, which would result in a decrease of the observed pseudo-first-order rate constant. Temperature was maintained at 298.2 K. PMID:9241204

  11. SENSITIVITY OF ASTROPHYSICAL REACTION RATES TO NUCLEAR UNCERTAINTIES

    SciTech Connect

    Rauscher, T. [Department of Physics, University of Basel, CH-4056 Basel (Switzerland)

    2012-08-01

    Sensitivities of nuclear reaction rates to a variation of nuclear properties are studied. Target nuclei range from proton- to neutron dripline for 10 {<=} Z {<=} 83. Reactions considered are nucleon- and {alpha}-induced reactions mediated by strong interaction. The contribution of reactions occurring on the target ground state to the total stellar rate is also given. General dependencies on various input quantities are discussed. Additionally, sensitivities of laboratory cross-sections of nucleon-, {alpha}-, and {gamma}-induced reactions are shown, allowing us to estimate the impact of cross-section measurements. Finally, recommended procedures to explore and improve reaction rate uncertainties using the present sensitivity data are outlined.

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

    PubMed

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

    2013-06-01

    Butanol (C4H9OH) is a potential biofuel alternative in fossil fuel gasoline and diesel formulations. The usage of butanol would necessarily lead to direct emissions into the atmosphere; thus, an understanding of its atmospheric processing and environmental impact is desired. Reaction with the OH radical is expected to be the predominant atmospheric removal process for the four aliphatic isomers of butanol. In this work, rate coefficients, k, for the gas-phase reaction of the n-, i-, s-, and t-butanol isomers with the OH radical were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to monitor its temporal profile. Rate coefficients were measured over the temperature range 221-381 K at total pressures between 50 and 200 Torr (He). The reactions exhibited non-Arrhenius behavior over this temperature range and no dependence on total pressure with k(296 K) values of (9.68 ± 0.75), (9.72 ± 0.72), (8.88 ± 0.69), and (1.04 ± 0.08) (in units of 10(-12) cm(3) molecule(-1) s(-1)) for n-, i-, s-, and t-butanol, respectively. The quoted uncertainties are at the 2? level and include estimated systematic errors. The observed non-Arrhenius behavior is interpreted here to result from a competition between the available H-atom abstraction reactive sites, which have different activation energies and pre-exponential factors. The present results are compared with results from previous kinetic studies, structure-activity relationships (SARs), and theoretical calculations and the discrepancies are discussed. Results from this work were combined with available high temperature (1200-1800 K) rate coefficient data and room temperature reaction end-product yields, where available, to derive a self-consistent site-specific set of reaction rate coefficients of the form AT(n) exp(-E/RT) for use in atmospheric and combustion chemistry modeling. PMID:23627621

  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. Let the microbes explicitly carry out the reactions: a new paradigm to the modeling of soil carbon-nutrient dynamics (Invited)

    NASA Astrophysics Data System (ADS)

    Tang, J.; Riley, W. J.; Bouskill, N.; Brodie, E.

    2013-12-01

    Soil carbon-nutrient dynamics are carried out by a broad spectrum of microbial functional guilds through a network of different reactions, all impacted by abiotic factors, including temperature, moisture, pH, redox, and mineralogy. Few existing soil biogeochemical models explicitly represent microbes and the related biotic and abiotic chemical reactions. Rather, these models usually assume microbes are perfectly adaptive such that their ecological impacts on carbon and nutrient dynamics can be sufficiently described by pseudo-first order decay parameters. These decay parameters are empirically formulated as functions of organic matter composition (e.g., lignocellulos index, CN ratio), soil temperature, and soil moisture that are obtained by ad hoc regression fitting to experimental and observational measurements. These pseudo-first order decay models claim predictability at large spatial and long temporal scales; however, their lack of explicit microbial ecology and microbe relevant biogeochemical and biogeophysical interactions have limited these models' capability to mechanistically explain some fundamental patterns, such as the divergent temperature response of decomposition, episodic emissions in drying-rewetting cycles, and predator-prey effects on organic matter decomposition. We here propose a new modeling paradigm that explicitly considers microbial ecology and reactions in modeling soil carbon-nutrient dynamics. We show this approach requires a new formulation of substrate kinetics to properly account for the intrinsic network structure of the biogeochemical processes and that the classical Michaelis-Menten kinetics is of limited use for this purpose. With a simple model based on this new paradigm, we mechanistically explained lignin dynamics in litter decomposition experiments without the ad hoc use of a lignin shielding effect. We further show, using existing experimental results, that decomposition dynamics are co-shaped by litter chemistry and associated microbial ecology. We also show that interactions between soil mineralogy and organic substrates can significantly reduce the microbial decomposition rate. Finally, we will discuss a few open questions and the data necessary to make such a model structure feasible for practical applications.

  15. Reaction of Tris(2-chloroethyl)phosphate with Reduced Sulfur Species

    PubMed Central

    Hilaire, Dickens Saint; Ismail, Kamal Z.; Jans, Urs

    2014-01-01

    Tris(2-chloroethyl)phosphates (TCEP) is a widely used flame retardant in the U.S. It has recently been identified as one of the most frequently detected contaminants in U.S. streams. This contaminant is of toxicological concern in sensitive coastal ecosystems such as estuaries and salt marshes. It is likely that reactions with reduced sulfur species such as polysulfides (Sn2?), bisulfide (HS?), and thiophenolate (PhS?) present in anoxic subregions of coastal water bodies could have a significant impact on rates of removal of such a contaminant. The kinetics of reaction of reduced sulfur species with tris(2-chloroethyl)phosphate have been determined in well-defined aqueous solutions under anoxic conditions. Reactions were monitored at varying concentrations of reduced sulfur species to obtain the second-order rate constants from the observed pseudo-first order rate constants. The determined second-order rate constant for the reaction of TCEP with polysulfide at 25°C is 5.0 (± 1.4) × 10?4 M?1 s?1, with thiophenolate at 50 °C is 34 (± 2) × 10?4 M?1 s?1 and with bisulfide at 50 °C is 0.9 × 10?4 M?1 s?1, respectively. In addition, the degradation products of hydrolysis and the reactions with polysulfides, thiophenolate, and bisulfide with TCEP were studied with GC-FID and LC-MS-MS and were quantified. PMID:21419471

  16. Statistical Methods for Thermonuclear Reaction Rates and Nucleosynthesis Simulations

    E-print Network

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

    2014-01-01

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

  17. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    E-print Network

    Suleimanov, Yu.V.

    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 ...

  18. Charged-Particle Thermonuclear Reaction Rates: II. Tables and Graphs of Reaction Rates and Probability Density Functions

    E-print Network

    Iliadis, Christian; Champagne, Art; Coc, Alain; Fitzgerald, Ryan

    2010-01-01

    Numerical values of charged-particle thermonuclear reaction rates for nuclei in the A=14 to 40 region are tabulated. The results are obtained using a method, based on Monte Carlo techniques, that has been described in the preceding paper of this series (Paper I). We present a low rate, median rate and high rate which correspond to the 0.16, 0.50 and 0.84 quantiles, respectively, of the cumulative reaction rate distribution. The meaning of these quantities is in general different from the commonly reported, but statistically meaningless expressions, "lower limit", "nominal value" and "upper limit" of the total reaction rate. In addition, we approximate the Monte Carlo probability density function of the total reaction rate by a lognormal distribution and tabulate the lognormal parameters {\\mu} and {\\sigma} at each temperature. We also provide a quantitative measure (Anderson-Darling test statistic) for the reliability of the lognormal approximation. The user can implement the approximate lognormal reaction rat...

  19. 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

  20. Hydro-Reactive Computations with a Temperature Dependent Reaction Rate

    Microsoft Academic Search

    Y. Partom

    2002-01-01

    Hydro-reactive computations are usually performed with a reaction model containing a pressure dependent reaction rate (PDRR). A well-known example is the ``Ignition & Growth'' (I&G) reaction model introduced by Lee and Tarver some twenty years ago. Performing such computations it has become evident that in many cases the results obtained seem unreliable. For these cases using a temperature dependent reaction

  1. The power-law reaction rate coefficient for an elementary bimolecular reaction

    NASA Astrophysics Data System (ADS)

    Yin, Cangtao; Du, Jiulin

    2014-02-01

    The power-law TST reaction rate coefficient for an elementary bimolecular reaction is studied when the reaction takes place in a nonequilibrium system with power-law distributions. We derive a generalized TST rate coefficient, which not only depends on a power-law parameter but also on the reaction coordinate frequency of transition state. The numerical analyses show a very strong dependence of the TST rate coefficient on the power-law parameter, and clearly indicate that a tiny deviation from unity in the parameter (thus from a Boltzmann-Gibbs distribution) would result in significant changes in the rate coefficient. We take an elementary reaction, F+H?FH+H, as an application example to calculate the reaction rate coefficient, and yield the rate values being exactly in agreement with the measurement values in all the experimental studies in the temperature range 190-765 K.

  2. Rate constant for OH,,2 ... reaction

    E-print Network

    Honvault, Pascal

    cloud by the ODIN satellite.7 This is the first evidence of O2 in inter- stellar clouds. Nevertheless Key Laboratory of Mesoscopic Chemistry, Institute of Theoretical and Computational Chemistry, School clouds, where the O2 molecule is produced predominantly by the title reaction. Today, there is still

  3. Charged-Particle Thermonuclear Reaction Rates: II. Tables and Graphs of Reaction Rates and Probability Density Functions

    E-print Network

    Christian Iliadis; Richard Longland; Art Champagne; Alain Coc; Ryan Fitzgerald

    2010-04-23

    Numerical values of charged-particle thermonuclear reaction rates for nuclei in the A=14 to 40 region are tabulated. The results are obtained using a method, based on Monte Carlo techniques, that has been described in the preceding paper of this series (Paper I). We present a low rate, median rate and high rate which correspond to the 0.16, 0.50 and 0.84 quantiles, respectively, of the cumulative reaction rate distribution. The meaning of these quantities is in general different from the commonly reported, but statistically meaningless expressions, "lower limit", "nominal value" and "upper limit" of the total reaction rate. In addition, we approximate the Monte Carlo probability density function of the total reaction rate by a lognormal distribution and tabulate the lognormal parameters {\\mu} and {\\sigma} at each temperature. We also provide a quantitative measure (Anderson-Darling test statistic) for the reliability of the lognormal approximation. The user can implement the approximate lognormal reaction rate probability density functions directly in a stellar model code for studies of stellar energy generation and nucleosynthesis. For each reaction, the Monte Carlo reaction rate probability density functions, together with their lognormal approximations, are displayed graphically for selected temperatures in order to provide a visual impression. Our new reaction rates are appropriate for bare nuclei in the laboratory. The nuclear physics input used to derive our reaction rates is presented in the subsequent paper of this series (Paper III). In the fourth paper of this series (Paper IV) we compare our new reaction rates to previous results.

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

    E-print Network

    Iliadis, Christian; Champagne, Art; Coc, Alain

    2010-01-01

    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. 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.

  6. 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.

  7. Symmetry numbers and chemical reaction rates

    Microsoft Academic Search

    Antonio Fernández-Ramos; Benjamin A. Ellingson; Rubén Meana-Pañeda; Jorge M. C. Marques; Donald G. Truhlar

    2007-01-01

    This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them\\u000a to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational\\u000a symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i)\\u000a if the reaction

  8. Heterogeneous reaction HOCl + HBr â BrCl + HâO on ice films

    Microsoft Academic Search

    Liang Chu

    1999-01-01

    Heterogeneous reactions on the surface of polar stratospheric clouds (PSCs) are critical to an understanding of the annual appearance of the Antarctic ozone hole. The heterogeneous reaction HOCl + HBr(s) â BrCl + HâO(s) on the ice surface at 189 and 220 K has been investigated in a flow reactor interfaced with a differentially pumped quadrupole mass spectrometer. Pseudo first-order

  9. Multidimensional reaction rate theory with anisotropic diffusion.

    PubMed

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

    2014-11-28

    An analytical expression is derived for the rate constant that describes diffusive transitions between two deep wells of a multidimensional potential. The expression, in contrast to the Kramers-Langer formula for the rate constant, is valid even when the diffusion is highly anisotropic. Our approach is based on a variational principle for the reactive flux and uses a trial function for the splitting probability or commitor. The theoretical result is validated by Brownian dynamics simulations. PMID:25429932

  10. Reactions of Three Halogenated Organophosphorus Flame Retardants with Reduced Sulfur Species

    PubMed Central

    Saint-Hilaire, Dickens; Jans, Urs

    2014-01-01

    Tris(haloalkyl)phosphates (THAPs) are among the most widely used flame retardants in the U.S. They have been identified as one of the most frequently detected contaminants in U.S. streams. These contaminants are of toxicological concern in sensitive coastal ecosystems such as estuaries and salt marshes. It is likely that reactions with reduced sulfur species such as polysulfides (Sn2?) and bisulfide (HS?), present in anoxic subregions of coastal water bodies could have a significant impact on rates of removal of such contaminants, especially since no significant degradation reactions in the environment (e.g., hydrolysis, biological degradation) is reported for these compounds. The kinetics of the reaction of reduced sulfur species with three structurally related THAPs have been determined in well-defined aqueous solutions under anoxic conditions. Reactions were monitored at varying concentrations of reduced sulfur species to obtain second-order rate constants from the observed pseudo-first order rate constants. The degradation products were studied with GC-FID and LC-MS. The reactivity of Sn2?, thiophenolate, and HS? were compared and steric, as well as electronic factors are used to explain the relative reactivity of the three THAPs with these three sulfur species. PMID:23948611

  11. Reactions of three halogenated organophosphorus flame retardants with reduced sulfur species.

    PubMed

    Saint-Hilaire, Dickens; Jans, Urs

    2013-11-01

    Tris(haloalkyl)phosphates (THAPs) are among the most widely used flame retardants in the U.S. They have been identified as one of the most frequently detected contaminants in U.S. streams. These contaminants are of toxicological concern in sensitive coastal ecosystems such as estuaries and salt marshes. It is likely that reactions with reduced sulfur species such as polysulfides (Sn(2-)) and bisulfide (HS(-)), present in anoxic subregions of coastal water bodies could have a significant impact on rates of removal of such contaminants, especially since no significant degradation reactions in the environment (e.g., hydrolysis, biological degradation) is reported for these compounds. The kinetics of the reaction of reduced sulfur species with three structurally related THAPs have been determined in well-defined aqueous solutions under anoxic conditions. Reactions were monitored at varying concentrations of reduced sulfur species to obtain second-order rate constants from the observed pseudo-first order rate constants. The degradation products were studied with GC-FID and LC-MS. The reactivity of Sn(2-), thiophenolate, and HS(-) were compared and steric, as well as electronic factors are used to explain the relative reactivity of the three THAPs with these three sulfur species. PMID:23948611

  12. Review of mathematical techniques applicable in astrophysical reaction rate theory

    NASA Astrophysics Data System (ADS)

    Mathai, A. M.; Haubold, H. J.

    2002-10-01

    An overview is presented on statistical techniques for the analytic evaluation of integrals for non-resonant, non-resonant depleted, non-resonant cut-off, non-resonant sccreened, and resonant thermonuclear reaction rates. The techniques are based on statistical distribution theory and the theory of Meijer's G-function and Fox's H-function. The implementation of Meijer's G-function in Mathematica constituts an additional utility for analytic manipulations and numerical computation of thermonuclear reaction rate integrals. Recent results in the astrophysical literature related to the use of analytic thermonuclear reaction rates are incorporated.

  13. Rate constant for reaction of atomic hydrogen with germane

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  14. Upscaling geochemical reaction rates using pore-scale networkmodeling

    SciTech Connect

    Li, L.; Peters, C.E.; Celia, M.A.

    2005-05-19

    Geochemical reaction rate laws are often measured usingcrushed minerals in well-mixed laboratory systems that are designed toeliminate mass transport limitations. Such rate laws are often useddirectly in reactive transport models to predict the reaction andtransport of chemical species in consolidated porous media found insubsurface environments. Due to the inherent heterogeneities of porousmedia, such use of lab-measured rate laws may introduce errors, leadingto a need to develop methods for upscaling reaction rates. In this work,we present a methodology for using pore-scale network modeling toinvestigate scaling effects in geochemical reaction rates. The reactivetransport processes are simulated at the pore scale, accounting forheterogeneities of both physical and mineral properties. Mass balanceprinciples are then used to calculate reaction rates at the continuumscale. To examine the scaling behavior of reaction kinetics, thesecontinuum-scale rates from the network model are compared to the ratescalculated by directly using laboratory-measured reaction rate laws andignoring pore-scale heterogeneities. In this work, this methodology isdemonstrated by upscaling anorthite and kaolinite reaction rates undersimulation conditions relevant to geological CO2 sequestration.Simulation results show that under conditions with CO2 present at highconcentrations, pore-scale concentrations of reactive species andreaction rates vary spatially by orders of magnitude, and the scalingeffect is significant. With a much smaller CO2 concentration, the scalingeffect is relatively small. These results indicate that the increasedacidity associated with geological sequestration can generate conditionsfor which proper scaling tools are yet to be developed. This workdemonstrates the use of pore-scale network modeling as a valuableresearch tool for examining upscaling of geochemical kinetics. Thepore-scale model allows the effects of pore-scale heterogeneities to beintegrated into system behavior at multiple scales, thereby identifyingimportant factors that contribute to the scaling effect.

  15. Reaction rate modeling of PBXN-110

    NASA Astrophysics Data System (ADS)

    Miller, P. J.; Sutherland, G. T.

    1996-05-01

    The reactive rate model for Navy explosive PBXN-110 has been determined. The rate parameters for the Lee-Tarver model were evaluated by comparing the results of DYNA2D hydrocode simulations to the embedded gauge data of gas-gun tests in which the shock loading is mostly one-dimensional. The model parameters were refined such that the failure diameter of the explosive could be reproduced in the calculations. The model was used to simulate a series of Navy sensitivity tests. These are reported here and include detonation curvature, detonation velocity dependency on charge diameter, Modified Gap, and Underwater Sensitivity tests.

  16. 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.

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

    Microsoft Academic Search

    2010-01-01

    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.

  18. 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.

  19. Workshop on Thermonuclear Reaction Rates for Astrophysics Applications

    E-print Network

    aspects of stellar evolution, as well as light- and heavy-element nucleosynthesis, ranging from the state, are the following: BBN, novae, hydrostatic and explosive stellar evolution compilation of thermonuclear reaction rates key reactions: experiment and theory s-, r- and p-process nucleosynthesis nuclear experiments

  20. A compilation of charged-particle induced thermonuclear reaction rates

    Microsoft Academic Search

    C. Angulo; M. Arnould; M. Rayet; P. Descouvemont; D. Baye; C. Leclercq-Willain; A. Coc; S. Barhoumi; P. Aguer; C. Rolfs; R. Kunz; J. W. Hammer; A. Mayer; T. Paradellis; S. Kossionides; C. Chronidou; K. Spyrou; S. Degl'Innocenti; G. Fiorentini; B. Ricci; S. Zavatarelli; C. Providencia; H. Wolters; J. Soares; C. Grama; J. Rahighi; A. Shotter; M. Lamehi Rachti

    1999-01-01

    Low-energy cross section data for 86 charged-particle induced reactions involving light (1 ? Z ? 14), mostly stable, nuclei are compiled. The corresponding Maxwellian-averaged thermonuclear reaction rates of relevance in astrophysical plasmas at temperatures in the range from 106 K to 1010 K are calculated. These evaluations assume either that the target nuclei are in their ground state, or that

  1. 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.

  2. 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

  3. 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. [Research Center for Nuclear Physics, Osaka University, Ibaraki, Osaka 567-0047 (Japan); Carter, J.; Donaldson, L.; Sideras-Haddad, E. [Schools of Physics, University of Witwatersrand, Johannesburg 2050 (South Africa); Furuno, T.; Kawabata, T. [Departments of Physics, Kyoto University, Sakyo, Kyoto, 606-8502 (Japan); Kamimura, M. [RIKEN Nishina Center, Wako, Saitama, 351-0198 (Japan); Nemulodi, F.; Neveling, R.; Smit, F. D.; Swarts, C. [iThemba Laboratory for Accelerator Based Sciences Somerset, West, 7129 (South Africa)

    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.

  4. 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.

  5. 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.

  6. Hydro-Reactive Computations with a Temperature Dependent Reaction Rate

    NASA Astrophysics Data System (ADS)

    Partom, Yehuda

    2001-06-01

    Hydro-reactive computations are usually performed with a reaction model that contains a pressure dependent reaction rate (PDRR). A well known example is the so called "Ignition and Growth" reaction model introduced by Lee and Tarver some twenty years ago. Performing such hydro-reactive computations for many shock initiation and detonation situations it has become evident that in many cases, the results obtained are inappropriate. For those cases it seems that using a temperature dependent reaction rate (TDRR) may produce more appropriate results. We're using a surface burn reaction model that we've developed some twenty years ago. Originally we used it with a TDRR. Several years ago we introduced it into the PISCES code and used it with a PDRR. In this work we add a TDRR to the model in PISCES with the purpose of comparing the performance of the two reaction rates. We first calibrate the two rates to reproduce the pop-plot of PBX-9502. Then we run the code with the two rates for several 1D and 2D situations such as: short shock initiation; double shock initiation; detonation in a rod and corner turning. The resulting differences are qualitatively as expected, but previousely we could not have estimated them quantatively.

  7. Hydro-Reactive Computations with a Temperature Dependent Reaction Rate

    NASA Astrophysics Data System (ADS)

    Partom, Y.

    2002-07-01

    Hydro-reactive computations are usually performed with a reaction model containing a pressure dependent reaction rate (PDRR). A well-known example is the "Ignition & Growth" (I&G) reaction model introduced by Lee and Tarver some twenty years ago. Performing such computations it has become evident that in many cases the results obtained seem unreliable. For these cases using a temperature dependent reaction rate (TDRR) may produce better results. We're using a surface burn reaction model that we've developed some twenty years ago. Originally we used it with a TDRR. Some years ago we introduced it into the PISCES code and used it with a PDRR. In this work we reintroduce the TDRR into the model with the purpose of comparing the performance of the two reaction rates. We first calibrate the rates to reproduce the pop-plot of PBX-9502. We then run the code with the two rates for several 1D and 2D situations. The resulting differences are qualitatively as expected, but previously we could not have estimated them quantitatively.

  8. Statistical Methods for Thermonuclear Reaction Rates and Nucleosynthesis Simulations

    E-print Network

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

    2014-09-19

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

  9. Temperature dependence of the reaction O/3P/ + OH/2 Pi/ yields O2 + H

    NASA Technical Reports Server (NTRS)

    Lewis, R. S.; Watson, R. T.

    1980-01-01

    Measurements of the absolute rate and temperature dependence of the rate constant for the reaction of ground state atomic oxygen with hydroxyl radicals to yield molecular oxygen and hydrogen atoms over the temperature range 211-499 K are presented. The reaction was monitored in a low-pressure discharge flow resonance fluorescence apparatus under pseudo-first-order conditions in which the oxygen concentration was greater than the hydroxyl concentration. An expression for the temperature dependence of the rate constant is derived from a least-squares fit to the observed bimolecular rate constants, which were found to range from 3.21 to 2.77 x 10 to the -11th cu cm/molecule per sec for temperatures from 211 to 499 K, indicative of a slight negative temperature dependence. Results are compared with those of previous workers, and the significance of the lower value of the rate constant obtained in the present study to models of HO(x) in the upper stratosphere is indicated.

  10. 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    Rajaram, Harihar; Arshadi, Masoud

    2015-04-01

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

  13. Photochemical reactions of 2,4-dinitrotoluene in surfactant solutions

    SciTech Connect

    Diehl, C.A.; Jafvert, C.T. [Purdue Univ., West Lafayette, IN (United States); Larson, R.A. [Univ. of Illinois, Champaign, IL (United States)

    1995-12-31

    Photochemical reactions ({lambda}=254 nm) of 2,4-dinitrotoluene were investigated in aqueous solutions containing various additives. These additives were a cationic surfactant (cetyltrimethylammonium bromide; CTAB) or a nonionic surfactant (Brij 58), a hydrogen donor (sodium borohydride; NaBH{sub 4}), and base (sodium hydroxide). All photochemical experiments were performed in a Rayonet RPR-100 photoreactor equipped with a merry-go-round apparatus. Light sources were two phosphor-coated low pressure mercury lamps that emit nearly monochromatic light at 253.7 nm. Illumination of a saturated solution of DNT in solutions containing either 1.9 mM Brij 58 and 1.9 mM NaBH{sub 4}, or 1.8 mM CTAB and 2.5 mM NaBH{sub 4} resulted in pseudo-first order half-lives of 77 minutes and 17 minutes, respectfully. In the presence of BH{sub 4}{sup -}, the reaction rate of 2,4-DNT was enhanced tremendously by addition of CTAB at concentrations above the critical micelle concentration (cmc=0.066 mM with 0.1 M NaCl).

  14. Glow Fast, Glow Slow: Alter the Rate of a Reaction!

    NSDL National Science Digital Library

    Oregon Museum of Science and Industry

    1997-01-01

    Learners investigate one factor affecting reaction rates: temperature. In a darkened room, two identical lightsticks are placed in water -- one in hot water and one in cold water. The lightstick in the hot water glows brighter than the lightstick in the cold water since the light-producing reaction is faster in hot water. This activity, located on page 2 of the PDF, is one of three activities in the Take Home guide for the Chemical Reactions unit in OMSI's Chemistry Lab. Also included on the PDF are two additional activities: Cloudy Globs and Gas Production.

  15. 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.

  16. Analysis of the Reaction Rate Coefficients for Slow Bimolecular Chemical Reactions

    E-print Network

    Kremer, Gilberto M

    2012-01-01

    Simple bimolecular reactions $A_1+A_2\\rightleftharpoons A_3+A_4$ are analyzed within the framework of the Boltzmann equation in the initial stage of a chemical reaction with the system far from chemical equilibrium. The Chapman-Enskog methodology is applied to determine the coefficients of the expansion of the distribution functions in terms of Sonine polynomials for peculiar molecular velocities. The results are applied to the reaction $H_2+Cl\\rightleftharpoons HCl+H$, and the influence of the non-Maxwellian distribution and of the activation-energy dependent reactive cross sections upon the forward and reverse reaction rate coefficients are discussed.

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

    SciTech Connect

    Searcy, J.Q.; Reinhardt, F.W.

    1980-12-01

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

  18. Vectorial redox reactions of physiological quinones. I. Requirement of a minimum length of the isoprenoid side chain.

    PubMed

    Futami, A; Hurt, E; Hauska, G

    1979-09-11

    Physiological quinones carrying isoprenoid side chains have been compared with homologues lacking the side chain, for their ability to carry electrons and protons from dithionite to ferricyanide, trapped in liposomes. Six differential observations were made: (1) Plastoquinone and ubiquinones, with a side chain of more than two isoprene units, are by far better mediators than their short-chain homologues. Also other benzoquinones lacking a long side chain are poor catalysts, except dimethyl-methylenedioxy-p-benzoquinone, a highly autooxidizable compound. Tocopherol is a good catalyst. (2) Vitamin K-1 and K-2 are poor mediators compared to vitamin K-3. (3) The reaction catalyzed by quinones carrying long isoprenoid side chains has an about three-fold higher activation energy, irrespective of the catalytic efficiency. (4) The reaction catalyzed by quinones lacking a long side chain follows pseudo first-order kinetics, while the reaction with quinones carrying a long side chain is of apparently higher order. (5) The rate with ubiquinone-1 is increasing pH, while with ubiquinone-9 it is decreasing. (6) The reaction mediated by short-chain quinones seems to be satuarated at lower dithionite concentration. We conclude that isoprenoid quinones are able to translocate electrons and protons in lipid membranes, and that the side chain has a strong impact on the mechanism. This and the relevance of the model reaction for electron and proton transport in photosynthesis and respiration is discussed. PMID:486435

  19. Fusion Reaction Rate Coefficient for Different Beam and Target Scenarios

    NASA Astrophysics Data System (ADS)

    Ou, Wei; Zeng, Xian-Jun; Deng, Bai-Quan; Gou, Fu-Jun

    2015-02-01

    Fusion power output is proportional not only to the fuel particle number densities participating in reaction but also to the fusion reaction rate coefficient (or reactivity), which is dependent on reactant velocity distribution functions. They are usually assumed to be dual Maxwellian distribution functions with the same temperature for thermal nuclear fusion circumstances. However, if high power neutral beam injection and minority ion species ICRF plasma heating, or multi-pinched plasma beam head-on collision, in a converging region are required and investigated in future large scale fusion reactors, then the fractions of the injected energetic fast ion tail resulting from ionization or charge exchange will be large enough and their contribution to the non-Maxwellian distribution functions is not negligible, hence to the fusion reaction rate coefficient or calculation of fusion power. In such cases, beam-target, and beam-beam reaction enhancement effect contributions should play very important roles. In this paper, several useful formulae to calculate the fusion reaction rate coefficient for different beam and target combination scenarios are derived in detail.

  20. 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.

  1. 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.

  2. EXPERIMENTAL PROTOCOL FOR DETERMINING HYDROXYL RADICAL REACTION RATE CONSTANTS

    EPA Science Inventory

    An experimental protocol for the determination of rate constants for the reactions of the hydroxyl (OH) radical with chemicals in the gas phase at room temperature has been developed and is described in detail. This protocol will thus provide a basis for evaluating the relative i...

  3. EXPERIMENTAL PROTOCOL FOR DETERMINING OZONE REACTION RATE CONSTANTS

    EPA Science Inventory

    An experimental protocol for the determination of room temperature rate constants for the reactions of ozone with chemicals in the gas phase has been developed and is described in detail. This protocol will thus provide a basis for evaluating the relative importance of one atmosp...

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

    PubMed Central

    1986-01-01

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

  5. EXPERIMENTAL PROTOCOL FOR DETERMINING PROTOLYSIS REACTION RATE CONSTANTS

    EPA Science Inventory

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

  6. 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

  7. Rate of reaction of OH with HNO3

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

  8. Nuclear fusion reaction rates for strongly coupled ionic mixtures

    SciTech Connect

    Chugunov, A. I.; DeWitt, H. E. [Ioffe Physical-Technical Institute, Politekhnicheskaya 26, RU-194021 St. Petersburg (Russian Federation); Lawrence Livermore National Laboratory, Livermore, California 94550 (United States)

    2009-07-15

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

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

    NASA Astrophysics Data System (ADS)

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

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

  10. 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.

  11. Degradation rates of advanced treatment effluents anticipated in the Trinity River Basin, Texas 

    E-print Network

    Esmond, Steven Earl

    1974-01-01

    of Advisory Committee: Dr. Harold W. Wolf The aerobic degradation rates of advanced treatment effluents were studied, and a kinetic model is proposed. Both the carbon- aceous and nitrogenous deoxygenation rates followed pseudo-first- order... at this point is relatively inert, and will not degrade much fur- ther by either biological or chemical treatment. However, the granular activated carbon columns are able to effect a 50/ TKN removal by adsorption, which routinely brings the final effluent...

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

    SciTech Connect

    Suda, Takuma; Fujimoto, Masayuki Y. [Department of Cosmosciences, Graduate School of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo 060-0810 (Japan); Hirschi, Raphael, E-mail: suda@astro1.sci.hokudai.ac.jp [Astrophysics Group, EPSAM, Keele University, Keele, Staffordshire ST5 5BG (United Kingdom)

    2011-11-01

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

  13. Evaluation of plutonium(IV) extraction rate between nitric acid and tri-n-butylphosphate solution using a glass chip microchannel.

    PubMed

    Yamamoto, Masahiko; Taguchi, Shigeo; Sato, Soichi; Surugaya, Naoki

    2015-05-01

    Extraction of Pu(IV) with tri-n-butylphosphate is performed using a glass chip microchannel to evaluate the extraction rate. Two-phase flow forms in the microchannel by introducing a solution of Pu(IV) and tri-n-butylphosphate with flow rates above 5 ?L/min. The Pu(IV) extraction reaction proceeds at the interface between the two phases. To evaluate the extraction rate, the contact time between the two phases is varied from 0.48 to 4.8 s by changing the confluent length of the microchannel and the flow rate. The Pu concentration of each phase collected from the microchannel is measured with an alpha liquid scintillation counter, and the contact time dependence of Pu(IV) extraction is obtained. An extraction model based on diffusion in the microchannel and the reaction at the interface is proposed and applied to determine the extraction rate. The extraction process is assumed to follow pseudo-first-order kinetics, and the extraction rate constant of Pu(IV) is determined to be 1.5 × 10(-2) cm/s. The investigation demonstrates that a microfluidic device can be a new tool to determine Pu(IV) extraction rates. PMID:25754948

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

    SciTech Connect

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

    1981-01-01

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

  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. 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.

  17. Alternative nonlinear model for estimating second-order rate coefficients for biodegradation.

    PubMed Central

    Suflita, J M; Smolenski, W J; Robinson, J A

    1987-01-01

    A modification of the second-order model for biodegradation was derived, applied to an example data set, and shown to be superior for describing the anaerobic biodegradation of p-cresol by an enriched bacterial consortium. The modified model circumvents the no-growth assumption implicit in the use of the second-order rate equation, but still requires the assumption of first-order kinetics over the course of substrate depletion. Violation of the no-growth assumption is particularly important since overestimates of the pseudo-first-order rate coefficient lead to underestimates of the time required for the removal of a xenobiotic chemical from a contaminated environment. Our calculations show that the errors introduced into the pseudo-first-order rate coefficient (and the resulting estimates of the second-order rate coefficient) approach 100% if one doubling occurs in activity over the course of substrate depletion. For an exemplary data set, use of a first-order model resulted in a 100% overestimate of the first-order decay coefficient, which would in turn lead to a corresponding overestimate of the second-order rate coefficient. The modified model we describe is a potential alternative to the pseudo-first-order model for the routine estimation of second-order rate coefficients. PMID:3606091

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

    SciTech Connect

    Itoh, Naoki; Kuwashima, Fumiyoshi; Munakata, Hiroharu (Sophia Univ., Tokyo (Japan) Tsurumi Univ., Yokohama (Japan))

    1990-10-01

    The enhancement factor of the thermonuclear reaction rates is calculated for the extremely dense stellar plasmas in the liquid phase where the condition 3Gamma/tau less than or equal to 1.6 is not necessarily imposed. Here the parameter 3Gamma/tau corresponds to the ratio of the classical turning point radius at the Gamow peak and the mean interionic distance in the case of the pure Coulomb potential. Direct double integration is carried out to obtain the thermonuclear reaction rates. The result is presented in the form of an analytic fitting formula to facilitate applications. The present fitting formula is valid for 3Gamma/tau = 0-5.4. The present calculation is intended to serve as the best available one for the case that ions are in the semiquantum regime. 7 refs.

  19. 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.

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

    SciTech Connect

    Suda, Takuma; Hirschi, Raphael; Fujimoto, Masayuki Y. [National Astronomical Observatory of Japan, Osawa 2-21-1, Mitaka, Tokyo 181-8588 (Japan); Keele University, Keele, Staffordshire ST5 5BG (United Kingdom) and Institute for the Physics and Mathematics of the Universe, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8583 (Japan); Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo 060-0810 (Japan)

    2012-11-12

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

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

    NASA Astrophysics Data System (ADS)

    Rauscher, T.

    2013-09-01

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

  2. 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)

  3. Charged-Particle Thermonuclear Reaction Rates: IV. Comparison to Previous Work

    E-print Network

    Iliadis, Christian; Champagne, Art; Coc, Alain

    2010-01-01

    We compare our Monte Carlo reaction rates (see Paper II of this series) to previous results that were obtained by using the classical method of computing thermonuclear reaction rates. For each reaction, the comparison is presented using two types of graphs: the first shows the change in reaction rate uncertainties, while the second displays our new results normalized to the previously recommended reaction rate. We find that the rates have changed significantly for almost all reactions considered here. The changes are caused by (i) our new Monte Carlo method of computing reaction rates (see Paper I of this series), and (ii) newly available nuclear physics information (see Paper III of this series).

  4. Charged-Particle Thermonuclear Reaction Rates: IV. Comparison to Previous Work

    E-print Network

    Christian Iliadis; Richard Longland; Art Champagne; Alain Coc

    2010-04-23

    We compare our Monte Carlo reaction rates (see Paper II of this series) to previous results that were obtained by using the classical method of computing thermonuclear reaction rates. For each reaction, the comparison is presented using two types of graphs: the first shows the change in reaction rate uncertainties, while the second displays our new results normalized to the previously recommended reaction rate. We find that the rates have changed significantly for almost all reactions considered here. The changes are caused by (i) our new Monte Carlo method of computing reaction rates (see Paper I of this series), and (ii) newly available nuclear physics information (see Paper III of this series).

  5. On the Rate of Boronate Ester Formation in ortho-Aminomethyl Functionalized Phenyl Boronic Acids‡

    PubMed Central

    Collins, Byron E.; Metola, Pedro

    2012-01-01

    The role of the ortho-aminomethyl functional group in phenyl boronic acids for sugar complexation is a topic of debate. To decipher its effect on the kinetics of boronate ester formation, we first performed pseudo-first order kinetics analyses at five pH values up to 4 mM in fructose, revealing a first-order kinetic dependence upon fructose. Under these conditions, the reaction is in equilibrium and does not reach completion, but at 50 mM fructose saturation is achieved revealing zero-order dependence upon fructose. This indicates rate-determining creation of an intermediate prior to reaction with fructose, which we propose involves leaving group departure of inserted solvent. Further, the region of kinetics displaying zero-order dependence has a kinetic isotope effect (KIE) of 1.42, showing involvement of a proton transfer in the leaving group departure. The ratio of forward and reverse rate constants branching from the intermediate shows that fructose is several thousand times more nucleophilic than the solvent. Overall, the data supports a mechanism where the o-aminomethyl group lowers the pKa of the proximal boronic acid and acts as a general-acid (as an ammonium) to facilitate leaving group departure. Consequently, by microscopic reversibility the resulting amine must perform general-base catalysis to deliver fructose. PMID:23441105

  6. Up-Scaling Geochemical Reaction Rates Accompanying Acidic CO2-Saturated Brine Flow in Sandstone Aquifers

    E-print Network

    New York at Stoney Brook, State University of

    -scaling of anorthite and kaolinite reaction rates from pore to core scales. Unique to our simulations is the use as by a volume-averaged-concentration method. For the anorthite reaction, which remains far from equilibrium, the volume-averaged reaction rate measured for anorthite exceeded the reaction rate of the network model

  7. 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

  8. Scanning electrochemical microscopy for direct imaging of reaction rates.

    PubMed

    Wittstock, Gunther; Burchardt, Malte; Pust, Sascha E; Shen, Yan; Zhao, Chuan

    2007-01-01

    Not only in electrochemistry but also in biology and in membrane transport, localized processes at solid-liquid or liquid-liquid interfaces play an important role at defect sites, pores, or individual cells, but are difficult to characterize by integral investigation. Scanning electrochemical microscopy is suitable for such investigations. After two decades of development, this method is based on a solid theoretical foundation and a large number of demonstrated applications. It offers the possibility of directly imaging heterogeneous reaction rates and locally modifying substrates by electrochemically generated reagents. The applications range from classical electrochemical problems, such as the investigation of localized corrosion and electrocatalytic reactions in fuel cells, sensor surfaces, biochips, and microstructured analysis systems, to mass transport through synthetic membranes, skin and tissue, as well as intercellular communication processes. Moreover, processes can be studied that occur at liquid surfaces and liquid-liquid interfaces. PMID:17285666

  9. Determination of the reaction mechanism for the acid catalyzed hydrolysis of 2-(p-methoxyphenoxy) tetrahydropyran by using solvent isotope effects and the proton inventory technique 

    E-print Network

    Vale, Glenda C

    1987-01-01

    3 Second Order Rate Constants and Solvent Isotope Effects for the Acid Catalyzed Hydrolysis of 2-(p-Methoxyphenoxy)tetrahydropyran in L20-CHSCN Mixtures of Varying Acetonitrile Volume Fractions XCH CN, I 1. 0 M 3 Pseudo First Order Rate Constants... the use of isotopic fractionation factors rests on two fundamental assumptions. The first of these is that the occurrence of isotopic substitution in one of the hydrogenic exchangeable sites of molecules with multiple labile positions does not affect...

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

    SciTech Connect

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

    1986-12-01

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

  11. 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.

  12. Reaction rates and apparent toxicity of Houston Ship Channel water 

    E-print Network

    Schneider, Peter William

    1969-01-01

    was the Warburg Constant yolume Respirometer manometric method and the second technique was the conventional BOD dilution method using the standard BOD glass bottle. Tests were run on samples of water taken from the Houston Ship Channel. Tests showed... that the specific rate of reaction constant varies with both the depth and the location of the sample. Apparent toxic or inhibitory effects as defined in the thesis were also fo' nd to be present in many samples. The conditions prevailing , prior to the sampling...

  13. Novel technique for constraining r-process (n, ?) reaction rates.

    PubMed

    Spyrou, A; Liddick, S N; Larsen, A C; Guttormsen, M; Cooper, K; Dombos, A C; Morrissey, D J; Naqvi, F; Perdikakis, G; Quinn, S J; Renstrøm, T; Rodriguez, J A; Simon, A; Sumithrarachchi, C S; Zegers, R G T

    2014-12-01

    A novel technique has been developed, which will open exciting new opportunities for studying the very neutron-rich nuclei involved in the r process. As a proof of principle, the ? spectra from the ? decay of ^{76}Ga have been measured with the SuN detector at the National Superconducting Cyclotron Laboratory. The nuclear level density and ?-ray strength function are extracted and used as input to Hauser-Feshbach calculations. The present technique is shown to strongly constrain the ^{75}Ge(n,?)^{76}Ge cross section and reaction rate. PMID:25526121

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

    NASA Technical Reports Server (NTRS)

    Kawano, Lawrence; Schramm, David; Steigman, Gary

    1988-01-01

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

  15. Ethyl methanesulphonate in a parenteral formulation of BMS-214662 mesylate, a selective farnesyltransferase inhibitor: formation and rate of hydrolysis.

    PubMed

    Nassar, Munir N; Cucolo, Michael; Miller, Scott A

    2009-01-01

    The objectives of the present study were to investigate the formation and rate of hydrolysis of ethyl methanesulphonate (EMS) in BMS-214662 mesylate drug substance and parenteral formulation by a gas chromatographic/mass spectrometric (GC/MS) method. EMS levels in the drug substance ranged between 0.3 microg/g and 0.8 microg/g. The parenteral formulation contains ethanol and the reaction between residual free methane sulphonic acid and ethanol may lead to the formation of EMS. Given that EMS is a potent mutagen, it is therefore of vital importance to eliminate or reduce the risk of human exposure. Data indicate no significant increase in the levels of EMS following storage of the drug product for 18 weeks at 25 degrees C or six weeks at 60 degrees C indicating that the potential reaction between ethanol and free methane sulphonic acid may not occur in the BMS-214662 formulation under the storage conditions evaluated and therefore causes no plausible safety concerns of EMS exposure in humans. Kinetic studies were conducted by spiking 200 ppb of EMS into water and the diluted and undiluted parenteral formulation. The rates of hydrolysis of EMS at 25 degrees C followed pseudo-first order kinetics and were determined to be 2.35 x 10(-4)min(-1), 67.4 x 10(-4)min(-1), and 1.32 x 10(-4)min(-1) in water, undiluted, and diluted drug product, respectively. PMID:19883257

  16. The reaction of nitrite with the haemocyanin of Astacus leptodactylus.

    PubMed Central

    Tahon, J P; Van Hoof, D; Vinckier, C; Witters, R; De Ley, M; Lontie, R

    1988-01-01

    The reaction of nitrite at pH 5.7 with deoxyhaemocyanin of Astacus leptodactylus yielded methaemocyanin in two one-electron steps, as nitrite was reduced to NO. This methaemocyanin could be almost fully regenerated by an anaerobic treatment with HONH2, in contrast with the methaemocyanin prepared with H2O2. A destruction of active sites on treating oxyhaemocyanin with HONH2 explains the partial regeneration of methaemocyanin under air, as traces of H2O2 are formed in the autoxidation of HONH2. The reaction rate of nitrite with deoxyhaemocyanin is almost 15 times that with oxyhaemocyanin. The slope of -1.0 for the logarithm of the pseudo-first-order rate constants plotted against pH indicates that HNO2 is the reacting species. Methaemocyanin was e.p.r.-undetectable, but a binuclear signal was observed at g = 2 on binding nitrite to methaemocyanin. This signal disappeared with a pKa of 6.50, suggesting that a mu-aquo bridging ligand, which can be replaced by nitrite, is deprotonated to a mu-hydroxo bridging ligand, which resists substitution by nitrite. The intensity of this triplet e.p.r. signal allowed the determination of the association constant of nitrite to the active site of Astacus methaemocyanin and yielded a value of 237 M-1 at pH 5.7. The interpretation by some authors of nitrosylhaemocyanin as a nitrite derivative of semimethaemocyanin is contradicted by this rapid reaction of nitrite with copper(I) in deoxyhaemocyanin and in semi-methaemocyanin and by the low binding constant of nitrite to the active site of methaemocyanin. PMID:2833232

  17. The reaction of nitrite with the haemocyanin of Astacus leptodactylus.

    PubMed

    Tahon, J P; Van Hoof, D; Vinckier, C; Witters, R; De Ley, M; Lontie, R

    1988-02-01

    The reaction of nitrite at pH 5.7 with deoxyhaemocyanin of Astacus leptodactylus yielded methaemocyanin in two one-electron steps, as nitrite was reduced to NO. This methaemocyanin could be almost fully regenerated by an anaerobic treatment with HONH2, in contrast with the methaemocyanin prepared with H2O2. A destruction of active sites on treating oxyhaemocyanin with HONH2 explains the partial regeneration of methaemocyanin under air, as traces of H2O2 are formed in the autoxidation of HONH2. The reaction rate of nitrite with deoxyhaemocyanin is almost 15 times that with oxyhaemocyanin. The slope of -1.0 for the logarithm of the pseudo-first-order rate constants plotted against pH indicates that HNO2 is the reacting species. Methaemocyanin was e.p.r.-undetectable, but a binuclear signal was observed at g = 2 on binding nitrite to methaemocyanin. This signal disappeared with a pKa of 6.50, suggesting that a mu-aquo bridging ligand, which can be replaced by nitrite, is deprotonated to a mu-hydroxo bridging ligand, which resists substitution by nitrite. The intensity of this triplet e.p.r. signal allowed the determination of the association constant of nitrite to the active site of Astacus methaemocyanin and yielded a value of 237 M-1 at pH 5.7. The interpretation by some authors of nitrosylhaemocyanin as a nitrite derivative of semimethaemocyanin is contradicted by this rapid reaction of nitrite with copper(I) in deoxyhaemocyanin and in semi-methaemocyanin and by the low binding constant of nitrite to the active site of methaemocyanin. PMID:2833232

  18. Accuracy of trajectory calculations and transition state theory for thermal rate constants of atom transfer reactions

    Microsoft Academic Search

    Donald G. Truhlar

    1979-01-01

    The reliability of several practical techniques for computing the equilibrium rate constant of elementary atom-transfer reactions is discussed. Conventional transition state theory and two generalizations, the canonical variational theory of reaction rates (also known as the method of free energy surfaces) and the adiabatic theory of reactions (also known as the microcanonical variational theory of reactions), are all considered. For

  19. 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.

  20. 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.

  1. 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.

  2. The effects of vacuum polarization on thermonuclear reaction rates

    NASA Technical Reports Server (NTRS)

    Gould, Robert J.

    1990-01-01

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

  3. Reaction rates for Neutron Capture Reactions to C-, N- and O-isotopes to the neutron rich side of stability

    E-print Network

    H. Herndl; R. Hofinger; J. Jank; H. Oberhummer; J. Goerres; M. Wiescher; F. -K. Thielemann; B. A. Brown

    1999-08-31

    The reaction rates of neutron capture reactions on light nuclei are important for reliably simulating nucleosynthesis in a variety of stellar scenarios. Neutron capture reaction rates on neutron-rich C-, N-, and O-isotopes are calculated in the framework of a hybrid compound and direct capture model. The results are tabulated and compared with the results of previous calculations as well as with experimental results.

  4. A Lorentzian-Function Approximation developed in calculating the charged-particle-induced nonresonant reaction rate

    NASA Astrophysics Data System (ADS)

    He, J. J.

    2007-07-01

    A Lorentzian-Function Approximation (LFA) has been developed in calculating the nonresonant reaction rate of charged-particle-induced reactions. The nonresonant reaction rate and the effective S -factor have been represented in terms of LFA. In the frame of LFA, the nonresonant reaction taken place within the Gamow window can be considered as a “resonance reaction” with a width of ? which is equal to that of 1/ e width (? in a well-known Gaussian-Function Approximation (GFA).

  5. 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

  6. Kinetics of the NCN + NO reaction over a broad temperature and pressure range.

    PubMed

    Welz, Oliver; Olzmann, Matthias

    2012-07-12

    Rate coefficients for the reaction (3)NCN + NO ? products (R3) were measured in the temperature range 251-487 K at pressures from 10 mbar up to 50 bar with helium as the bath gas. The experiments were carried out in slow-flow reactors by using pulsed excimer laser photolysis of NCN(3) at 193 or 248 nm for the production of NCN. Pseudo-first-order conditions ([NCN](0) ? NO) were applied, and NCN was detected time-resolved by resonant laser-induced fluorescence excited near 329 nm. The measurements at the highest pressures yielded values of k(3) ? 8 × 10(-12) cm(3) s(-1) virtually independent of temperature and pressure, which indicates a substantially smaller high-pressure limiting value of k(3) than predicted in earlier works. Our experiments at pressures below 1 bar confirm the negative temperature and positive pressure dependence of the rate coefficient k(3) found in previous investigations. The falloff behavior of k(3) was rationalized by a master equation analysis based on a barrierless association step (3)NCN + NO ? NCNNO((2)A?) followed by a fast internal conversion NCNNO((2)A?) ? NCNNO((2)A'). From 251-487 K and above 30 mbar, the rate coefficient k(3) is well represented by a Troe parametrization for a recombination/dissociation reaction, k(3)(T,P) = k(4)(?)k(4)(0)[M]F(k(4)(0)[M] + k(4)(?))(-1), where k(4) represents the rate coefficient for the recombination reaction (3)NCN + NO. The following parameters were determined (30% estimated error of the absolute value of k(3)): k(4)(0)[M=He] = 1.91 × 10(-30)(T/300 K)(-3.3) cm(6) s(-1)[He], k(4)(?) = 1.12 × 10(-11) exp(-23 K/T) cm(3) s(-1), and F(C) = 0.28 exp(173 K/T). PMID:22694482

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

    Microsoft Academic Search

    Donald J. Olbris; Judith Herzfeld

    2002-01-01

    Depletion is a game that reinforces central concepts of reaction rate theory through simulation. Each player buys chemicals and guides them through a series of reactions, thereby earning money to buy more chemicals. The reactions occur when players roll a high enough value on two dice to overcome an activation barrier. The reactions may be accelerated by buying heat (which

  8. 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.

  9. Charged-Particle Thermonuclear Reaction Rates: I. Monte Carlo Method and Statistical Distributions

    E-print Network

    Longland, Richard; Champagne, Art; Newton, Joe; Ugalde, Claudio; Coc, Alain; Fitzgerald, Ryan

    2010-01-01

    A method based on Monte Carlo techniques is presented for evaluating thermonuclear reaction rates. We begin by reviewing commonly applied procedures and point out that reaction rates that have been reported up to now in the literature have no rigorous statistical meaning. Subsequently, we associate each nuclear physics quantity entering in the calculation of reaction rates with a specific probability density function, including Gaussian, lognormal and chi-squared distributions. Based on these probability density functions the total reaction rate is randomly sampled many times until the required statistical precision is achieved. This procedure results in a median (Monte Carlo) rate which agrees under certain conditions with the commonly reported recommended "classical" rate. In addition, we present at each temperature a low rate and a high rate, corresponding to the 0.16 and 0.84 quantiles of the cumulative reaction rate distribution. These quantities are in general different from the statistically meaningles...

  10. 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

  11. 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

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

    ERIC Educational Resources Information Center

    Murdoch, Joseph R.

    1981-01-01

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

  13. Kinetics study of heterogeneous reactions of ozone with erucic acid using an ATR-IR flow reactor.

    PubMed

    Leng, Chunbo; Hiltner, Joseph; Pham, Hai; Kelley, Judas; Mach, Mindy; Zhang, Yunhong; Liu, Yong

    2014-03-01

    The ozone initiated heterogeneous oxidation of erucic acid (EA) thin film was investigated using a flow system combined with attenuated total reflection infrared spectroscopy (ATR-IR) over wide ranges of ozone concentrations (0.25-60 ppm), thin film thickness (0.1-1.0 ?m), temperatures (263-298 K), and relative humidities (0-80% RH) for the first time. Pseudo-first-order rate constants, kapp, and overall reactive uptake coefficients, ?, were obtained through changes in the absorbance of C[double bond, length as m-dash]O stretching bands at 1695 cm(-1), which is assigned to the carbonyl group in carboxylic acid. Results showed that the reaction followed the Langmuir-Hinshelwood mechanism and kapp was largely dominated by surface reaction over bulk phase reaction. In addition, both the kapp and the ? values showed very strong temperature dependences (?two orders of magnitude) over the temperature range; in contrast, they only slightly increased with increasing RH values from 0-80%. According to the kapp values as a function of temperature, the activation energy for the heterogeneous reaction was estimated to be 80.6 kJ mol(-1). Our results have suggested that heterogeneous reactions between ozone and unsaturated solid surfaces likely have a substantially greater temperature dependence than liquid ones. Moreover, the hygroscopic properties of EA thin films before and after exposure to ozone were also studied by measurement of water uptake. Based on the hygroscopicity data, the insignificant RH effect on reaction kinetics was probably due to the relatively weak water uptake by the unreacted and reacted EA thin films. PMID:24457621

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

    SciTech Connect

    Veshchunov, M. S., E-mail: vms@ibrae.ac.ru [Russian Academy of Sciences, Nuclear Safety Institute (IBRAE) (Russian Federation)

    2012-04-15

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

  15. Reaction rate prediction for elementary reactions in binary mixed solvents assuming an additive solvation of reactant(s) 

    E-print Network

    Van Woert, Howard Clark

    1976-01-01

    Clark Van Woert Jr. , B. A. , Capitol University Chairman of Advisory Committee: Dr. David E. Bergbreiter The second-order reaction of pyridine with methyl io- dide in the binary mixed solvent system acetone-benzene over the solvent range 65...-10+ acetone has been studied. A rate equation was derived assuming the additive solvation of reactants. The rates calculated from this equation for the reaction of pyridine with methyl iodide in the binary mixed solvent system acetone-benzene were compared...

  16. Optimal reconstruction of reaction rates from particle distributions

    NASA Astrophysics Data System (ADS)

    Fernandez-Garcia, Daniel; Sanchez-Vila, Xavier

    2010-05-01

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

  17. 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.

  18. Effect of Macromolecular Crowding on Reaction Rates: A Computational and Theoretical Study

    PubMed Central

    Kim, Jun Soo; Yethiraj, Arun

    2009-01-01

    The effect of macromolecular crowding on the rates of association reactions are investigated using theory and computer simulations. Reactants and crowding agents are both hard spheres, and when two reactants collide they form product with a reaction probability, prxn. A value of prxn < 1 crudely mimics the fact that proteins must be oriented properly for an association reaction to occur. The simulations show that the dependence of the reaction rate on the volume fraction of crowding agents varies with the reaction probability. For reaction probabilities close to unity where most of encounters between reactants lead to a reaction, the reaction rate always decreases as the volume fraction of crowding agents is increased due to the reduced diffusion coefficient of reactants. On the other hand, for very small reaction probabilities where, in most of encounters, the reaction does not occur, the reaction rate increases with the volume fraction of crowding agents—in this case, due to the increase probability of a recollision. The Smoluchowski theory refined with the radiation boundary condition and the radial distribution function at contact is in quantitative agreement with simulations for the reaction rate constant and allows the quantitative analysis of both effects separately. PMID:19217851

  19. Charged-Particle Thermonuclear Reaction Rates: I. Monte Carlo Method and Statistical Distributions

    E-print Network

    Richard Longland; Christian Iliadis; Art Champagne; Joe Newton; Claudio Ugalde; Alain Coc; Ryan Fitzgerald

    2010-04-23

    A method based on Monte Carlo techniques is presented for evaluating thermonuclear reaction rates. We begin by reviewing commonly applied procedures and point out that reaction rates that have been reported up to now in the literature have no rigorous statistical meaning. Subsequently, we associate each nuclear physics quantity entering in the calculation of reaction rates with a specific probability density function, including Gaussian, lognormal and chi-squared distributions. Based on these probability density functions the total reaction rate is randomly sampled many times until the required statistical precision is achieved. This procedure results in a median (Monte Carlo) rate which agrees under certain conditions with the commonly reported recommended "classical" rate. In addition, we present at each temperature a low rate and a high rate, corresponding to the 0.16 and 0.84 quantiles of the cumulative reaction rate distribution. These quantities are in general different from the statistically meaningless "minimum" (or "lower limit") and "maximum" (or "upper limit") reaction rates which are commonly reported. Furthermore, we approximate the output reaction rate probability density function by a lognormal distribution and present, at each temperature, the lognormal parameters miu and sigma. The values of these quantities will be crucial for future Monte Carlo nucleosynthesis studies. Our new reaction rates, appropriate for bare nuclei in the laboratory, are tabulated in the second paper of this series (Paper II). The nuclear physics input used to derive our reaction rates is presented in the third paper of this series (Paper III). In the fourth paper of this series (Paper IV) we compare our new reaction rates to previous results.

  20. Cross sections and reaction rates of relevance to aeronomy

    SciTech Connect

    Fox, J.L. (USAF, Geophysics Laboratory, Hanscom AFB, MA (United States))

    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.

  1. 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

  2. Rate and equilibrium constants for reactions of coordinated cyclohexadienyl cations

    Microsoft Academic Search

    Martin Galvin

    2007-01-01

    In this work, the nucleophilic reactions of ironcarbonyl coordinated cyclohexadienyl cations with water and hydroxide to produce the corresponding coordinated arene hydrate analogues was examined. These nucleophilic reactions are a key step in a synthetic route to convert arene cis-dihydrodiols to their trans-isomers via their tricarbonyliron coordinated complexes. The arene trans-dihydrodiols produced have significant potential to be used as chiral

  3. 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.

  4. 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

  5. Chemical reaction rates using the semiclassical Van Vleck initial value representation

    E-print Network

    Miller, William H.

    Chemical reaction rates using the semiclassical Van Vleck initial value representation Charulatha gas phase H+CH4 reaction to a model for a chemical reaction in a polar solvent.15 However, as any, California 94720; and Chemical Sciences Division, Lawrence Berkeley National Laboratory, University

  6. Isotope effects for formaldehyde plus hydrogen addition and abstraction reactions: rate calculations including tunnelling

    Microsoft Academic Search

    T. P. M. Goumans

    2011-01-01

    Tunnelling plays a crucial role in the low-temperature chemistry in the interstellar medium (ISM), in particular for reactions involving hydrogen atoms. Using harmonic quantum transition state theory we studied reaction rates down to 20 K including tunnelling effects for the gas phase reaction of formaldehyde with hydrogen atoms, paying particular attention to isotope effects. Hydrogen atoms can either add to

  7. Fundamental Kinetic Modeling: ab initio rate constant calculations of elementary reactions

    E-print Network

    Jenks, Richard Lee

    1998-01-01

    . . . IV . . . . . . 3 . . . . . . 4 . . 7 . . . . . . 9 . . 15 . . . 15 . . . 15 . . . 17 17 24 Addition of Phosgene to Aniline to Form Arylcarbamoyl Chloride . . . . . . . 26 Elimination of Hydrogen Chloride from Arylcarbamoyl Chloride... to aniline. . . . . . . . . . . . 26 Table 13. Calculated reaction parameters for reaction (5), phosgene addition to aniline , . . . . 28 Table 14. AS"" of various species. Table 15. Rate constants for reaction (6), conversion of carbamoyl chloride...

  8. Development of a Lorentzian-Function Approximation Utilizing in the - Particle-Induced Nonresonant Reaction Rate

    NASA Astrophysics Data System (ADS)

    He, J. J.; Li, L.; Hu, J.; Zhang, L. Y.; Xu, S. W.; Yu, X. Q.; Liu, M. L.

    A development has been made for the charged-particle-induced nonresonant reaction-rate equations. The forms of reaction-rate equations for nonresonant and resonant reactions have been united in a frame of Lorentzian-Function Approximation (LFA) mathematically. In the frame of LFA, the nonresonant reaction taken place within the Gamow window can be considered, in form, as a "resonance" reaction with a full width at half maximum (FWHM, ?nr) equal to the 1/e width (?) in a well-known Gaussian-Function Approximation (GFA).

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

    SciTech Connect

    Lippincott, E.P.; McElroy, W.N.; Preston, C.C. (comps.)

    1980-09-01

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

  10. THE {sup 8}Li({alpha}, n){sup 11}B REACTION RATE AT ASTROPHYSICAL TEMPERATURES

    SciTech Connect

    La Cognata, Marco; Del Zoppo, Antonio, E-mail: delzoppo@lns.infn.it [INFN-Laboratori Nazionali del Sud, Via S. Sofia 62, I95123 Catania (Italy)

    2011-08-01

    At temperatures (0.5-1.2) x 10{sup 9} K, the {sup 8}Li + {sup 4}He {yields} {sup 11}B+n reaction can allow for {sup 12}C and heavier element production in the framework of the inhomogeneous big bang nucleosynthesis. At temperatures (2.5-5) x 10{sup 9} K, it can influence the production of seed nuclei, later burnt to heavier elements by means of rapid neutron capture reactions, during Type II supernova explosions. Previous determinations of the reaction rate show an untenable disagreement. In this work, a new reaction rate calculation is proposed for the intervals of astrophysical interest. This new recommendation turns out to be up to a factor of five larger than the most recent rate in the literature, thus enforcing the role of {sup 8}Li + {sup 4}He {yields} {sup 11}B+n as a candidate for key astrophysical reactions. The analytical expression of the recommended reaction rate is given.

  11. Acceleration of Key Reactions as a Strategy to Elucidate the Rate-Limiting Chemistry Underlying

    E-print Network

    Wensel, Theodore G.

    Acceleration of Key Reactions as a Strategy to Elucidate the Rate-Limiting Chemistry Underlying of accelerating each step separately, while monitoring the rate of formation of the end product of the series of phototransduction turn-off. These reactions were accelerated separately and to- gether by adding hydroxylamine and

  12. Overall Rate Constant Measurements of the Reaction of Chloroalkylperoxy Radicals with Nitric Oxide

    E-print Network

    Elrod, Matthew J.

    Overall Rate Constant Measurements of the Reaction of Chloroalkylperoxy Radicals with Nitric Oxide of the NO reaction with chloroalkylperoxy radicals derived from the Cl-initiated oxidation of several atmospherically the OH-initiated oxidation of alkenes) with NO yielded identical rate constants for all of the alkenes

  13. Acidbase chemical reaction model for nucleation rates in the polluted atmospheric boundary layer

    E-print Network

    Acid­base chemical reaction model for nucleation rates in the polluted atmospheric boundary layer for modeling nucleation rates, based on a sequence of acid­base reactions. The model uses empirical estimates- spheric boundary layer are positively correlated with concentra- tions of sulfuric acid vapor. However

  14. Pore-scale heterogeneous reaction rates on a dissolving limestone surface Yael Levensona

    E-print Network

    Simon, Emmanuel

    Pore-scale heterogeneous reaction rates on a dissolving limestone surface Yael Levensona , Simon simulations to show that this difference cannot be explained using a simple diffusion - surface reaction model that the rate of calcite dissolution within micron-size pores at the surface of a limestone sample is much lower

  15. Enhancement of Diffusion-Controlled Reaction Rates by Surface-Induced Orientational Restriction

    E-print Network

    Dinner, Aaron

    Enhancement of Diffusion-Controlled Reaction Rates by Surface-Induced Orientational Restriction-controlled reaction to an interface can enhance the kinetics. One well- known way that a surface can facilitate the means by which immobilization of a substrate on a surface can increase the rate of a diffusion

  16. RATE CONSTANT FOR THE REACTION OF OH RADICALS WITH DIACETYLENE AT 297 + OR - 2K

    EPA Science Inventory

    Using a relative rate technique, the rate constant for the gas phase reaction of OH radicals with diacetylene, a reaction considered to be of importance in fuel-rich acetylene oxidation, has been determined at 297 + or - 2 K and atmospheric pressure....

  17. 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.

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

    NASA Astrophysics Data System (ADS)

    Zaveri, R. A.; Easter, R. C.; Shilling, J. E.; Seinfeld, J. H.

    2013-11-01

    This paper describes and evaluates a new formulation for modeling kinetic gas-particle partitioning of secondary organic aerosol (SOA) that takes into account diffusion and chemical reaction within the particle phase. The new formulation uses a combination of: (a) an analytical quasi-steady-state treatment for the diffusion-reaction process within the particle phase for fast-reacting organic solutes, and (b) a two-film theory approach for slow- and non-reacting solutes. The formulation is amenable for use in regional and global atmospheric models, although it currently awaits specification of the actual species and particle-phase reactions that are important for SOA formation. Here, the formulation is applied within the framework of the computationally efficient Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) to investigate the competitive growth dynamics of the Aitken and accumulation mode particles. Results show that the timescale of SOA partitioning and the associated size distribution dynamics depend on the complex interplay between organic solute volatility, particle-phase bulk diffusivity, and particle-phase reactivity (as exemplified by a pseudo-first-order reaction rate constant), each of which can vary over several orders of magnitude. In general, the timescale of SOA partitioning increases with increase in volatility and decrease in bulk diffusivity and rate constant. At the same time, the shape of the aerosol size distribution displays appreciable narrowing with decrease in volatility and bulk diffusivity and increase in rate constant. A proper representation of these physicochemical processes and parameters are needed in the next generation models to reliably predict not only the total SOA mass, but also its composition and number size distribution, all of which together determine its overall optical and cloud-nucleating properties.

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

    PubMed

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

    2015-04-17

    Chemoselective ligation reactions have contributed immensely to the development of organic synthesis and chemical biology. However, the ligation of stoichiometric amounts of large molecules for applications such as protein-protein conjugates is still challenging. Conjugation reactions need to be fast enough to proceed under dilute conditions and chemoselective in the presence of unprotected functional groups; the starting materials and products must be stable under the reaction conditions. To compare known ligation reactions for their suitability under these conditions, we determined the second-order rate constants of ligation reactions using peptide substrates with unprotected functional groups. The reaction conditions, the chemoselectivity of the reactions, and the stability of the starting materials and products were carefully evaluated. In some cases, the stability could be improved by modifying the substrate structure. These data obtained under the ligation conditions provide a useful guide to choose an appropriate ligation reaction for synthesis of large molecules by covalent ligation reactions of unprotected substrates in water. PMID:25572124

  20. Imidazole C-2 Hydrogen/Deuterium Exchange Reaction at Histidine for Probing Protein Structure and Function with MALDI Mass Spectrometry

    PubMed Central

    Hayashi, Naoka; Kuyama, Hiroki; Nakajima, Chihiro; Kawahara, Kazuki; Miyagi, Masaru; Nishimura, Osamu; Matsuo, Hisayuki; Nakazawa, Takashi

    2015-01-01

    We present a mass spectrometric method for analyzing protein structure and function, based on the imidazole C-2 or histidine C?1 hydrogen/deuterium (H/D) exchange reaction, which is intrinsically second order with respect to the concentrations of the imidazolium cation and OD? in D2O. The second-order rate constant (k2) of this reaction was calculated from the pH-dependency of the pseudo-first-order rate constant (k?) obtained from the change of average mass ?Mr (0 ? ?Mr < 1) of a peptide fragment containing a defined histidine residue at incubation time (t) such that k? = ? [ln(1??Mr)]/t. We preferred using k2 rather than k? because k2max (maximal value of k2) was empirically related to pKa as illustrated with a Brønsted plot: logk2max=-0.7pKa+? (? is an arbitrary constant), so that we could analyze the effect of structure on the H/D-exchange rate in terms of log(k2max/k2) representing the deviation of k2 from k2max. In the catalytic site of bovine ribonuclease A, His12 showed much larger change in log(k2max/k2) compared with His119 upon binding with cytidine 3?-monophosphate, as anticipated from the X-ray structures and the possible change in solvent accessibility. However, there is a need of considering the hydrogen bonds of the imidazole group with non-dissociable groups to interpret an extremely slow H/D exchange rate of His48 in partially solvent-exposed situation. PMID:24606199

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

    SciTech Connect

    Wariishi, Hiroyuki; Gold, M.H. (Oregon Graduate Center, Beaverton (United States)); Dunford, H.B.; MacDonald, I.D. (Univ. of Alberta, Edmonton (Canada))

    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.

  2. 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

  3. Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids

    NASA Astrophysics Data System (ADS)

    Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian

    2015-05-01

    The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2]3+ (1), cis-[Co(dp)2(C12H25NH2)2]3+ (2), cis-[Co(trien)(C12H25NH2)2]3+ (3), cis-[Co(bpy)2(C12H25NH2)2]3+ (4) and cis-[Co(phen)2(C12H25NH2)2]3+ (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2?-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe2+ ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323 K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ?H‡ and entropy of activation ?S‡) of the reaction have been calculated which substantiate the kinetics of the reaction.

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

    SciTech Connect

    Keek, L. [National Superconducting Cyclotron Laboratory, Department of Physics and Astronomy, and Joint Institute for Nuclear Astrophysics, Michigan State University, East Lansing, MI 48824 (United States); Cyburt, R. H. [National Superconducting Cyclotron Laboratory and Joint Institute for Nuclear Astrophysics, Michigan State University, East Lansing, MI 48824 (United States); Heger, A., E-mail: l.keek@gatech.edu [Monash Center for Astrophysics, School of Mathematical Sciences, Monash University, Vic 3800 (Australia)

    2014-06-01

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

  5. 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.

  6. Systematic study of (g,n) reaction rates for Z>=78 isotopes

    E-print Network

    K. Sonnabend; K. Vogt; D. Galaviz; S. Mueller; A. Zilges

    2005-01-06

    The (g,n) reaction rates of the isotopes 196,198,204-Hg and 204-Pb have been determined using the photoactivation technique in an energy region relevant for p process nucleosynthesis. The systematic study of the ground-state (g,n) reaction rates on even-even nuclei in the mass region Z>=78 is complemented with these experiments. The data are compared to rates predicted in the framework of two statistical model approaches.

  7. Diffusion-controlled reaction rate to an active site

    NASA Astrophysics Data System (ADS)

    Traytak, S. D.

    1995-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  9. Survey of Reaction Rate Constants in the Reaction System of Hydrazine and NTO

    NASA Astrophysics Data System (ADS)

    Ohminami, Kaori; Ogawa, Hiroyuki

    Hydrazine (N2H4) and NTO (dinitrogen tetroxide: N2O4) mixtures are used in spacecraft bipropellant systems, having the advantage, for sampling missions, of having no carbon composition. However, no reasonable combustion model of hydrazine and NTO has been developed, although an N/H/O kinetic reaction model has been investigated. To construct a hydrazine and NTO combustion model that is useful for bipropellant thruster simulation, we surveyed the literature concerned with elementary hydrazine and NTO mixture reactions for N/H/O systems. A total of 245 reactions found in 16 available studies are dealt with in the present paper.

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

    SciTech Connect

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

    1999-11-01

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

  11. 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. Error ratemore »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,Taqpolymerase, AccuPrime-Taq High Fidelity, KOD Hot Start, clonedPfupolymerase, Phusion Hot Start, andPwopolymerase, we find the lowest error rates withPfu, Phusion, andPwopolymerases. Error rates are comparable for these 3 enzymes and are >10x lower than the error rate observed withTaqpolymerase. 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

  12. 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.

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

    SciTech Connect

    Grosjean, D. (DGA, Inc., Ventura, CA (United States))

    1990-10-01

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

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

    SciTech Connect

    Judd, J.L.

    1981-12-01

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

  15. 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.

  16. Calcite dissolution and Ca/Na ion-exchange reactions in columns with different flow rates through high ESR soil

    E-print Network

    Navarre, Audrey

    1999-01-01

    of stability was used to calculate rate constants which were then compared for the influence of flow rate on overall reaction rate. The rate constant approximately doubled as the flow rate was doubled, which implied flow rate control of the reactions...

  17. Rate and pathways for the reaction of OH with the biogenic p-cymene, an alkylated aromatic

    NASA Astrophysics Data System (ADS)

    Strekowski, R.; Rayez, M.-T.; Rayez, J.-C.; Zetzsch, C.

    2009-04-01

    Aromatics are known to contribute strongly to tropospheric formation of ozone, and p-cymene (4-isopropyltoluene) is one of only a few biogenic, volatile aromatic hydrocarbons. In spite of its symmetry, this molecule (CH3 - °-CH(CH3)2) has a multitude of potential pathways of its reaction with OH radicals. Addition of OH is well-known to be the predominating primary step in the tropospheric transformation of aromatic hydrocarbons. The addition is expected to occur preferably at a non-occupied position, where four positions are available: two equivalent ones ortho to the methyl group and two equivalent ones ortho to the isopropyl group. Furthermore, various C-H bonds (4 aromatic and 10 aliphatic) are available for abstraction, leading to benzyl-type radicals in two cases. The present study combines theoretical calculations with kinetic experiments in the gas phase. The theoretical calculations are based on electronic quantum chemistry DFT method for the investigation of the possible pathways in the potential energy surface of the reaction. The experiments are carried out by the flash photolysis/resonance fluorescence technique. OH radicals are produced by pulsed vacuum-UV photolysis of H2O (> 115 nm) in the presence of p-cymene in a slow flow of He as carrier gas. Their pseudo-first-order decays are monitored by resonance fluorescence, storing the photon counts by multichannel scaling in a PC and accumulating 50 decays each; see Koch et al. (2007) for details of the technique and evaluation of data. The temperature was varied between room temperature (295 K) and 345K, the He pressure was 250 mbar, and the level of p-cymene was increased stepwise, up to 3 x 1013 molecules/cm3. The decays of OH were observed to be exponential at room temperature, becoming clearly biexponential at higher temperatures, thus indicating reversible addition of OH according to the equilibration OH + p-cymene â?? p-cymene-OH (1, -1) These reactions might be accompanied by various abstraction channels, summarized as OH + p-cymene â?? alkylbenzyl + H2O (2) A value of 1.4 x 10-11 cm3 s-1 at 295 K is obtained for the sum k1 + k2, in good agreement with a value of 1.51 x 10-11 cm3 s-1determined by Corchnoy and Atkinson (1990) in a smog chamber at 295 K. The sum k1 + k2 decreases slightly with increasing temperature, falling below 10-11 cm3 s-1 at 345 K. The Arrhenius plot reveals a curved behaviour with a negative activation energy, approximately 1 x 10-12 exp (60 K/T) cm3 s-1. The biexponential behaviour corresponds to an apparent equilibrium constant of k1/k-1 = 8 x 10-25 exp [(-8500 ± 400) K/T] cm3 s-1. On the other hand, the bond energy of OH in the adduct can hardly be obtained from this biexponential behaviour alone since the abstraction of H atoms from the alkyl groups of p-cymene can be estimated to contribute markedly. Extrapolating the respective abstraction channels of toluene and the xylenes to two methyl substituents would yield k2= 1.6 x 10-18 T2exp (-38 K/T) cm3 s-1 (Atkinson, 1989). This amounts to 1.2x10-12 cm3 s-1 at 295 K (about 9% of the observed reactivity) and 1.7x10-12 cm3 s-1 at 345K (>17% of the observed reactivity) and does not even take the possibly largerreactivity of the isopropyl group (as compared to CH3) into account. The abstraction channel has been found to predominate in the analogous reaction of atomic Cl with p-cymene (Finlayson-Pitts et al, 1999), and further experiments by other methods are required to clarify the reaction channels for OH radicals. References Atkinson, R. (1989) Kinetics and Mechanisms of the Gas-Phase Reactions of the Hydroxyl Radical with Organic Compounds. J. Phys. Chem. Ref. Data, Monograph 1, Am. Chem. Soc./Am. Inst. Phys./NIST, p. 229. Corchnoy, S.B., Atkinson, R. (1990) Kinetics of the gas-phase reactions of OH and NO3 radicals with 2-Carene, 1,8-CineoIe, p-Cymene, and Terpinolene. Environ. Sci. Technol. 24, 1497-1502. Finlayson-Pitts, B. J., Keoshian, C.J., Buehler, B., Ezell, A.A. (1999) Kinetics of reaction of chlorine atoms with some biogenic organics. Int

  18. Reaction of diphtheria toxin channels with sulfhydryl-specific reagents: observation of chemical reactions at the single molecule level.

    PubMed Central

    Mindell, J A; Zhan, H; Huynh, P D; Collier, R J; Finkelstein, A

    1994-01-01

    The diphtheria toxin channel is believed to be a homooligomer of its T domain in which each subunit consists of two alpha-helices, lying within the membrane, connected by a short interhelical loop of four amino acids (residues 349-352). To investigate the validity and implications of this model, we singly mutated each of these amino acids to cysteines, formed channels with the mutant T-domain proteins in planar lipid bilayers, and added to the trans compartment sulfhydryl-specific reagents [methanethiosulfonate derivatives (MTS-ER)] that introduce a positive or negative charge to reacted cysteines. The introduction of a positive charge at residue 351 or 352 (through the MTS-ER reactions) resulted in a step decrease in single-channel conductance, whereas the introduction of a negative charge resulted in a step increase. The opposite sign of these effects indicates the predominantly electrostatic nature of the phenomenon and implies that residues 351 and 352 lie close to the channel entrance. The same reactions at residue 350 resulted in very little change in channel conductance but instead changed the character of the natural rapid flickering of the channel between open and closed states to one in which the channel spent more time in the closed state; this may have resulted from the group introduced at position 350 acting as a tethered channel blocker. The MTS derivatives had no effect on channels containing a cysteine at position 349, suggesting that this residue faces away from the channel entrance. We propose that the step changes in conductance or flickering pattern result from the chemical reaction of one MTS-ER molecule with one cysteine, and thus a bimolecular chemical reaction is being witnessed at the single molecule level. From the distribution of waiting times between the appearance (i.e., the opening) of a channel and the step change in its conductance or flickering pattern, we can calculate a pseudo-first-order rate constant, which can then be converted to a second-order rate constant, for the chemical reaction. Images PMID:7515494

  19. Rate constant and mechanism of the reaction of atomic oxygen with 1, 2-dichlorethane

    Microsoft Academic Search

    L. I. Avramenko; R. V. Kolesnikova; N. L. Kuznetsova

    1961-01-01

    1.Absolute values of the rate constant for the reaction of atomic oxygen with 1, 2-dichlorethane in the temperature range 353–473° K and at pressures of 2 and 4.3mm Hg were measured. The activation energy of the reaction was determined.2.In a study of the mechanism of the interaction of atomic oxygen with 1, 2-dichlorethane it was shown lhat the main reaction

  20. Investigation of solvent effects on the rate and stereoselectivity of the Henry reaction.

    PubMed

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

    2012-01-01

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

  1. Thermochemistry and accurate quantum reaction rate calculations for H2\\/HD\\/D2 + CH3

    Microsoft Academic Search

    Gunnar Nyman; Rob van Harrevelt; Uwe Manthe

    2007-01-01

    Accurate quantum-mechanical results for thermodynamic data, cumulative reaction probabilities (for J = 0), thermal rate constants, and kinetic isotope effects for the three isotopic reactions H-2 + CH3 -> CH4 + H, HD + CH3 -> CH4 + D, and D-2 + CH3 -> CH3D + D are presented. The calculations are performed using flux correlation functions and the multiconfigurational

  2. Cosmic-Ray Records and Reaction Rates in Iron Meteorites

    NASA Astrophysics Data System (ADS)

    Lavielle, B.; Marti, K.; Jeannot, J.-P.

    1995-09-01

    We present a new approach to the study of exposure histories of iron meteorites based on calibrations of the noble gas production rates on the 40K / 41K data base of Voshage [1,2]. Our approach also modifies some of the basic assumptions made by Voshage, and it permits the calculation of exposure ages for a larger number of iron meteorites, including those with shorter exposure ages. Our model adopts an exponential dependence of the production rates with shielding depth and we use the equality of noble gas exposure ages and 40K - 41K ages for samples from the central locations. We only make the restricting assumption of a long-term constancy of the cosmic radiation. The response of the production ratio P(40K) / P(41K) to varying Fe / Ni ratios is calculated from spallation systematics. The production rate P38(So) at the centers of assumed spherical irons depends on meteorite size and, following the initial build-up of secondaries is expected to decrease exponentially with the shielding parameter So. In order to select an appropriate data set for the 38Ar- 40K- 41K calibration we classify the available data base, based on the availability of more than one independent data set with documented shielding parameter and C38 and M parameter measurements. This allows us to exclude cases with complex exposure histories. The quality classes a and b provide a total of 15 data sets which permits a calibration. A few iterations provides fits to the P(So) and the Mo(So) parameters simultaneously. The resulting coefficients a1 to a7 show variations corresponding to 5% changes in the calculated exposure ages. There is one important exception: meteorites with very old potassium ages can not be fitted with the same parameter sets; this may indicate a variation of the cosmic ray intensity over a > 1 Ga time- scale. The calculated production rates P38(So) of 38Ar in iron meteorites is shown in Figure 1 for varying S=4He/21Ne values and for values So= 252, 348, and 433. Corrections to the production rates for off-center locations are derived from P(So) by using an exponential factor with 2 parameters: a8 and a9. These parameters are calculated by fitting production rate profiles of documented iron meteorites such as Carbo or Grant, which have distinct So values. References: [1] Voshage H. (1967) Z. Naturforsch., 22, 477-506 [2] Voshage H. (1979) EPSL, 45, 293-308. Fig. 1. Production rate P38 of 38Ar in iron meteorites versus the ratio S=4He/21Ne used as shielding monitor. P(So) represents the production rate curve at the centers of meteorites. The depth dependance is shown for 3 meteorites of different sizes, A77283, Grant and Carbo.

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

    PubMed Central

    Lizana, L.; Bauer, B.; Orwar, O.

    2008-01-01

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

  4. Resonance Fluorescence kinetic Study of the O(3P) + CH4 Reaction over the Temperature Range 474K to 1156K

    SciTech Connect

    Klemm, R.B.; Tanzawa, T.; Skolnik, E.G.; Michael, J.V.

    1980-01-01

    The bimolecular rate constant for the reaction of O(3P) with CH4 was measured directly over a wide range in temperature in a study that utilized two independent experimental techniques. The flash photolysis-resonance fluorescence method was employed to obtain rate constants at 474K and 520K at total pressure (in argon diluent) of 100 to 200 torr. At higher temperatures (548K to 1156K), a discharge flow-resonance fluorescence apparatus equipped with a quartz tube was employed. Rate data were obtained, using both techniques, not only under pseudo-first-order conditions but also free from the effects of secondary reactions. Stoichiometric corrections were thus not applied to the derived rate constants. The results at thirteen temperatures yield a linear Arrhenius plot that is described by the expression: k1(T) = (2.15 ± .30) x 10-10 exp(-10872 ± 192/RT) cm3 molec-1s-1. This result is compared to previous ones and an extrapolation to higher temperatures, based on a collision model, is discussed. Finally, the present data were combined with the shock tube results of Brabbs and Brokaw, and Roth and Just to obtain the following expression that fits the results of all three studies over the temperature range 475 to 2205K: k1(T) = (5.28 ± .15) x 10-12 T1/2 exp (-10302 ± 48/RT) cm3molec-1s-1.

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

    SciTech Connect

    Gasques, L. R. [Department of Nuclear Physics, Research School of Physical Sciences and Engineering, Australian National University, Canberra, ACT 0200 (Australia); Wiescher, M. [Department of Physics and The Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, IN 46556 (United States); Yakovlev, D. G. [Ioffe Physico-Technical Institute, Poliekhnicheskaya 26, 194021 Saint-Petersburg (Russian Federation)

    2007-10-26

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

  6. A method for measuring the rate of reaction by molecular microwave absorption spectroscopy 

    E-print Network

    Brown, Allan Neil

    1954-01-01

    A METHOD FOR MEASURING THE RATE OF REACTION BT MOLECULAR MICROWAVE ABSORPTION SPECTROSCOPY A Dissertation 9$r Allan Neil Brown Approved as to style and content by: Head of the Departme Chairman of Committee June AM ET LIBRARY A A M COLLEGE... OF TZXAS A METHOD FOR MEASURING THE RATE OF REACTION BT MOLECULAR MICROiTAVE ABSORPTION SPECTROSCOFT A Dissertation Allan Neil Brown % ? ? Submitted to the Graduate School of the Agricultural and Mechanical College of Texas in partial fulfillment...

  7. Measurement of positional isotope exchange rates in enzyme catalyzed reactions by fast atom bombardment mass spectrometry 

    E-print Network

    Hilscher, Larry Wayne

    1985-01-01

    of the requiremer ts for the degree of MASTEP. QF SCIENCE August 1985 Major Subject: Chemistry MEASUREMENT OF POSITIONAL ISOTOPE EXCHANGE RATES IN ENZYME CATALYZED REACTIONS BY FAST ATOM BOMBARDMENT MASS SPECTROMETRY A Thesis LARRY NAYNE HILSCHER Approved...MEASUREMENT OF POSITIONAL ISOTOPE EXCHANGE RATES IN ENZYME CATALYZED REACTIONS BY FAST ATOM BOMBARDMENT MASS SPECTROMETRY A Thesis by LARRY NAYNE HILSCHER Submitted to the Gradu te College of Texas A&M University in partial fulfil" mert...

  8. Determination of rate constants for the reaction between methyldiethanolamine and carbon dioxide

    E-print Network

    Brabson, Charles Meade

    1985-01-01

    DETERMINATION OF RATE CONSTANTS FOR THE REACTION BETWEEN METHYLDIETHANOLAMINE AND CARBON DIOXIDE A Thesis by CHARLES MEADE BRABSON, JR. Submitted to the Graduate College of Texas A6M University in partial fulfillment of the requirements... for the degree of MASTER OF SCIENCE August 1985 Major Subject: Chemical Engineering DETERMINATION OF RATE CONSTANTS FOR THE REACTION BETWEEN METHYLDIETHANOLAMINE AND CARBON DIOXIDE A Thesis by CHARLES MEADE BRABSONp JR. Approved as to style and content...

  9. Measurements of the rate of the uranium-water vapour reaction

    NASA Astrophysics Data System (ADS)

    Ritchie, A. G.; Greenwood, R. C.; Randles, S. J.; Netherton, D. R.; Whitehorn, Miss J. P.

    1986-10-01

    The rate of the uranium-water vapour reaction has been measured between 30 and 80°C. The measured reaction rate obeys the rate equation: k = 3.0 × 10 9r {1}/{2} exp(-15.5 kcal/RT) mg U/cm 2 h = 4.0 × 10 8r {1}/{2} exp(-15.5 kcal/RT) mg weight gain/cm 2 h, where r is the fractional relative humidity. This rate equation agrees remarkably well with the literature equation which was derived from much more limited experimental evidence and so the present equation is preferred.

  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. 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.

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

    SciTech Connect

    Sallaska, A. L. [National Institute of Standards and Technology, Gaithersburg, MD 20899-8462 (United States); Iliadis, C.; Champange, A. E. [University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3255 (United States); Goriely, S. [Institut d'Astronomie et d'Astrophysique, Universite Libre de Bruxelles, C.P. 226, B-1050 Brussels (Belgium); Starrfield, S.; Timmes, F. X., E-mail: anne.sallaska@nist.gov [Arizona State University, Tempe, AZ 85287-1504 (United States)

    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.

  13. On the curvature in logarithmic plots of rate coefficients for chemical reactions

    PubMed Central

    2011-01-01

    In terms of the reduced potential energy barrier ? = ?uTS/kT, the rate coefficients for chemical reactions are usually expressed as proportional to e-?. The coupling between vibrational modes of the medium to the reaction coordinate leads to a proportionality of the regularized gamma function of Euler Q(a,?) = ?(a,?)/?(a), with a being the number of modes coupled to the reaction coordinate. In this work, the experimental rate coefficients at various temperatures for several chemical reactions were fitted to the theoretical expression in terms of Q(a,?) to determine the extent of its validity and generality. The new expression affords lower deviations from the experimental points in 29 cases out of 38 and it accounts for the curvature in the logarithmic plots of rate coefficients versus inverse temperature. In the absence of tunneling, conventional theories predict the curvature of these plots to be identically zero. PMID:21545752

  14. 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

  15. Laboratory studies of gas phase ion-neutral reaction rate constants relevant to the interstellar medium

    NASA Astrophysics Data System (ADS)

    Betts, Nicholas B.

    Interest in interstellar space has led to research of the chemistry of the interstellar medium (ISM). Ion-neutral reactions are an important class of reactions in the ISM. Reactions of polycyclic aromatic hydrocarbon (PAH) cations with the most abundant interstellar species are investigated. PAH cations react rapidly with H and O atoms, while the reactivity with N atoms decreases with increasing cation size. H2 is not reactive with any parent molecular PAH cation. Ion-neutral reaction pathways to form observed neutral species are also studied. Other researchers have postulated mechanisms for many of the observed interstellar species; these involve cationic precursors or interstellar grains. New formation mechanisms are reported in this thesis via anionic reaction pathways for glycine and cyanoacetylene. Reactions of C + with NH 3 , CH 4 , H 2 O, C 2 H 2 , and O 2 are studied to improve interstellar modeling efforts. Recommendations of rate constants and branching ratios are made to produce improved modeling databases.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

  18. 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

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

    EPA Science Inventory

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

  20. Reaction rate prediction for elementary reactions in binary mixed solvents assuming an additive solvation of reactant(s)

    E-print Network

    Van Woert, Howard Clark

    1976-01-01

    and nonpolar component. Franks and Ives have reviewed 23 alcohol-water mixtures. They have stated that no one solvation force such as hydrogen bonding can adequately be invoked to explain all observed variances between sol- vents in binary systems... weight $ acetone. These points fit the assumption of an additive reaction rate in a binary mixed solvent system wherein the reactants undergo no preferred solvation. Arnett has observed that small 22 additions of alcohols to water at first increase...

  1. 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.

  2. Reaction rate and energy-loss rate for photopair production by relativistic nuclei

    NASA Technical Reports Server (NTRS)

    Chodorowski, Michal J.; Zdziarski, Andrzej A.; Sikora, Marek

    1992-01-01

    The process of e(+/-) pair production by relativistic nuclei on ambient photons is considered. The process is important for cosmic-ray nuclei in interstellar and intergalactic space as well as in galactic and extragalactic compact objects. The rate of this process is given by an integral of the cross section over the photon angular and energy distribution. In the case of isotropic photons, the angular integration is performed to provide an expression for the rate at given photon energy in the nucleus rest frame. The total rate then becomes a single integral of that rate over the photon energy distribution. Formulas are also given for the fractional energy loss of a relativistic nucleus colliding with a photon of a given energy in the rest frame. The nucleus energy-loss rate is integrated over the photon angular distribution in the case of isotropic photons, and simple fits are provided.

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

    PubMed Central

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

    2008-01-01

    This article demonstrates that the rate of mixing can regulate the rate and outcome of both biological and nonbiological autocatalytic reaction systems that display a threshold response to the concentration of an activator. Plug-based microfluidics was used to control the timing of reactions, the rate of mixing, and surface chemistry in blood clotting and its chemical model. Initiation of clotting of human blood plasma required addition of a critical concentration of thrombin. Clotting could be prevented by rapid mixing when thrombin was added near the critical concentration, and mixing also affected the rate of clotting when thrombin was added at concentrations far above the critical concentration in two clinical clotting assays for human plasma. This phenomenon was modeled by a simple mechanism—local and global competition between the clotting reaction, which autocatalytically produces an activator, and mixing, which removes the activator. Numerical simulations showed that the Damköhler number, which describes this competition, predicts the effects of mixing. Many biological systems are controlled by thresholds, and these results shed light on the dynamics of these systems in the presence of spatial heterogeneities and provide simple guidelines for designing and interpreting experiments with such systems. PMID:18424502

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

    PubMed

    Szyma?ska, Paulina; Kocha?czyk, Marek; Mi?kisz, Jacek; Lipniacki, Tomasz

    2015-02-01

    We investigate the kinetics of the ubiquitous phosphorylation-dephosphorylation cycle on biological membranes by means of kinetic Monte Carlo simulations on the triangular lattice. We establish the dependence of effective macroscopic reaction rate coefficients as well as the steady-state phosphorylated substrate fraction on the diffusion coefficient and concentrations of opposing enzymes: kinases and phosphatases. In the limits of zero and infinite diffusion, the numerical results agree with analytical predictions; these two limits give the lower and the upper bound for the macroscopic rate coefficients, respectively. In the zero-diffusion limit, which is important in the analysis of dense systems, phosphorylation and dephosphorylation reactions can convert only these substrates which remain in contact with opposing enzymes. In the most studied regime of nonzero but small diffusion, a contribution linearly proportional to the diffusion coefficient appears in the reaction rate. In this regime, the presence of opposing enzymes creates inhomogeneities in the (de)phosphorylated substrate distributions: The spatial correlation function shows that enzymes are surrounded by clouds of converted substrates. This effect becomes important at low enzyme concentrations, substantially lowering effective reaction rates. Effective reaction rates decrease with decreasing diffusion and this dependence is more pronounced for the less-abundant enzyme. Consequently, the steady-state fraction of phosphorylated substrates can increase or decrease with diffusion, depending on relative concentrations of both enzymes. Additionally, steady states are controlled by molecular crowders which, mostly by lowering the effective diffusion of reactants, favor the more abundant enzyme. PMID:25768526

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  6. The thermonuclear rate for the 19F(a,p)22Ne reaction at stellar temperatures

    E-print Network

    Claudio Ugalde; Richard Azuma; Aaron Couture; Joachim Görres; Hye-Young Lee; Edward Stech; Elizabeth Strandberg; Wanpeng Tan; Michael Wiescher

    2008-03-04

    The $^{19}$F($\\alpha$,p)$^{22}$Ne reaction is considered to be one of the main sources of fluorine depletion in AGB and Wolf-Rayet stars. The reaction rate still retains large uncertainties due to the lack of experimental studies available. In this work the yields for both exit channels to the ground state and first excited state of $^{22}$Ne have been measured and several previously unobserved resonances have been found in the energy range E$_{lab}$=792-1993 keV. The level parameters have been determined through a detailed R-matrix analysis of the reaction data and a new reaction rate is provided on the basis of the available experimental information.

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

    SciTech Connect

    Matos, M. [Louisiana State University; Blackmon, Jeff C [ORNL; Linhardt, Laura [Louisiana State University; Bardayan, Daniel W [ORNL; Nesaraja, Caroline D [ORNL; Clark, Jason [Argonne National Laboratory (ANL); Diebel, C. [Yale University; O'Malley, Patrick [Rutgers University; Parker, P.D. [Yale University

    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.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

    Olbris, Donald J.; Herzfeld, Judith

    2002-10-01

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

  10. The global geochemical cycles of iron and calcium: using novel isotope systems to understand weathering, global mass budgets, natural reaction rates, and paleoclimate

    E-print Network

    Fantle, Matthew

    weathering, global mass budgets, natural reaction rates, and paleoclimate by Matthew Scott Fantle B systems to understand weathering, global mass budgets, natural reaction rates, and paleoclimate Copyright novel isotope systems to understand weathering, global mass budgets, natural reaction rates

  11. 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.

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

    NASA Technical Reports Server (NTRS)

    Girimaji, Sharath S.

    1991-01-01

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

  13. 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.

  14. A kinetics study of the O( sup 3 P) + CH sub 3 Cl reaction over the 556-1485 K range by the HTP and LP-ST techniques

    SciTech Connect

    Ko, Taeho; Fontijn, A. (Rensselaer Polytechnic Inst., Troy, NY (United States). High-Temperature Reaction Kinetics Lab.); Lim, K.P.; Michael, J.V. (Argonne National Lab., IL (United States))

    1991-12-01

    The high-temperature photochemistry (HTP) and laser photolysis-shock tube (LP-ST) techniques have been combined to study the kinetics of the reaction between ground-state oxygen atoms with CH{sub 3}Cl over the temperature range, 556--1485 K. In the HTP reactor, used for the 556--1291 K range, O atoms were generated by flash photolysis of O{sub 2}, CO{sub 2} or SO{sub 2}, and the atom concentrations were monitored by resonance fluorescence, while with the LP-ST technique, used for the 916--1485 K range, O atoms were generated by the photolysis of either SO{sub 2} or NO with the 193 nm light from a pulsed ArF excimer laser, and atomic resonance absorption spectroscopy (ARAS) was used to monitor (O){sub t}. In both studies, rate coefficients were derived from the (O) profiles under the pseudo-first-order condition, (O){much lt}(CH{sub 3}Cl). The data obtained by the two techniques are in excellent agreement and are best represented by the expression, k(T) = 2.57 {times} 10{sup {minus}11} (T/K){sup 0.31} exp({minus}5633 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} with a 2{sigma} precision varying from {plus minus}6 {plus minus}22% and an estimated 2{sigma} accuracy of {plus minus}21% to {plus minus}30%, depending on temperature. The rate coefficients for the title reaction are essentially identical to those for the O + CH{sub 4} reaction over the observed temperature range, the reasons for which are discussed.

  15. A kinetics study of the O({sup 3}P) + CH{sub 3}Cl reaction over the 556-1485 K range by the HTP and LP-ST techniques

    SciTech Connect

    Ko, Taeho; Fontijn, A. [Rensselaer Polytechnic Inst., Troy, NY (United States). High-Temperature Reaction Kinetics Lab.; Lim, K.P.; Michael, J.V. [Argonne National Lab., IL (United States)

    1991-12-01

    The high-temperature photochemistry (HTP) and laser photolysis-shock tube (LP-ST) techniques have been combined to study the kinetics of the reaction between ground-state oxygen atoms with CH{sub 3}Cl over the temperature range, 556--1485 K. In the HTP reactor, used for the 556--1291 K range, O atoms were generated by flash photolysis of O{sub 2}, CO{sub 2} or SO{sub 2}, and the atom concentrations were monitored by resonance fluorescence, while with the LP-ST technique, used for the 916--1485 K range, O atoms were generated by the photolysis of either SO{sub 2} or NO with the 193 nm light from a pulsed ArF excimer laser, and atomic resonance absorption spectroscopy (ARAS) was used to monitor [O]{sub t}. In both studies, rate coefficients were derived from the [O] profiles under the pseudo-first-order condition, [O]{much_lt}[CH{sub 3}Cl]. The data obtained by the two techniques are in excellent agreement and are best represented by the expression, k(T) = 2.57 {times} 10{sup {minus}11} (T/K){sup 0.31} exp({minus}5633 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} with a 2{sigma} precision varying from {plus_minus}6 {plus_minus}22% and an estimated 2{sigma} accuracy of {plus_minus}21% to {plus_minus}30%, depending on temperature. The rate coefficients for the title reaction are essentially identical to those for the O + CH{sub 4} reaction over the observed temperature range, the reasons for which are discussed.

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

    SciTech Connect

    Ishikawa, Souichi [Hosei University, 2-17-1 Fujimi, Chiyoda, Tokyo 102-8160 (Japan)

    2012-11-12

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

  17. Rate-promoting vibrations and coupled hydrogen-electron transfer reactions in the condensed phase: A model for enzymatic catalysis

    Microsoft Academic Search

    Joshua S. Mincer; Steven D. Schwartz

    2004-01-01

    A model is presented for coupled hydrogen-electron transfer reactions in condensed phase in the presence of a rate promoting vibration. Large kinetic isotope effects (KIEs) are found when the hydrogen is substituted with deuterium. While these KIEs are essentially temperature independent, reaction rates do exhibit temperature dependence. These findings agree with recent experimental data for various enzyme-catalyzed reactions, such as

  18. Rate-promoting vibrations and coupled hydrogen–electron transfer reactions in the condensed phase: A model for enzymatic catalysis

    Microsoft Academic Search

    Joshua S. Mincer; Steven D. Schwartz

    2004-01-01

    A model is presented for coupled hydrogen–electron transfer reactions in condensed phase in the presence of a rate promoting vibration. Large kinetic isotope effects (KIEs) are found when the hydrogen is substituted with deuterium. While these KIEs are essentially temperature independent, reaction rates do exhibit temperature dependence. These findings agree with recent experimental data for various enzyme-catalyzed reactions, such as

  19. 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

  20. 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

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

    PubMed

    da Silva, Gabriel; Bozzelli, Joseph W

    2012-12-14

    The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O(2). In this study the reaction of benzyl with ground-state atomic oxygen, O((3)P), is examined using quantum chemistry and statistical reaction rate theory. C(7)H(7)O energy surfaces are generated at the G3SX level, and include several novel pathways. Transition state theory is used to describe elementary reaction kinetics, with canonical variational transition state theory applied for barrierless O atom association with benzyl. Apparent rate constants and branching ratios to different product sets are obtained as a function of temperature and pressure from solving the time-dependent master equation, with RRKM theory for microcanonical k(E). These simulations indicate that the benzyl + O reaction predominantly forms the phenyl radical (C(6)H(5)) plus formaldehyde (HCHO), with lesser quantities of the C(7)H(6)O products benzaldehyde, ortho-quinone methide, and para-quinone methide (+H), along with minor amounts of the formyl radical (HCO) + benzene. Addition of O((3)P) to the methylene site in benzyl produces a highly vibrationally excited C(7)H(7)O* adduct, the benzoxyl radical, which can ?-scission to benzaldehyde + H and phenyl + HCHO. In order to account for the experimental observation of benzene as the major reaction product, a roaming radical mechanism is proposed that converts the nascent products phenyl and HCHO to benzene + HCO. Oxygen atom addition at the ortho and para ring sites in benzyl, which has not been previously considered, is shown to lead to the quinone methides + H; these species are less-stable isomers of benzaldehyde that are proposed as important combustion intermediates, but are yet to be identified experimentally. Franck-Condon simulations of the benzaldehyde, o-quinone methide, and p-quinone methide photoelectron spectra suggest that these C(7)H(6)O isomers could be distinguished using tunable VUV photoionization mass spectrometry. PMID:23108328

  2. ARTICLE Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method

    NASA Astrophysics Data System (ADS)

    Zhang, Zhi-ping; Wang, Chen; Fu, Yao; Guo, Qing-xiang

    2010-12-01

    The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods (B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method) were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM(CCSD(T)/6-311++G(2df,2p):B3LYP/6-311++G(2df,2p))// B3LYP/6-31G(d)/PCM/UFF) method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.

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

    SciTech Connect

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

    2013-03-15

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

  4. Studying exothermic reactions in the Ni-Al system at rapid heating rates using a nanocalorimeter

    NASA Astrophysics Data System (ADS)

    Swaminathan, P.; Grapes, M. D.; Woll, K.; Barron, S. C.; LaVan, D. A.; Weihs, T. P.

    2013-04-01

    Heats of reaction and heat capacity changes were measured using scanning nanocalorimetry for a nickel and aluminum bilayer where initial heating rates of 104 K/s were achieved. Multiple exotherms were observed on the initial heating, but the number of intermediate exotherms decreased with increasing heating rate. The final phase was the B2 NiAl intermetallic. Results from the nanocalorimeter were compared with a conventional differential scanning calorimeter (operating at 0.7 K/s) to understand the effect of significant (10 000×) increases in heating rate on the phase transformation sequence. The high heating rate in the nanocalorimeter delays reaction initiation, causes the exothermic peaks to shift to higher temperatures, and appears to suppress the formation of intermediate, metastable phases. Potential explanations for this apparent suppression are discussed.

  5. Photochemistry of Solutes in Different Locations in/on Ice. Part II: Reaction Rate Measurements

    NASA Astrophysics Data System (ADS)

    Hullar, T.; Anastasio, C.

    2014-12-01

    Particularly in polar regions, photochemical reactions in snowpacks can be an important mechanism for transforming organic and inorganic compounds. Chemicals within snow and ice are found in three different compartments: distributed in the bulk ice, concentrated in liquid-like regions (LLRs) within the ice matrix (such as at grain boundaries), or in quasi-liquid layers at the air-ice interface. While some experiments suggest reaction rates may vary in these different compartments, it is not clear if the reaction rates are different or if the changes are due to variations in the reaction environment (such as photon flux). A companion presentation discusses our work identifying solute location in laboratory ice samples; here, we describe experimental measurements of reaction rates in different ice compartments. Polycyclic aromatic hydrocarbons (PAHs) are common pollutants in snow and ice. We first prepared aqueous solutions of a single PAH. We then froze these samples using various methods that segregate the solute into different locations in the ice matrix. With simulated sunlight, we illuminated these samples and measured photon flux (using 2-nitrobenzaldehyde) and the photodecay of the PAH. We will discuss differences in PAH photochemistry as a function of location in the ice sample and the implications of these results for environmental snow and ice.

  6. 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.

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

    SciTech Connect

    Aziz, Azni Abdul; Yusof, Norhasliza; Idris, Mahirah; Kassim, Hasan Abu [Department of Physics, University of Malaya, 50603 Kuala Lumpur (Malaysia)

    2011-03-30

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

  8. 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.

  9. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

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

    E-print Network

    Peters, Catherine A.

    clustered and oriented parallel to flow. Conversely, spatial distributions that enhance mass transport transport of chemical species in natural porous media is important for many problems [Lichtner et al., 1996 directly to calculate reaction rates in natural porous media. Because laboratory systems are often designed

  12. 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 of the polymer backbone, completing the microscopic description of protein folding presented in the preceding

  13. Should Thermostatted Ring Polymer Molecular Dynamics be used to calculate reaction rates?

    E-print Network

    Hele, Timothy J H

    2015-01-01

    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 (TST) limit is identical to rigorous Quantum Transition-State Theory, and we find that its long-time limit is independent of the location of the dividing surface. TRPMD rate theory is then applied to one-dimensional model systems, the atom-diatom bimolecular reactions H+H$_2$, D+MuH and F+H$_2$, and the prototypical polyatomic reaction H+CH$_4$. Above the crossover temperature, the TRPMD rate is virtually invariant to the strength of the friction applied to the internal ring-polymer normal modes, and beneath the crossover temperature the TRPMD rate generally decreases with increasing friction, in agreement with the predictions of Kramers theory. We therefore find that TRPMD is less accurate than Ring Polymer Molecular Dynamics (RPMD) for symmetric reactions, and in certain asymmetric systems closer to the q...

  14. 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.

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

    SciTech Connect

    Karraker, D.G.

    2001-03-28

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

  16. Upscaling geochemical reaction rates accompanying acidic CO2-saturated brine flow in sandstone aquifers

    Microsoft Academic Search

    D. Kim; C. A. Peters; W. B. Lindquist

    2011-01-01

    Network flow models were used to simulate the flow of CO2-saturated brine in the pore networks corresponding to three different sandstones. The simulations were used to study upscaling of anorthite and kaolinite reaction rates from pore to core scales. Unique to our simulations is the use of computed tomography to capture the mineral distribution in the samples as well as

  17. Reaction rates for the s-process neutron source 22Ne+?

    E-print Network

    Richard Longland; Christian Iliadis; Amanda I. Karakas

    2012-06-18

    The 22Ne({\\alpha},n)25Mg reaction is an important source of neutrons for the s-process. In massive stars responsible for the weak component of the s-process, 22Ne({\\alpha},n)25Mg is the dominant source of neutrons, both during core helium burning and in shell carbon burning. For the main s-process component produced in Asymptotic Giant Branch (AGB) stars, the 13C({\\alpha},n)16O reaction is the dominant source of neutrons operating during the interpulse period, with the 22Ne+{\\alpha} source affecting mainly the s-process branchings during a thermal pulse. Rate uncertainties in the competing 22Ne({\\alpha},n)25Mg and 22Ne({\\alpha},{\\gamma})26Mg reactions result in large variations of s-process nucleosynthesis. Here, we present up-to-date and statistically rigorous 22Ne+{\\alpha} reaction rates using recent experimental results and Monte Carlo sampling. Our new rates are used in post-processing nucleosynthesis calculations both for massive stars and AGB stars. We demonstrate that the nucleosynthesis uncertainties arising from the new rates are dramatically reduced in comparison to previously published results, but several ambiguities in the present data must still be addressed. Recommendations for further study to resolve these issues are provided.

  18. Reconsideration of the rate constant for the reaction of hydroxyl radicals with nitric acid

    Microsoft Academic Search

    Steven S. Brown; Ranajit K. Talukdar; A. R. Ravishankara

    1999-01-01

    The authors report rate coefficients for the reaction of OH with HNOâ, kâ, between 10 and 500 Torr of He, SFâ, Nâ, and Oâ and at 10 different temperatures between 200 and 375 K. They generated OH via pulsed photolysis of HNOâ and monitored the [OH] temporal profile via pulsed laser induced fluorescence. Below 300 K the value of kâ

  19. The Temperature Dependence of the Rate Constant for the Reaction of Hydroxyl Radicals With Nitric Acid

    Microsoft Academic Search

    Michael J. Kurylo; Kenneth D. Cornett; Jennifer L. Murphy

    1982-01-01

    The flash photolysis resonance fluorescence technique has been used to measure the rate constant for the reaction OH + HONO2 - products over the temperature range 225-443 K. The data below room temperature can be fit to the expression k = (1.05 _+ 0.40) x 10 TM exp [(759 -+ 100)\\/T] cm 3 molec - s -. This equation, however,

  20. Atmospheric degradation of saturated alcohols: Room temperature rate coefficients for NO3 radical reactions

    NASA Astrophysics Data System (ADS)

    Moreno, Alberto; Salgado, Sagrario; Taccone, Raul; Martín, Pilar; Cabañas, Beatriz

    2014-10-01

    Rate coefficients for the reactions of NO3 radicals with a series of saturated alcohols are reported here using the relative rate technique. Experiments were performed using air as bath gas in a 50 L glass-pyrex reaction chamber at room temperature (298 ± 2) K with long-path FTIR spectroscopy used to monitor the reaction at atmospheric pressure (708 ± 8) Torr. The reference compounds used and their rate coefficients are: propanal kNO3 = (6.0 ± 0.6) × 10-15, methyl methacrylate kNO3 = (3.55 ± 0.62) × 10-15, acetaldehyde kNO3 = (2.62 ± 0.29) × 10-15 and propene kNO3 = (9.50 ± 1.9) × 10-15, in cm3 molecule-1 s-1. Rate coefficients obtained were (in units cm3 molecule-1 s-1): (1.87 ± 0.14) × 10-15, (2.39 ± 0.20) × 10-15, (2.28 ± 0.17) × 10-15, (1.80 ± 0.13) × 10-15 and (3.52 ± 0.19) × 10-15 for 1-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3,3-dimethyl-1-butanol and 3,3-dimethyl-2-butanol respectively. Reactivity trend can be explained in terms of the different types of hydrogen inside the hydrocarbon chain. The reaction occurs by an initial H-atom abstraction mainly from C-H groups of the alcohols by the NO3 radical being NO3 more reactive towards an H atom attached to a tertiary carbon than that attached to a secondary or primary carbon. Reactivity trend is compared with their similar structural 2-butanol and with the corresponding alkanes. Atmospheric implications are also discussed calculating lifetimes of the saturated alcohols studied here due to the reaction with NO3 radicals in comparison to their reactions with the other major atmospheric oxidants.

  1. Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates

    NASA Astrophysics Data System (ADS)

    Panasci, Adele F.; McAlpin, J. Gregory; Ohlin, C. André; Christensen, Shauna; Fettinger, James C.; Britt, R. David; Rustad, James R.; Casey, William H.

    2012-02-01

    Mineral oxides differ from aqueous ions in that the bound water molecules are usually attached to different metal centers, or vicinal, and thus separated from one another. In contrast, for most monomeric ions used to establish kinetic reactivity trends, such as octahedral aquo ions (e.g., Al(H 2O) 63+), the bound waters are closely packed, or geminal. Because of this structural difference, the existing literature about ligand substitution in monomer ions may be a poor guide to the reactions of geochemical interest. To understand how coordination of the reactive functional groups might affect the rates of simple water-exchange reactions, we synthesized two structurally similar Rh(III) complexes, [Rh(phen) 2(H 2O) 2] 3+ [ 1] and [Rh(phen) 2(H 2O)Cl] 2+ [ 2] where (phen) = 1,10-phenanthroline. Complex [ 1] has two adjacent, geminal, bound waters in the inner-coordination sphere and [ 2] has a single bound water adjacent to a bound chloride ion. We employed Rh(III) as a trivalent metal rather than a more geochemically relevant metal like Fe(III) or Al(III) to slow the rate of reaction, which makes possible measurement of the rates of isotopic substitution by simple mass spectrometry. We prepared isotopically pure versions of the molecules, dissolved them into isotopically dissimilar water, and measured the rates of exchange from the extents of 18O and 16O exchange at the bound waters. The pH dependency of rates differ enormously between the two complexes. Pseudo-first-order rate coefficients at 298 K for water exchanges from the fully protonated molecules are close: k0298 = 5 × 10 -8(±0.5 × 10 -8) s -1 for [ 1] and k0298 = 2.5 × 10 -9(±1 × 10 -9) for [ 2]. Enthalpy and entropy activation parameters (? H‡ and ? S‡) were measured to be 119(±3) kJ mol -1, and 14(±1) J mol -1 K -1, respectively for [ 1]. The corresponding parameters for the mono-aquo complex, [ 2], are 132(±3) kJ mol -1 and 41.5(±2) J mol -1 K -1. Rates increase by many orders of magnitude upon deprotonation of one of the bound waters in complex [ 1] because of the close proximity of a transferable proton that can convert the bound hydroxyl to a bound water. This interconversion allows the oxygen to exchange as a bound water, rather than as a bound hydroxyl, which is slow at near-neutral pH conditions.

  2. CF3CF=CH2 and CF3CF=CHF: Temperature Dependent OH Rate Coefficients and Global Warming Potentials

    NASA Astrophysics Data System (ADS)

    Burkholder, J. B.; Papadimitriou, V. C.; Talukdar, R. K.; Portmann, R. W.; Ravishankara, A. R.

    2007-12-01

    Rate coefficients, k(T), over the temperature range 206-380 K are reported for the gas phase reaction of OH radicals with 2,3,3,3-tetrafluoropropene (CF3CF=CH2) and 1,2,3,3,3-pentafluoropropene (CF3CF=CHF), which are major components in proposed substitutes for HFC134a (CF3CFH2) in mobile air conditioning units. Rate coefficients were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH and laser induced fluorescence to detect it. For CF3CF=CH2, the rate coefficients are given by the Arrhenius expression k1(T) = (1.26 ± 0.11) × 10-12 exp[( 35 ± 10)/T] cm3 molecule-1 s-1 where k1(296 K) = (1.12 ± 0.09) × 10-12 cm3 molecule-1 s-1. For CF3CF=CHF, the rate coefficients are given by the non-Arrhenius expression k2(T) = (1.6 ± 0.2) × 10-18 T2 exp[(655 ± 50)/T] cm3 molecule-1 s-1 where k2(296 K) = (1.29 ± 0.06) × 10-12 cm3 molecule-1 s-1. The global warming potentials for CF3CF=CH2 and CF3CF=CHF were calculated to be <4.4 and <3.6, respectively, for the 100 year time horizon using infrared absorption cross sections measured in this work and atmospheric lifetimes of 11.9 and 10.0 days, based solely on OH reactive loss.

  3. [Determination of trace amounts of nitrite and its chemical reaction kinetics].

    PubMed

    Luo, Zhi-yong; Zheng, Huai-li

    2014-06-01

    A catalytic kinetic spectrophotometric method for the determination of nitrite, NO2(-)-S2O8(2-)-MR, was developed. It is based on the fading reaction of methyl red (MR) oxidized by potassium persulfate which can be catalyzed by NO2- in the medium of dilute HCl. The optimum experimental conditions were gained by combining single factor experiments with orthogonal experiments. Calibration curve, detection limit, precision, and anti-interference under the optimum experimental conditions were researched. Its kinetics principles and parameters were discussed. Its quantitative principle was investigated. The results show that the optimum experimental conditions of this method should be as follows: 1.0 mL 0.3 mol x L(-1) HCl, 1.0 mL 0.01 mol x L(-1) K2S2O8, 0.6 mL 0.2 g x L(-1) MR, reaction temperature 80 degrees C and reaction time 9 min. The principles for the quantitative determination of trace nitrite is that variation of MR concentration at the maximum absorption wavelength of 518 nm, ln(A0/A), shows a good linear relationship with the concentration of NO2- under the optimum experimental conditions. Its determination range is 0.01-0.80 mg x L(-1) and its detection limit is 0.007 mg x L(-1). The kinetic characteristics are that the reaction order in NO2- is 1 and the fading reaction is a pseudo first order reaction. Its apparent activation energy is 85.04 kJ x mol(-1). Its apparent rate constant is 0.021 4 min(-1), and the half-life is 32.39 min at 80 degrees C. The kinetic principle is that the variation of MR concentration is directly proportional to the concentration of NO2-, ln(A0/A) = kc(NO2-). This new method for the determination of trace nitrite has never previously been reported in the published literature so far. It is highly sensitive and selective. Most of the common ions don't interfere with the determination of nitrite. This method has the advantages of convenient operation and the regents used are cheap and nontoxic. It was applied to the determination of trace nitrite in food and water samples with satisfactory results. PMID:25358175

  4. Reaction Rates Uncertainties and the Production of F19 in AGB Stars

    E-print Network

    Maria Lugaro; Claudio Ugalde; Amanda I. Karakas; Joachim Gorres; Michael Wiescher; John C. Lattanzio; Robert C. Cannon

    2004-07-27

    We present nucleosynthesis calculations and the resulting 19F stellar yields for a large set of models with different masses and metallicity. We find that the production of fluorine depends on the temperature of the convective pulses, the amount of primary 12C mixed into the envelope by third dredge up and the extent of the partial mixing zone. Then we perform a detailed analysis of the reaction rates involved in the production of 19F and the effects of their uncertainties. We find that the major uncertainties are associated with the 14C(alpha,gamma)18O and the 19F(alpha,p)22Ne reaction rates. For these two reactions we present new estimates of the rates and their uncertainties. The importance of the partial mixing zone is reduced when using our estimate for the 14C(alpha,gamma)18O rate. Taking into account both the uncertainties related to the partial mixing zone and those related to nuclear reactions, the highest values of 19F enhancements observed in AGB stars are not matched by the models. This is a problem that will have to be revised by providing a better understanding of the formation and nucleosynthesis in the partial mixing zone, also in relation to reducing the uncertainties of the 14C(alpha,gamma)18O reaction rate. At the same time the possible effect of Cool Bottom Processing at the base of the convective envelope should be included in the computation of AGB nucleosynthesis. This process could in principle help matching the highest 19F abundances observed by decreasing the C/O ratio at the surface of the star, while leaving the 19F abundance unchanged.

  5. Rates of grain boundary diffusion through enstatite and forsterite reaction rims

    Microsoft Academic Search

    Richard A. Yund

    1997-01-01

    The growth rates of enstatite rims produced by reaction of Fo92 and SiO2 were determined at 250–1500 MPa and 900–1100°C for a wide range of water contents. Growth rates were also determined for\\u000a forsterite rims between MgO and Mg2Si2O6 and between MgO and SiO2. Rim growth rates are parabolic indicating diffusion-controlled growth of the polycrystalline rims which are composed of?˜?2

  6. Equilibrium density fluctuations and the rate of a Langmuir-Hinshelwood type reaction on microcrystal particles

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.; Titov, S. V.

    2013-01-01

    We investigate the effect of restricting the area of planes of microcrystals and equilibrium density fluctuations in components of binary mixtures on partial isotherms of the adsorption of binary mixtures of molecules and the rate of a surface reaction of the Langmuir-Hinshelwood type. Adsorption of components of mixture is considered in a large canonical assembly, and the rate of an elementary step is calculated in kinetic regime. The value of a section of the surface on a plane contains a number of adsorption centers in the range of 10 to 105. The effect of the structure of a heterogeneous surface on the rate of the considered reaction is studied. The effect of the density fluctuations of adsorbed molecules on partial adsorption isotherms and fluctuations in the rate of reaction on heterogeneous surfaces is discussed. It is shown that the greatest effect of density fluctuations on the rate of a step is observed at low fillings of each plane of a particle and at the almost complete filling of a plane.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    In the present paper, reaction and energy relaxation rates as well as the normal stress are studied for viscous gas flows with vibrational and chemical non-equilibrium. Using the modified Chapman-Enskog method, multi-temperature models based on the Treanor and Boltzmann vibrational distributions are developed for the general case taking into account all kinds of vibrational energy transitions, exchange reactions, dissociation, and recombination. Integral equations specifying the first-order corrections to the normal mean stress and reaction rates are derived, as well as approximate systems of linear equations for their numerical computation. Generalized thermodynamic driving forces associated with all non-equilibrium processes are introduced. It is shown that normal stresses and rates of non-equilibrium processes can be expressed in terms of the same driving forces; the symmetry of kinetic coefficients in these expressions is proven. The developed general model is applied to a particular case of a pure N2 viscous flow with slow VT relaxation. Normal stress and rates of vibrational relaxation are studied for various ratios of vibrational and translational temperatures. The cross effects between different vibrational transitions in viscous flows are evaluated, along with the influence of anharmonicity and flow compressibility on the first-order corrections to the relaxation rate. Limits of validity for the widely used Landau-Teller model of vibrational relaxation are indicated.

  8. 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.

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

    SciTech Connect

    Ogata, Kazuyuki; Kan, Masataka [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Kamimura, Masayasu [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); RIKEN Nishina Center, Wako 351-0198 (Japan)

    2010-06-01

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

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

    SciTech Connect

    Ogata, Kazuyuki; Kan, Masataka [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Kamimura, Masayasu [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); RIKEN Nishina Center, Wako 351-0198 (Japan)

    2010-08-12

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

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

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

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

  12. Proton transfer in a polar solvent from ring polymer reaction rate theory

    NASA Astrophysics Data System (ADS)

    Collepardo-Guevara, Rosana; Craig, Ian R.; Manolopoulos, David E.

    2008-04-01

    We have used the ring polymer molecular dynamics method to study the Azzouz-Borgis model for proton transfer between phenol (AH) and trimethylamine (B) in liquid methyl chloride. When the A-H distance is used as the reaction coordinate, the ring polymer trajectories are found to exhibit multiple recrossings of the transition state dividing surface and to give a rate coefficient that is smaller than the quantum transition state theory value by an order of magnitude. This is to be expected on kinematic grounds for a heavy-light-heavy reaction when the light atom transfer coordinate is used as the reaction coordinate, and it clearly precludes the use of transition state theory with this reaction coordinate. As has been shown previously for this problem, a solvent polarization coordinate defined in terms of the expectation value of the proton transfer distance in the ground adiabatic quantum state provides a better reaction coordinate with less recrossing. These results are discussed in light of the wide body of earlier theoretical work on the Azzouz-Borgis model and the considerable range of previously reported values for its proton and deuteron transfer rate coefficients.

  13. 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

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

    SciTech Connect

    Gong, R [Georgia Institute of Technology; Lu, C [Georgia Institute of Technology; Luo, Jian [Georgia Institute of Technology; Wu, Wei-min [Stanford University; Cheng, H. [Stanford University; Criddle, Craig [Stanford University; Kitanidis, Peter K. [Stanford University; Gu, Baohua [ORNL; Watson, David B [ORNL; Jardine, Philip M [ORNL; Brooks, Scott C [ORNL

    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.

  15. Kinetics of Several Oxygen-Containing Carbon-Centered Free Radical Reactions with Nitric Oxide.

    PubMed

    Rissanen, Matti P; Ihlenborg, Marvin; Pekkanen, Timo T; Timonen, Raimo S

    2015-07-16

    Kinetics of four carbon-centered, oxygen-containing free radical reactions with nitric oxide (NO) were investigated as a function of temperature at a few Torr pressure of helium, employing flow tube reactors coupled to a laser-photolysis/resonance-gas-discharge-lamp photoionization mass spectrometer (LP-RPIMS). Rate coefficients were directly determined from radical (R) decay signals under pseudo-first-order conditions ([R]0 ? [NO]). The obtained rate coefficients showed negative temperature dependences, typical for a radical-radical association process, and can be represented by the following parametrizations (all in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO) = (4.76 × 10(-21)) × (T/300 K)(15.92) × exp[50700/(RT)] (T = 266-363 K, p = 0.79-3.44 Torr); k(CH3CHOH + NO) = (1.27 × 10(-16)) × (T/300 K)(6.81) × exp[28700/(RT)] (T = 241-363 K, p = 0.52-3.43 Torr); k(CH3OCH2 + NO) = (3.58 ± 0.12) × 10(-12) × (T/300 K)(-3.17±0.14) (T = 221-363 K, p = 0.50-0.80 Torr); k(T)3 = 9.62 × 10(-11) × (T/300 K)(-5.99) × exp[-7100/(RT)] (T = 221-473 K, p = 1.41-2.95 Torr), with the uncertainties given as standard errors of the fits and the overall uncertainties estimated as ±20%. The rate of CH3OCH2 + NO reaction was measured in two density ranges due to its observed considerable pressure dependence, which was not found in the studied hydroxyalkyl reactions. In addition, the CH3CO + NO rate coefficient was determined at two temperatures resulting in k298K(CH3CO + NO) = (5.6 ± 2.8) × 10(-13) cm(3) molecule(-1) s(-1). No products were found during these experiments, reasons for which are briefly discussed. PMID:26000890

  16. 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.

  17. 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

    2015-07-22

    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

  18. 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.

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

    PubMed

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

    2007-04-01

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

  20. 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

  1. ?-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products

    NASA Astrophysics Data System (ADS)

    Jones, Brian T.; Ham, Jason E.

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

  2. Determination of the rate coefficient for the N2/+/ + O reaction in the ionosphere

    NASA Technical Reports Server (NTRS)

    Torr, D. G.; Torr, M. R.; Orsini, N.; Hanson, W. B.; Hoffman, J. H.; Walker, J. C. G.

    1977-01-01

    Using approximately 400 simultaneous measurements of ion and neutral densities and temperatures, and the spectrum of the solar flux measured by the Atmosphere Explorer C satellite, we have determined the rate constant k1 for the reaction between N2(+) and O in the ionosphere for ion temperatures between 600 and 700 K. We find that k1 = 1.1 x 10 to the minus 10th power cu cm per sec, with a standard deviation of + or - 15%. If we use the temperature dependence for this reaction determined in the laboratory then at 300 K we find excellent agreement with the recommended laboratory value.

  3. Amino Acid and Anticodon Enhance Metabolic Reaction Rates Weakly but Specifically: Genetic Code World

    NASA Astrophysics Data System (ADS)

    Shimizu, Mikio

    2007-05-01

    Some hydrophilic amino acids such as glutamic acid, lysine, cysteine, and tyrosine having the side chains whose pKR are in or near the physiological pH range were shown to act as rate-enhancers or catalysts in various metabolic reactions weakly but specifically, as well as histidine discussed earlier. Anticodonic tri-ribonucleotides corresponding to the above amino acid catalysts (for example, UpUpU to lysine) also acted as catalysts similarly in each metabolic reaction. The primitive cell containing these molecules and metabolites could be the first minimal biomolecular system with metabolism and inheritance, possibly called as genetic code world.

  4. Two effects relevant for the study of astrophysical reaction rates: {gamma} transitions in capture reactions and Coulomb suppression of the stellar enhancement

    SciTech Connect

    Rauscher, Thomas [Departement Physik, Universitaet Basel, CH-4056 Basel (Switzerland)

    2009-01-28

    Nucleosynthesis processes involve reactions on several thousand nuclei, both close to and far off stability. The preparation of reaction rates to be used in astrophysical investigations requires experimental and theoretical input. In this context, two interesting aspects are discussed: (i) the relevant {gamma} transition energies in astrophysical capture reactions, and (ii) the newly discovered Coulomb suppression of the stellar enhancement factor. The latter makes a number of reactions with negative Q value more favorable for experimental investigation than their inverse reactions, contrary to common belief.

  5. Two effects relevant for the study of astrophysical reaction rates: gamma transitions in capture reactions and Coulomb suppression of the stellar enhancement

    E-print Network

    T. Rauscher

    2008-08-27

    Nucleosynthesis processes involve reactions on several thousand nuclei, both close to and far off stability. The preparation of reaction rates to be used in astrophysical investigations requires experimental and theoretical input. In this context, two interesting aspects are discussed: (i) the relevant gamma transition energies in astrophysical capture reactions, and (ii) the newly discovered Coulomb suppression of the stellar enhancement factor. The latter makes a number of reactions with negative Q value more favorable for experimental investigation than their inverse reactions, contrary to common belief.

  6. High-pressure rate rules for alkyl + O2 reactions. 2. The isomerization, cyclic ether formation, and ?-scission reactions of hydroperoxy alkyl radicals.

    PubMed

    Villano, Stephanie M; Huynh, Lam K; Carstensen, Hans-Heinrich; Dean, Anthony M

    2012-05-31

    The unimolecular reactions of hydroperoxy alkyl radicals (QOOH) play a central role in the low-temperature oxidation of hydrocarbons as they compete with the addition of a second O(2) molecule, which is known to provide chain-branching. In this work we present high-pressure rate estimation rules for the most important unimolecular reactions of the ?-, ?-, and ?-QOOH radicals: isomerization to RO(2), cyclic ether formation, and selected ?-scission reactions. These rate rules are derived from high-pressure rate constants for a series of reactions of a given reaction class. The individual rate expressions are determined from CBS-QB3 electronic structure calculations combined with canonical transition state theory calculations. Next we use the rate rules, along with previously published rate estimation rules for the reactions of alkyl peroxy radicals (RO(2)), to investigate the potential impact of falloff effects in combustion/ignition kinetic modeling. Pressure effects are examined for the reaction of n-butyl radical with O(2) by comparison of concentration versus time profiles that were obtained using two mechanisms at 10 atm: one that contains pressure-dependent rate constants that are obtained from a QRRK/MSC analysis and another that only contains high-pressure rate expressions. These simulations reveal that under most conditions relevant to combustion/ignition problems, the high-pressure rate rules can be used directly to describe the reactions of RO(2) and QOOH. For the same conditions, we also address whether the various isomers equilibrate during reaction. These results indicate that equilibrium is established between the alkyl, RO(2), and ?- and ?-QOOH radicals. PMID:22548467

  7. 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

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

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L.

    1986-01-01

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

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

    SciTech Connect

    Beste, Ariana [ORNL; Buchanan III, A C [ORNL

    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.

  10. Dependence of the Rate of an Interfacial Diels-Alder Reaction on the Steric Environment of the Immobilized Dienophile

    E-print Network

    Mrksich, Milan

    Dependence of the Rate of an Interfacial Diels-Alder Reaction on the Steric Environment for an interfacial Diels-Alder reaction and the steric environment around the reacting molecules. The study used catalysis,8 and combinatorial libraries.9 In this paper we use as a model reaction the Diels

  11. Reaction Rates for H-burning in Stars from Experiments with Radioactive Nuclear Beams

    SciTech Connect

    Trache, Livius [Cyclotron Institute, Texas A and M University, College Station, TX 77843-3366 (United States)

    2008-01-24

    In this lecture some of the indirect methods for nuclear astrophysics that can be applied to extract reaction rates for H-burning in stars are treated. Instead of reviewing all methods, I chose for exemplification four different experiments of our Texas A and M group, each involving a different method, but all related to the study of the proton rich nucleus {sup 23}Al. They involve the use of radioactive nuclear beams. I will describe the use of one-nucleon transfer reactions (the ANC method), breakup reactions at intermediate energies, {beta}-decay and {beta}-delayed proton-decay to extract nuclear structure information that is then used for nuclear astrophysics. I will show the specificities of each method, talk about their complementarities and redundancies.

  12. 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.

  13. Rate coefficients for the reaction of iodine oxide with methyl peroxy radicals.

    PubMed

    Dillon, Terry J; Tucceri, María E; Crowley, John N

    2010-12-17

    Pulsed laser photolysis radical generation is used to study the title reaction IO+CH(3)O(2)?products. Sensitive and selective laser-induced fluorescence detection of IO allows excess CH(3)O(2) conditions to be maintained throughout, ensuring minimal interference from other fast IO reactions. The rate coefficients, k(5)(296 K)=(3.4±1.4)×10(-12) cm(3) molecule(-1) s(-1), are obtained relative to a well-characterised reference value (k(3) for IO+HO(2)). This result agrees well with a previous determination from this laboratory and demonstrates that the above reaction proceeds an order of magnitude slower than suggested in other recent experimental and theoretical studies. Implications for HOx production/O(3) destruction within the marine boundary layer are briefly discussed. PMID:20963744

  14. An investigation of the relationships between rate and driving force in simple uncatalysed and enzyme-catalysed reactions with applications of the findings to chemiosmotic reactions.

    PubMed Central

    Stoner, C D

    1992-01-01

    Both the rate and the driving force of a reaction can be expressed in terms of the concentrations of the reactants and products. Consequently, rate and driving force can be expressed as a function of each other. This has been done for a single-reactant, single-product, uncatalysed reaction and its enzyme-catalysed equivalent using the van't Hoff reaction isotherm and Haldane's generalized Michaelis-Menten rate equation, the primary objective being explanation of the exponential and sigmoidal relationships between reaction rate and delta mu H+ commonly observed in studies on chemiosmotic reactions. Acquisition of a purely thermodynamic rate vs. driving-force relationship requires recognition of the intensive and extensive variables and maintenance of the extensive variables constant. This relationship is identical for the two reactions and is hyperbolic or sigmoidal, depending on whether the equilibrium constant is smaller or larger than unity. In the case of the catalysed reaction, acquisition of the purely thermodynamic relationship requires the assumption that the enzyme be equally effective in catalysing the forward and backward reactions. If this condition is not met, the relationship is modified by the enzyme in a manner which can be determined from the ratio of the Michaelis constants of the reactant and product. Under conditions of enzyme saturation in respect to reactant+product, the rate vs. driving-force relationship is determined exclusively by the thermodynamics of the reaction and a single kinetic parameter, the magnitude of which is determined by the relative effectiveness of the enzyme in catalysing the forward and backward reactions. In view of this finding, it is pointed out that, since the catalytic components of chemiosmotic reactions appear to be saturated with respect to the reactant-product pair that is varied in experimental rate vs. delta mu H+ determinations, and that, since many complex enzymic reactions conform to the simple Michaelis-Menten equation with respect to a single reactant-product pair when the concentrations of all other reactants and products are maintained constant, one might expect to be capable of simulating the experimental relationships simply from knowledge of the thermodynamics of the reaction and the relative effectiveness of the catalytic component in catalysing the forward and backward reactions using the simple Michaelis-Menten equation. That this expectation appears to be largely correct is demonstrated with model reactions.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:1533514

  15. Rates of hydration reactions in crustal shear zones and their implications for temporal variations in rheology

    NASA Astrophysics Data System (ADS)

    Yardley, B. W. D.; Harlov, D. E.; Heinrich, W.

    2009-04-01

    Crustal shear zones are commonly accompanied by retrograde metamorphism of pre-existing higher grade rocks. The retrograde reactions involve hydration, but the localisation of the retrogression suggests that reaction is limited by either the availability of water or the effect of deformation on reaction kinetics. Depending on the rate of retrograde hydration reactions, shear zones may either be uniformly wet for long periods of time during their deformation history, or may be dry for much of the time, experiencing brief periods where free water is present. If the latter scenario is correct, their strength will fluctuate markedly according to the presence or absence of water. In order to evaluate the likely residence time of water in mid-crustal shear zones, we have carried out experiments to investigate the rate of hydration of a natural granulite under greenschist to amphibolite facies metamorphic conditions (300-500C, 3-5 kbar). Seived and cleaned grains of powdered hornblende granulite were loaded in gold capsules with weighed amounts of water and reacted for periods of between 3 days and 12 weeks. The water consumed by hydration reactions was determined by weighing at the end of the run and combined with estimated surface areas to calculate the rate at which water was lost during the reaction. Results are of the order 10-7 to 10-8 g/s/m2 surface area, and are comparable to previous published data for the rate of hydration of K-feldspar + andalusite. SEM observation of the run charges shows that retrograde minerals including actinolite and sheet silicates were produced. There are no obvious differences in reaction rate between experiments at different P-T conditions. These reaction rates imply that if water infiltrates along a fracture surface in high grade rocks under mid-crustal conditions, forming a film with a half thickness of 100 microns, it will survive for around 10-100 years only before being consumed by hydration reactions. The film thickness has been estimated based on thicknesses of secondary fluid inclusion planes (normally less than 50 microns) and of mineral growth zones in secondary minerals. These times are short even relative to the repeat rate of earthquakes on major fault systems and suggest that a free water phase is absent from shear zone rocks for most of their history. We propose that shear zones are dry and relatively strong for much of their history but become weakened and deform when water is able to gain access from water-bearing fractures in overlying crust or, possibly, overpressured reservoirs at depth. Each episode of strain in response to water infiltration lasts for times of the order of tens to hundreds of years, and terminates when all the water has been consumed in hydrous minerals, thereby inhibiting further deformation by water-assisted mechanisms. We conclude that strain localisation in shear zones is normally the result of focussed introduction of water from an external source such as a fault at higher levels.

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

    SciTech Connect

    Hatakeyama, Shiro; Leu, Mingtaun (California Institute of Technology, Pasadena (USA))

    1989-07-27

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

  17. Site-specific rate coefficients for reaction of OH with ethanol from 298 to 900 K.

    PubMed

    Carr, Scott A; Blitz, Mark A; Seakins, Paul W

    2011-04-21

    The rate coefficients for reactions of OH with ethanol and partially deuterated ethanols have been measured by laser flash photolysis/laser-induced fluorescence over the temperature range 298-523 K and 5-100 Torr of helium bath gas. The rate coefficient, k(1.1), for reaction of OH with C(2)H(5)OH is given by the expression k(1.1) = 1.06 × 10(-22)T(3.58)?exp(1126/T) cm(3) molecule(-1) s(-1), and the values are in good agreement with previous literature. Site-specific rate coefficients were determined from the measured kinetic isotope effects. Over the temperature region 298-523 K abstraction from the hydroxyl site is a minor channel. The reaction is dominated by abstraction of the ? hydrogens (92 ± 8)% at 298 K decreasing to (76 ± 9)% with the balance being abstraction at the ? position where the errors are 2?. At higher temperatures decomposition of the CH(2)CH(2)OH product from ? abstraction complicates the kinetics. From 575 to 650 K, biexponential decays were observed, allowing estimates to be made for k(1.1) and the fractional production of CH(2)CH(2)OH. Above 650 K, decomposition of the CH(2)CH(2)OH product was fast on the time scale of the measured kinetics and removal of OH corresponds to reaction at the ? and OH sites. The kinetics agree (within ±20%) with previous measurements. Evidence suggests that reaction at the OH site is significant at our higher temperatures: 47-53% at 865 K. PMID:21443222

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  19. 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.

  20. 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.

  1. Oxygen consumption rates in subseafloor basaltic crust derived from a reaction transport model.

    PubMed

    Orcutt, Beth N; Wheat, C Geoffrey; Rouxel, Olivier; Hulme, Samuel; Edwards, Katrina J; Bach, Wolfgang

    2013-01-01

    Oceanic crust is the largest potential habitat for life on Earth and may contain a significant fraction of Earth's total microbial biomass; yet, empirical analysis of reaction rates in basaltic crust is lacking. Here we report the first assessment of oxygen consumption in young (~8?Ma) and cool (<25?°C) basaltic crust, which we calculate from modelling dissolved oxygen and strontium pore water gradients in basal sediments collected during Integrated Ocean Drilling Program Expedition 336 to 'North Pond' on the western flank of the Mid-Atlantic Ridge. Dissolved oxygen is completely consumed within the upper to middle section of the sediment column, with an increase in concentration towards the sediment-basement interface, indicating an upward supply from oxic fluids circulating within the crust. A parametric reaction transport model of oxygen behaviour in upper basement suggests oxygen consumption rates of 1?nmol? cm(-3)ROCK d(-1) or less in young and cool basaltic crust. PMID:24071791

  2. Modelling of silicon oxynitridation by nitrous oxide using the reaction rate approach

    NASA Astrophysics Data System (ADS)

    Dominique Krzeminski, Christophe

    2013-12-01

    Large technological progress in oxynitridation processing leads to the introduction of silicon oxynitride as ultra-thin gate oxide. On the theoretical side, few studies have been dedicated to the process modelling of oxynitridation. Such an objective is a considerable challenge regarding the various atomistic mechanisms occurring during this fabrication step. In this article, some progress performed to adapt the reaction rate approach for the modelling of oxynitride growth by a nitrous ambient are reported. The Ellis and Buhrman's approach is used for the gas phase decomposition modelling. Taking into account the mass balance of the species at the interface between the oxynitride and silicon, a minimal kinetic model describing the oxide growth has been calibrated and implemented. The influence of nitrogen on the reaction rate has been introduced in an empirical way. The oxidation kinetics predicted with this minimal model compares well with several experiments.

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

    NASA Astrophysics Data System (ADS)

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-12-01

    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 N2 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.

  4. The 23Na({\\alpha},p) 26Mg reaction rate at astrophysically relevant energies

    E-print Network

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

    2015-01-01

    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.

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

    Microsoft Academic Search

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

    2001-01-01

    The effects of the highly damped modes in the energy and reaction rates in a plasma are discussed. These modes, with wave numbers k≫kD, even being only weakly excited, with less than kBT 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

  6. Structures and reaction rates of the gaseous oxidation of SO2 by an O-

    E-print Network

    Meskhidze, Nicholas

    Structures and reaction rates of the gaseous oxidation of SO2 by an O- 3 (H2O)0-5 cluster - an ab initio study N. Bork, T. Kurt´en, M.B. Enghoff, J.O.P. Pedersen, K.V. Mikkelsen, and H. Svensmark shown in Fig. 7 in the main article. Sulfur (yellow), oxygen (red), hydrogen (white). #12;Table SI-2: T1

  7. 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.

  8. Absolute rate of the reaction of Cl/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.

    1977-01-01

    Rate constants for the reaction Cl + CH4 yields HCl + CH3 were measured in the range 200-500 K by the plot flash photolysis-resonance fluorescence technique. An Arrhenius plot of the mean rate constant observed at 14 equally spaced temperatures is best fit by the expression k = 5.44 times 10 to the minus 19th times T to the exponent 2.50 times exp(-608/T) cu cm per molecule per sec. Appropriate expressions are also given for the rate constant in the two ranges 200-299 K and 299-500 K. These results are compared with a number of other existing determinations of the rate constant by other methods and in different temperature ranges. Most discrepancies are attributed to the nonlinear Arrhenius behavior.

  9. 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).

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

    NASA Technical Reports Server (NTRS)

    Herbst, E.

    1982-01-01

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

  11. 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.

  12. Rate coefficients for reaction of OH with acetone between 202 and 395 K

    SciTech Connect

    Wollenhaupt, M.; Carl, S.A.; Horowitz, A.; Crowley, J.N.

    2000-03-30

    The kinetics of the title reaction were investigated between 202 and 395 K and at 20, 50, and 100 Torr of Ar or N{sub 2} bath gas using pulsed laser photolysis (PLP) generation of OH combined with both resonance fluorescence (RF) and laser-induced fluorescence (LIF) detection. OH was generated either by the sequential 439 nm, two-photon dissociation of NO{sub 2} in the presence of H{sub 2}, or by HONO photolysis at 351 nm. The accuracy of the rate constants obtained was enhanced by optical absorption measurements of acetone concentrations both before and after the photolysis reactor. The temperature dependence is not describe by a simple Arrhenius expression but by k{sub 1} (202--395 K) = 8.8 x 10{sup {minus}12} exp({minus}1,320/T) + 1.7 x 10{sup {minus}14} exp(423/T) cm{sup 3} s{sup {minus}1}, indicating that a simple H atom abstraction may not be the only reaction mechanism. The estimated total error (95% confidence) associated wit the rate coefficient derived from this expression is estimated as 5% and is independent of temperature. The curvature in the Arrhenius plot results in a significantly larger rate coefficient at low temperatures than obtained by extrapolation of the previous measurement and implies greater significance for the reaction with OH as a sink for acetone in the upper troposphere than presently assumed.

  13. 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.

  14. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

    PubMed

    Gallis, Michael A; Bond, Ryan B; Torczynski, John R

    2009-09-28

    Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases. PMID:19791885

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Dissolved CO2 during geological CO2 storage may react with minerals in fractured rocks, confined aquifers, or faults, resulting in mineral precipitation and dissolution. The overall rate of reaction can be affected by coupled processes among hydrodynamics, transport, and reactions at the (sub) pore-scale. In this research pore-scale modeling of coupled fluid flow, reactive transport, and heterogeneous reaction at the mineral surface is applied to account for permeability alterations caused by precipitation-induced pore-blocking. This work is motivated by the observed CO2 seeps from a natural analog to geologic CO2 sequestration at Crystal Geyser, Utah. A key observation is the lateral migration of CO2 seep sites at a scale of ~ 100 meters over time. A pore-scale model provides fundamental mechanistic explanations of how calcite precipitation alters flow paths by pore plugging under different geochemical compositions and pore configurations. In addition, response function of reaction rates will be constructed from pore-scale simulations which account for a range of reaction regimes characterized by the Damkohler and Peclet numbers. Newly developed response functions will be used in a continuum scale model that may account for large-scale phenomena mimicking lateral migration of surface CO2 seeps. Comparison of field observations and simulations results will provide mechanistic explanations of the lateral migration and enhance our understanding of subsurface processes associated with the CO2 injection. This work is supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  16. Enzymatic reaction of silent substrates: kinetic theory and application to the serine protease chymotrypsin.

    PubMed

    Case, April; Huskey, W Phillip; Stein, Ross L

    2003-04-29

    Investigating the selectivity that an enzyme expresses toward its substrates can be technically challenging if reaction of these substrates is not accompanied by a conveniently monitored change in some physicochemical property. In this paper, we describe a simple method for determining steady-state kinetic parameters for enzymatic turnover of such "silent" substrates. According to this method, silent substrate S is allowed to compete for enzymic reaction with signal-generating substrate S*, whose conversion to product can be conveniently monitored. Full reaction progress curves are collected under conditions of [S*](o) < K(m)* and [S](o) >or= 3K(m). Progress curves collected under these conditions are characterized by an initial lag phase of duration tau that is followed by the pseudo-first-order reaction of S. Steady-state kinetic parameters for the silent substrate can be obtained by one of two methods. One method combines least-squares fitting with numerical integration of appropriate rate equations to analyze the progress curves, while the other method relies on direct graphical analysis in which K(m) is the value of [S](o) that reduces the control velocity by a factor of 2 and V(max) is shown to simply equal the ratio [S](o)/tau. We use these methods to analyze the alpha-chymotrypsin-catalyzed hydrolysis of silent substrate Suc-Ala-Phe-AlaNH(2) with signal generator Suc-Ala-Phe-pNA. From the curve-fitting method, k(c) = 0.9 +/- 0.2 s(-1) and K(m) = 0.4 +/- 0.1 mM, while by direct graphical analysis, k(c) = 1.1 +/- 0.1 s(-1) and K(m) = 0.51 +/- 0.03 mM. As validation of this new method, we show agreement of these values with those determined independently by HPLC analysis of the hydrolysis of Suc-Ala-Phe-AlaNH(2) by alpha-CT, where k(c) = 1.1 +/- 0.1 s(-1) and K(m) = 0.5 +/- 0.1 mM. PMID:12705836

  17. 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.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

    Funaki, Yasuro

    2015-04-01

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

  20. 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).

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

    PubMed

    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+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. PMID:25416891

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

    NASA Astrophysics Data System (ADS)

    Orkin, Vladimir; Kurylo, Michael

    2015-04-01

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

  3. 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.

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

    SciTech Connect

    Suzuki, Toshio [Department of Physics and Graduate School of Integrated Basic Sciences, College of Humanities and Sciences, Nihon University Sakurajosui 3-25-40, Setagaya-ku, Tokyo 156-8550 (Japan); Center for Nuclear Study, University of Tokyo, Hirosawa, Wako-shi, Saitama 351-0198 (Japan); National Astronomical Observatory of Japan, Mitaka, Tokyo 181-8588 (Japan); Honma, Michio [Center for Mathematical Sciences, University of Aizu, Aizu-Wakamatsu, Fukushima 965-8580 (Japan); Mao, Helene [ENSPS, Pole API-Parc d'Innovation, Boulevard Sebastien Brant, BP 10413, F-67412 Illkirch Cedex (France); Otsuka, Takaharu [Department of Physics and Center for Nuclear Study, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, Michigan 48824 (United States); Kajino, Toshitaka [National Astronomical Observatory of Japan, Mitaka, Tokyo 181-8588 (Japan); Deaprtment of Astronomy, Graduate School of Science, University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)

    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.

  5. 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.

  6. 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. (Geological Survey, Menlo Park, CA (United States)); Hacker, B.R.; Mosenfelder, J.L. (Stanford Univ., Stanford, CA (United States). 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

  7. Multi-Dimensional Simulations of Fluorocarbon Plasmas with Ion Energy Resolved Surface Reaction Rates

    NASA Astrophysics Data System (ADS)

    Zhou, Ning; Kolobov, Vladimir; Kudriavtsev, Vladimir

    2001-10-01

    The commercial CFD-ACE+ software has been extended to account for ion energy dependent surface reactions. The ion energy distribution function and the mean ion energy at a biased wafer were obtained using the Riley sheath model extended by the NASA group (Bose et al., J. Appl. Phys. v.87, 7176(2000)). The plasma chemistry model (by P. Ho et al., SAND2001-1292) consisting of 132-step gas-phase reactions and 55-step ion energy dependent surface reactions, was implemented to simulate the C2F6 plasma etching of silicon dioxide in an Inductively Coupled Plasma. Validation studies have been performed against the experimental data by Anderson et al. of UNM for a lab-scale GEC reactor. For a wide range of operating conditions (pressure: 5-25 mTorr; plasma power: 205-495 Watts; bias power: 22-148 Watts), the average etch rate calculated by CFD-ACE+ 2-D simulations agrees very well with those by 0-D AURORA predictions and the experimental data. The CFD-ACE+ simulations allow one to study the radial uniformity of the etch rate depending on discharge conditions.

  8. Rates and mechanisms of reaction of hydrogen sulfide with iron chelates. Topical report, April 1993

    SciTech Connect

    DeBerry, D.W.

    1993-04-01

    Chelated iron liquid redox sulfur recovery processes hold promise for providing economical removal of hydrogen sulfide from natural gas with conversion to solid sulfur. They are complex chemical systems. An objective of this project is to identify and characterize the chemical interactions occurring in these liquid redox systems and determine which process parameters impact performance. This report presents the results of this project concerning the mechanism of oxidation of hydrogen sulfide by iron-based compounds in the liquid phase. The rates of reactions of chelated iron sorbing reagents with reduced sulfur species were measured over a wide range of conditions. The effects of relative reactant concentrations, pH, and ionic strength on these rates have been determined using a number of different methods. Effects of temperature and chelate type on the reaction of chelate iron with sulfide are also presented here. A kinetic model was developed to interpret these results and provide an overall framework for the reaction mechanism. This model has proven to be useful for integrating and explaining the results of the kinetics measurements. In addition, the model may become a useful tool for optimizing process chemistry and a key component of a general chemical process model. Details of the model and verification runs are given in this report.

  9. Standard Test Method for Measuring Reaction Rates by Radioactivation of Uranium-238

    E-print Network

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This test method covers procedures for measuring reaction rates by assaying a fission product (F.P.) from the fission reaction 238U(n,f)F.P. 1.2 The reaction is useful for measuring neutrons with energies from approximately 1.5 to 7 MeV and for irradiation times up to 30 to 40 years. 1.3 Equivalent fission neutron fluence rates as defined in Practice E 261 can be determined. 1.4 Detailed procedures for other fast-neutron detectors are referenced in Practice E 261. 1.5 The values stated in SI units are to be regarded as standard. No other unites of measurement are included in this standard. 1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

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

    SciTech Connect

    West, Christopher; Heger, Alexander [Minnesota Institute for Astrophysics, School of Physics and Astronomy, University of Minnesota, Minneapolis, MN 55455 (United States); Austin, Sam M., E-mail: west0482@umn.edu, E-mail: alexander.heger@monash.edu, E-mail: austin@nscl.msu.edu [Joint Institute for Nuclear Astrophysics, Notre Dame, IN 46556 (United States)

    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.

  11. 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.

  12. 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.

  13. Can interstellar H2S be formed via gas-phase reactions? Calculations concerning the rates of the ternary and radiative association reactions between HS+ and H2.

    PubMed

    Herbst, E; DeFrees, D J; Koch, W

    1989-01-01

    Based on laboratory work involving the ternary association reaction of HS+ and H2 at 80 K, we have estimated the rate of the analogous radiative association reaction under interstellar conditions. Both the ternary and radiative association reactions appear to occur via a mechanism in which the electronic spin of the H3S+ complex changes before the complex is stabilized. Although this spin change is of low probability, it leads to a radiative association rate coefficient at 80 K of 7 x 10(-16) cm3 s-1 if radiative stabilization occurs at a rate of 10(3) s-1. This value of the radiative association rate coefficient at 80 K is large enough to lead to the observed abundance of H2S in the ambient ridge source in Orion. PMID:11542171

  14. Rate Coefficient Determinations for the Reaction of Br-Atoms with a Series of Oxygenated VOCs

    NASA Astrophysics Data System (ADS)

    Orlando, J. J.; Tyndall, G. S.

    2014-12-01

    Bromine atoms are known to be prevalent in marine regions, and to contribute to the ozone budget there. In polar springtime, Br-atom levels can be in the range 107-109 cm-3 in the marine boundary layer, while values over the open ocean may fall in the 105 ? 107 cm-3 range. It is also known that many VOCs and oxygenated VOCs have oceanic/cryogenic emission sources, and reactions of Br with these (O)VOCs can then play a role in the partitioning of inorganic Br, acting as a sink for reactive Br/BrO. Thus, there is a need to develop a more complete and more reliable database for Br/(O)VOC kinetic data than what is currently available. We have embarked on a relative-rate study of the rate coefficients for reaction of Br-atoms with ?15 (O)VOCs, including alcohols, ethers, aldehydes, isoprene, other unsaturated compounds, and various multifunctional species. Progress on these rate coefficient determinations, and trends in Br-atom reactivity with organics, will be reported.

  15. Unimolecular reaction rate constants of NO{sub 2} just above D{sub 0}

    SciTech Connect

    Bezel, I.; Stolyarov, D.; Wittig, C.

    1999-12-09

    Photoinitiated unimolecular decomposition on a barrierless potential energy surface (PES) has been studied for the reaction NO{sub 2} {yields} O({sup 3}P{sub 2}) + NO(X{sup 2}{Pi}{sub 1/2}, {nu} = 0) for excess energies up to approximately 17 cm{sup {minus}1} above the dissociation threshold (i.e., D{sub 0} for nonrotating molecules) by using expansion-cooled samples and the time-resolved pump-probe technique. To examine the threshold region with enough energy resolution to discern abrupt changes in the rate constant, should they occur, a pump-probe cross-correlation temporal width of {approximately}25 ps and a pump line width {le}2 cm{sup {minus}1} has been used. These are the first direct observations of the reaction rate constants in this energy regime. The rate constant was found to increase by an order of magnitude, varying from {approximately}2 x 10{sup 10} s{sup {minus}1} to {ge}10{sup 11} s{sup {minus}1}, the latter being a rough lower bound imposed by the experimental arrangement. The rate constant does not display the energy dependence predicted by using phase space theory, at least in detail. Rather, it appears to reflect the highly complex nature of the levels and the multiple PESs that are believed to be responsible for the anomalously high vibronic level density which has been observed just below D{sub 0}. These results bridge the gap between spectroscopic studies which have been carried out at energies just above D{sub 0} and ultrafast experiments which have measured rate constants in this energy region with pump laser spectral widths of {approximately}30 cm{sup {minus}1}.

  16. Redox reaction rates in shallow aquifers: Implications for nitrate transport in groundwater and streams

    USGS Publications Warehouse

    Tesoriero, Anthony J.

    2012-01-01

    Groundwater age and water chemistry data along flow paths from recharge areas to streams were used to evaluate the trends and transformations of agricultural chemicals. Results from this analysis indicate that median nitrate recharge concentrations in these agricultural areas have increased markedly over the last 50 years from 4 mg N/L in samples collected prior to 1983 to 7.5 mg N/L in samples collected since 1983. The effect that nitrate accumulation in shallow aquifers will have on drinking water quality and stream ecosystems is dependent on the rate of redox reactions along flow paths and on the age distribution of nitrate discharging to supply wells and streams.

  17. Rate of Influenza Vaccination and Its Adverse Reactions Seen in Health Care Personnel in a Single Tertiary Hospital in Korea

    Microsoft Academic Search

    Chang-Seop Lee; Kang-Hyu Lee; Min-Hee Jung; Heung-Bum Lee

    2008-01-01

    SUMMARY: To determine the vaccination rate and its adverse reactions after influenza vaccination, we admin- istered an anonymous questionnaire survey during the last three influenza seasons from 2005 - 2006 to 2007 - 2008. In total, the rate of influenza vaccination was 82.3% in health-care personnel. Dividing the subjects into four groups by work category, the vaccine coverage rates were

  18. RATE CONSTANTS FOR THE REACTION OF OH RADICALS WITH A SERIES OF ALKENES AND DIALKENES AT 295 + OR - 1 K

    EPA Science Inventory

    Using a relative rate technique, rate constants for the gas phase reactions of the OH radical with n-butane, n-hexane and a series of alkenes and dialkenes, relative to that for propene, have been determined in one atmosphere of air at 295 + or - 1K. The resulting rate constant d...

  19. Organic photochemistry. 20. A method for estimating gas-phase rate constants for reactions of hydroxyl radicals with organic compounds from their relative rates of reaction with hydrogen peroxide under photolysis in 1,1,2-trichlorotrifluoroethane solution

    Microsoft Academic Search

    Wendell L. Dilling; Stanley J. Gonsior; Glenn U. Boggs; Celia G. Mendoza

    1988-01-01

    The reaction with hydroxyl radicals appears to be the major transformation route for many organic compounds in the atmosphere. To avoid the difficulties of measuring the rate constants for these reactions in the gas phase for some compounds, we have developed a solution-phase system for measuring relative rates. This system involves photolysis of continuously extracted 90% hydrogen peroxide into 1,1,2-trichlorotrifluoroethane

  20. 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.

  1. Informing Neutron-Capture Rates through (d,p) Reactions on Neutron-Rich Tin Isotopes

    NASA Astrophysics Data System (ADS)

    Manning, B.; Cizewski, J. A.; Kozub, R. L.; Ahn, S.; Allmond, J. M.; Bardayan, D. W.; Chae, K. Y.; Chipps, K. A.; Howard, M. E.; Jones, K. L.; Liang, J. F.; Matos, M.; Nunes, F. M.; Nesaraja, C. D.; O'Malley, P. D.; Pain, S. D.; Peters, W. A.; Pittman, S. T.; Ratkiewicz, A.; Schmitt, K. T.; Shapira, D.; Smith, M. S.; Titus, L.

    2014-03-01

    Level energies and spectroscopic information for neutron-rich nuclei provide important input for r-process nucleosynthesis calculations; specifically, the location and strength of single-neutron l = 1 states when calculating neutron-capture rates. Surman and collaborators have performed sensitivity studies to show that varying neutron-capture rates can significantly alter final r-process abundances. However, there are many nuclei important to the r-process that cannot be studied. Extending studies to more neutron-rich nuclei will help constrain the nuclear shell-model in extrapolating to nuclei even further from stability. The (d,p) reaction has been measured with radioactive ion beams of 126Sn and 128Sn to complete the set of (d,p) studies on even mass tin isotopes from doubly-magic 132 to stable 124Sn. Work supported in part by the U.S. Department of Energy and National Science Foundation.

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

    SciTech Connect

    Hessler, J.P. [Argonne National Laboratory, IL (United States)

    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.

  3. Enskog's kinetic theory of dense gases for chemically reacting binary mixtures. I. Reaction rate and viscosity coefficients

    Microsoft Academic Search

    Adriano W. Silva; Giselle M. Alves; Gilberto M. Kremer

    2008-01-01

    The symmetric moderately dense reaction A+A&rlhar2;B+B is analyzed within the framework of Enskog's equation by using the Chapman Enskog method. For the last stage of a chemical reaction where the affinity is considered a small quantity the constitutive equations for the reaction rate densities and the pressure tensor of the mixture are calculated in terms of the thermodynamic forces: affinity,

  4. Enskog’s kinetic theory of dense gases for chemically reacting binary mixtures. I. Reaction rate and viscosity coefficients

    Microsoft Academic Search

    Adriano W. Silva; Giselle M. Alves; Gilberto M. Kremer

    2008-01-01

    The symmetric moderately dense reaction A+A?B+B is analyzed within the framework of Enskog’s equation by using the Chapman–Enskog method. For the last stage of a chemical reaction–where the affinity is considered a small quantity–the constitutive equations for the reaction rate densities and the pressure tensor of the mixture are calculated in terms of the thermodynamic forces: affinity, divergence and gradient

  5. 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.

  6. Measuring rates of reaction in supercooled organic particles with implications for atmospheric aerosol.

    PubMed

    Hearn, John D; Smith, Geoffrey D

    2005-07-01

    The kinetics of heterogeneous reactions involving supercooled organic droplets is reported for the first time. Reactions between ozone and internally-mixed sub-micrometre particles containing an unsaturated alkenoic acid, oleic acid, and an n-alkanoic acid, myristic acid, were studied as a simple model for the oxidation of meat-cooking aerosol. The reactions were followed by monitoring the rate of oleic acid loss using an Aerosol CIMS (chemical ionization mass spectrometry) instrument for real-time particle analysis. Evidence of as much as 32 degrees C supercooling at room temperature was observed depending on particle composition. FTIR spectra of the aerosol also demonstrate features indicative of supercooling. Particles in which crystallization was induced by cooling below room temperature demonstrated decreased reactivity by a factor of 12 compared to supercooled particles of the same composition. This drastic difference in reactivity could have significant implications for the lifetimes of reactive species in ambient aerosol as well as for the accurate source apportionment of particulate matter. PMID:16189562

  7. 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.

  8. 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.

  9. Revised Production Rates for Na-22 and Mn-54 in Meteorites Using Cross Sections Measured for Neutron-induced Reactions

    NASA Technical Reports Server (NTRS)

    Sisterson, J. M.; Kim, K. J.; Reedy, R. C.

    2004-01-01

    The interactions of galactic cosmic rays (GCR) with extraterrestrial bodies produce small amounts of radionuclides and stable isotopes. The production rates of many relatively short-lived radionuclides, including 2.6-year Na-22 and 312-day Mn-54, have been measured in several meteorites collected very soon after they fell. Theoretical models used to calculate production rates for comparison with the measured values rely on input data containing good cross section measurements for all relevant reactions. Most GCR particles are protons, but secondary neutrons make most cosmogenic nuclides. Calculated production rates using only cross sections for proton-induced reactions do not agree well with measurements. One possible explanation is that the contribution to the production rate from reactions initiated by secondary neutrons produced in primary GCR interactions should be included explicitly. This, however, is difficult to do because so few of the relevant cross sections for neutron-induced reactions have been measured.

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

    E-print Network

    Iliadis, Christian; Chieffi, Alessandro; Limongi, Marco

    2011-01-01

    We investigate the effects of thermonuclear reaction rate variations on 26Al production in massive stars. The dominant production sites in such events were recently investigated by using stellar model calculations: explosive neon-carbon burning, convective shell carbon burning, and convective core hydrogen burning. Post-processing nucleosynthesis calculations are performed for each of these sites by adopting temperature-density-time profiles from recent stellar evolution models. For each profile, we individually multiplied the rates of all relevant reactions by factors of 10, 2, 0.5 and 0.1, and analyzed the resulting abundance changes of 26Al. Our simulations are based on a next-generation nuclear physics library, called STARLIB, which contains a recent evaluation of Monte Carlo reaction rates. Particular attention is paid to quantifying the rate uncertainties of those reactions that most sensitively influence 26Al production. For stellar modelers our results indicate to what degree predictions of 26Al nucle...

  11. 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.

  12. Reaction Rate Theory of Radiation Exposure and Scaling Hypothesis in Mutation Frequency

    NASA Astrophysics Data System (ADS)

    Manabe, Yuichiro; Nakamura, Issei; Bando, Masako

    2014-11-01

    We have developed a kinetic reaction model for cells with irradiated DNA molecules due to ionizing radiation exposure. Our theory simultaneously accounts for the time-dependent reactions of DNA damage, DNA mutation and DNA repair, and the proliferation and apoptosis of cells in a tissue with a minimal set of model parameters. In contrast to existing theories of radiation exposition, we do not assume the relationships between the total dose and the induced mutation frequency. Our theory provides a universal scaling function that reasonably explains the mega-mouse experiments by Russell and Kelly [Proc. Natl. Acad. Sci. U.S.A. 79, 542 (1982)] with different dose rates. Furthermore, we have estimated the effective dose rate, which is biologically equivalent to the ionizing effects other than those caused by artificial irradiation. This value is 1.11 × 10?3 Gy/h, which is significantly larger than the effect caused by natural background radiation.

  13. Temperature and Pressure-Dependent Rate Coefficients for the Reaction of Vinyl Radical with Molecular Oxygen.

    PubMed

    Goldsmith, C Franklin; Harding, Lawrence B; Georgievskii, Yuri; Miller, James A; Klippenstein, Stephen J

    2015-07-16

    State-of-the-art calculations of the C2H3O2 potential energy surface are presented. A new method is described for computing the interaction potential for R + O2 reactions. The method, which combines accurate determination of the quartet potential along the doublet minimum energy path with multireference calculations of the doublet/quartet splitting, decreases the uncertainty in the doublet potential and thence the rate constants by more than a factor of 2. The temperature- and pressure-dependent rate coefficients are computed using variable reaction coordinate transition-state theory, variational transition-state theory, and conventional transition-state theory, as implemented in a new RRKM/ME code. The main bimolecular product channels are CH2O + HCO at lower temperatures and CH2CHO + O at higher temperatures. Above 10 atm, the collisional stabilization of CH2CHOO directly competes with these two product channels. CH2CHOO decomposes primarily to CH2O + HCO. The next two most significant bimolecular products are OCHCHO + H and (3)CHCHO + OH, and not C2H2 + HO2. C2H3 + O2 will be predominantly chain branching above 1700 K. Uncertainty analysis is presented for the two most important transition states. The uncertainties in these two barrier heights result in a significant uncertainty in the temperature at which CH2CHO + O overtakes all other product channels. PMID:25978112

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  16. 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

    2011-01-01

    Reactions of hydroxyl (OH) radicals with 1-butene (k{sub 1}), trans-2-butene (k{sub 2}), and cis-2-butene (k{sub 3}) 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, (CH{sub 3}){sub 3}?CO?OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R{sub 1}(5) line of the OH A?X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C{sub 5} 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.

  17. Perchlorate Reduction by Autotrophic Bacteria in the

    E-print Network

    ) h-1 and a half-velocity constant (Ks) of 8900 µg L-1. The overall rate of perchlorate reduction followed pseudo-first- order reaction rates with constants of 0.059 and 0.033 h-1 at initial pH 7 and 8, 12). However, the low solubility of H2 in water and its hazardous (

  18. Kinetic theory of oxygen isotopic exchange between minerals and water

    Microsoft Academic Search

    R. E. Criss; R. T. Gregory; H TAYLORJR

    1987-01-01

    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in ''closed'' and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation

  19. Reaction rate theory: what it was, where is it today, and where is it going?

    PubMed

    Pollak, Eli; Talkner, Peter

    2005-06-01

    A brief history is presented, outlining the development of rate theory during the past century. Starting from Arrhenius [Z. Phys. Chem. 4, 226 (1889)], we follow especially the formulation of transition state theory by Wigner [Z. Phys. Chem. Abt. B 19, 203 (1932)] and Eyring [J. Chem. Phys. 3, 107 (1935)]. Transition state theory (TST) made it possible to obtain quick estimates for reaction rates for a broad variety of processes even during the days when sophisticated computers were not available. Arrhenius' suggestion that a transition state exists which is intermediate between reactants and products was central to the development of rate theory. Although Wigner gave an abstract definition of the transition state as a surface of minimal unidirectional flux, it took almost half of a century until the transition state was precisely defined by Pechukas [Dynamics of Molecular Collisions B, edited by W. H. Miller (Plenum, New York, 1976)], but even this only in the realm of classical mechanics. Eyring, considered by many to be the father of TST, never resolved the question as to the definition of the activation energy for which Arrhenius became famous. In 1978, Chandler [J. Chem. Phys. 68, 2959 (1978)] finally showed that especially when considering condensed phases, the activation energy is a free energy, it is the barrier height in the potential of mean force felt by the reacting system. Parallel to the development of rate theory in the chemistry community, Kramers published in 1940 [Physica (Amsterdam) 7, 284 (1940)] a seminal paper on the relation between Einstein's theory of Brownian motion [Einstein, Ann. Phys. 17, 549 (1905)] and rate theory. Kramers' paper provided a solution for the effect of friction on reaction rates but left us also with some challenges. He could not derive a uniform expression for the rate, valid for all values of the friction coefficient, known as the Kramers turnover problem. He also did not establish the connection between his approach and the TST developed by the chemistry community. For many years, Kramers' theory was considered as providing a dynamic correction to the thermodynamic TST. Both of these questions were resolved in the 1980s when Pollak [J. Chem. Phys. 85, 865 (1986)] showed that Kramers' expression in the moderate to strong friction regime could be derived from TST, provided that the bath, which is the source of the friction, is handled at the same level as the system which is observed. This then led to the Mel'nikov-Pollak-Grabert-Hanggi [Mel'nikov and Meshkov, J. Chem. Phys. 85, 1018 (1986); Pollak, Grabert, and Hanggi, ibid. 91, 4073 (1989)] solution of the turnover problem posed by Kramers. Although classical rate theory reached a high level of maturity, its quantum analog leaves the theorist with serious challenges to this very day. As noted by Wigner [Trans. Faraday Soc. 34, 29 (1938)], TST is an inherently classical theory. A definite quantum TST has not been formulated to date although some very useful approximate quantum rate theories have been invented. The successes and challenges facing quantum rate theory are outlined. An open problem which is being investigated intensively is rate theory away from equilibrium. TST is no longer valid and cannot even serve as a conceptual guide for understanding the critical factors which determine rates away from equilibrium. The nonequilibrium quantum theory is even less well developed than the classical, and suffers from the fact that even today, we do not know how to solve the real time quantum dynamics for systems with "many" degrees of freedom. PMID:16035918

  20. Ground reaction forces and loading rates associated with parkour and traditional drop landing techniques.

    PubMed

    Puddle, Damien L; Maulder, Peter S

    2013-01-01

    Due to the relative infancy of Parkour there is currently a lack of empirical evidence on which to base specific technique instruction upon. The purpose of this study was to compare the ground reaction forces and loading rates involved in two Parkour landing techniques encouraged by local Parkour instructors and a traditional landing technique recommended in the literature. Ten male participants performed three different drop landing techniques (Parkour precision, Parkour roll, and traditional) onto a force plate. Compared to the traditional technique the Parkour precision technique demonstrated significantly less maximal vertical landing force (38%, p < 0.01, ES = 1.76) and landing loading rate (54%, p < 0.01, ES = 1.22). Similarly, less maximal vertical landing force (43%, p < 0.01, ES = 2.04) and landing loading rate (63%, p < 0.01, ES = 1.54) were observed in the Parkour roll technique compared to the traditional technique. It is unclear whether or not the Parkour precision technique produced lower landing forces and loading rates than the Parkour roll technique as no significant differences were found. The landing techniques encouraged by local Parkour instructors such as the precision and roll appear to be more appropriate for Parkour practitioners to perform than a traditional landing technique due to the lower landing forces and loading rates experienced. Key pointsParkour precision and Parkour roll landings were found to be safer than a traditional landing technique, resulting in lower maximal vertical forces, slower times to maximal vertical force and ultimately lesser loading rates.Parkour roll may be more appropriate (safer) to utilize than the Parkour precision during Parkour landing scenarios.The Parkour landing techniques investigated n this study may be beneficial for landing by non-Parkour practitioners in everyday life. PMID:24149735

  1. Ground Reaction Forces and Loading Rates Associated with Parkour and Traditional Drop Landing Techniques

    PubMed Central

    Puddle, Damien L.; Maulder, Peter S.

    2013-01-01

    Due to the relative infancy of Parkour there is currently a lack of empirical evidence on which to base specific technique instruction upon. The purpose of this study was to compare the ground reaction forces and loading rates involved in two Parkour landing techniques encouraged by local Parkour instructors and a traditional landing technique recommended in the literature. Ten male participants performed three different drop landing techniques (Parkour precision, Parkour roll, and traditional) onto a force plate. Compared to the traditional technique the Parkour precision technique demonstrated significantly less maximal vertical landing force (38%, p < 0.01, ES = 1.76) and landing loading rate (54%, p < 0.01, ES = 1.22). Similarly, less maximal vertical landing force (43%, p < 0.01, ES = 2.04) and landing loading rate (63%, p < 0.01, ES = 1.54) were observed in the Parkour roll technique compared to the traditional technique. It is unclear whether or not the Parkour precision technique produced lower landing forces and loading rates than the Parkour roll technique as no significant differences were found. The landing techniques encouraged by local Parkour instructors such as the precision and roll appear to be more appropriate for Parkour practitioners to perform than a traditional landing technique due to the lower landing forces and loading rates experienced. Key points Parkour precision and Parkour roll landings were found to be safer than a traditional landing technique, resulting in lower maximal vertical forces, slower times to maximal vertical force and ultimately lesser loading rates. Parkour roll may be more appropriate (safer) to utilize than the Parkour precision during Parkour landing scenarios. The Parkour landing techniques investigated n this study may be beneficial for landing by non-Parkour practitioners in everyday life. PMID:24149735

  2. Experimental values of rate constants and ion product distributions for reactions of a series of ions with CS2

    NASA Astrophysics Data System (ADS)

    Molek, Christopher D.; McLain, Jason L.; Adams, Nigel G.; Babcock, Lucia M.; Gibbs, Laura L.

    2004-07-01

    Rate constants and product ion distributions have been determined in a Selected Ion Flow Tube (SIFT) for the reactions of He+, He2+, Ar+, N2+, N+, CO+, CO2+, O+, D+, CS+, C+, S+, CS2+, S2+ and D3+ with CS2 at 297 K. These ions have recombination energies varying from 2372 kJ/mol (24.58 eV) for He+ to 903 kJ/mol (9.36 eV) for S2+. The reactions, except for the Ar+, S2+ and CS2+ reactions proceed at, or close to, the collisional rate with charge transfer (both dissociative and non-dissociative) being an important mechanism. S+ is a common product and, in the case of D3+, exothermic proton transfer is rapid. For the slower reaction of CS2+, ternary association occurs. The reactions are discussed relative to the reactivity of these ions with the analogues, OCS and CO2.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  4. 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. [Kernfysisch Versneller Instituut, University of Groningen, Zernikelaan 25, NL-9747 AA Groningen (Netherlands); Department of Physics and the Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Research Center for Nuclear Physics, Osaka University, Ibaraki, Osaka 560-0047 (Japan); Department of Physics, Osaka University, Toyonaka, Osaka 560-0043 (Japan); School of Physics, University of the Witwatersrand, PO Wits, Johannesburg 2050 (South Africa); Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Physics Division, Argonne National Laboratory, 9700 S. Cass. Avenue, Argonne, Illinois 60439 (United States); Department of Physics, University of Surrey (United Kingdom); National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, Michigan 48824 (United States)

    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.

  5. Diagnostic technique for measuring fusion reaction rate for inertial confinement fusion experiments at Shen Guang-III prototype laser facility

    NASA Astrophysics Data System (ADS)

    Wang, Feng; Peng, Xiao-Shi; Kang, Dong-Guo; Liu, Shen-Ye; Xu, Tao

    2013-11-01

    A study is conducted using a two-dimensional simulation program (Lared-s) with the goal of developing a technique to evaluate the effect of Rayleigh-Taylor growth in a neutron fusion reaction region. Two peaks of fusion reaction rate are simulated by using a two-dimensional simulation program (Lared-s) and confirmed by the experimental results. A neutron temporal diagnostic (NTD) system is developed with a high temporal resolution of ~ 30 ps at the Shen Guang-III (SG-III) prototype laser facility in China, to measure the fusion reaction rate history. With the shape of neutron reaction rate curve and the spherical harmonic function in this paper, the degree of Rayleigh-Taylor growth and the main source of the neutron yield in our experiment can be estimated qualitatively. This technique, including the diagnostic system and the simulation program, may provide important information for obtaining a higher neutron yield in implosion experiments of inertial confinement fusion.

  6. 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.

  7. The 31S(p,?)32Cl reaction rate in novae

    NASA Astrophysics Data System (ADS)

    Afanasieva, L.; Blackmon, J. C.; Deibel, C. M.; Lai, J.; Lauer, A.; Rasco, B. C.; Seweryniak, D.; Alcorta, M.; Bertone, P. F.; Clark, J. A.; Janssens, R. V. F.; Hoffman, C. R.; Marley, S. T.; Rogers, A. M.; Zhu, S.; Lotay, G.; Woods, P. J.

    2013-10-01

    The 31S(p, ?)32Cl reaction is important for understanding the production of sulfur and heavier elements in novae. The rate of the 31S(p, ?)32Cl reaction is not established well due to the uncertain properties of proton resonances in 32Cl. We performed high accuracy 32Cl excitation energy measurements using Gammasphere and the FMA at the ATLAS facility. A beam of 24Mg at 75 MeV and current of impinged on a 200 ?g/cm2 10B target to produce 32Cl. Ions recoiling from the target were separated from the beam and identified in the FMA. Gammas emitted from the levels above the proton threshold in 32Cl were detected in Gammasphere in coincidence with the recoils, which allowed 32Cl level structure to be determined. In addition, spin assignments for resonances in 32Cl were constrained based on gamma-ray angular distributions. This work is supported by the U.S. DOE, Office of Nuclear Physics, under Contract No. DEAC02-06CH11357, No. DE-FG02-96ER40978.

  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. 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

  10. 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.

  11. 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.

  12. Solubility and Reaction Rates of Aluminum Solid Phases Under Hydrothermal Conditions

    SciTech Connect

    Benezeth, P.; Palmer, D.A.; Wesolowski, D.

    1999-11-14

    Experimental studies involving equilibrium solubility and dissolution/precipitation rates were initiated on boehmite (AIOOH) using a hydrogen-electrode concentration cell (HECC). This cell provides continuous, accurate in situ pH measurements of solid/solution mixtures to 295 C with provision for either removing solution samples for analysis of the metal content, or adding either of two titrants. This cell has been recently used to measure the solubility of minerals such as brucite; boehmite, zincite, arid magnetite. The ability to perturb pH, isothermally by addition of acidic or basic titrant opens the door for studies of the kinetics of dissolution/precipitation, even for relatively fast reactions. By monitoring the change in pH, with time, detailed kinetic information can be obtained without the need for sampling.

  13. The plutonium\\/hydrogen reaction: The pressure dependence of reaction initiation time and nucleation rate controlled by a plutonium dioxide over-layer

    Microsoft Academic Search

    Gordon W. McGillivray; John P. Knowles; Ian M. Findlay; Marina J. Dawes

    2011-01-01

    As part of an ongoing programme to quantify those parameters which influence the early stages of the plutonium hydriding reaction, the hydrogen pressure dependence of both plutonium hydriding initiation time (It) and hydriding nucleation rate (Nr) have been determined for plutonium covered in a reproducible dioxide over-layer. The data show that initiation time is inversely proportional to hydrogen pressure, while

  14. 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).

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

    SciTech Connect

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

    1984-07-01

    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).

  16. Degradation of picloram by the electro-Fenton process

    Microsoft Academic Search

    Ali Özcan; Yücel ?ahin; A. Sava? Koparal; Mehmet A. Oturan

    2008-01-01

    The degradation of the picloram, a widely used herbicide, has been undertaken by the electrochemical advanced oxidation process, namely electro-Fenton in aqueous solution. This process generates catalytically hydroxyl radicals that are strong oxidizing reagents for the oxidation of organic substances. Degradation kinetics of picloram was investigated. Kinetic results evidence a pseudo first-order degradation, with a rate constant of reaction between

  17. Kinetics of lycopene degradation in tomato pulp solids under different processing and storage conditions

    Microsoft Academic Search

    Shri K. Sharma; Marc Le Maguer

    1996-01-01

    Kinetics of lycopene degradation during heating of tomato pulp at 100 °C under different conditions followed a pseudo first order reaction. When concentrating tomato pulp during heating, the rate of lycopene degradation was higher (K = 0.0023 min?1) compared with when heating was done without concentration (K = 0.0017 min?1). In another case, when water insoluble tomato pulp solids were

  18. 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.

  19. Fast and quantitative differentiation of single-base mismatched DNA by initial reaction rate of catalytic hairpin assembly.

    PubMed

    Li, Chenxi; Li, Yixin; Xu, Xiao; Wang, Xinyi; Chen, Yang; Yang, Xiaoda; Liu, Feng; Li, Na

    2014-10-15

    The widely used catalytic hairpin assembly (CHA) amplification strategy generally needs several hours to accomplish one measurement based on the prevailingly used maximum intensity detection mode, making it less practical for assays where high throughput or speed is desired. To make the best use of the kinetic specificity of toehold domain for circuit reaction initiation, we developed a mathematical model and proposed an initial reaction rate detection mode to quantitatively differentiate the single-base mismatch. Using the kinetic mode, assay time can be reduced substantially to 10 min for one measurement with the comparable sensitivity and single-base mismatch differentiating ability as were obtained by the maximum intensity detection mode. This initial reaction rate based approach not only provided a fast and quantitative differentiation of single-base mismatch, but also helped in-depth understanding of the CHA system, which will be beneficial to the design of highly sensitive and specific toehold-mediated hybridization reactions. PMID:24768863

  20. 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. [Dipartimento di Metodologie Fisiche e Chimiche per l'Ingegneria, Universita di Catania, and INFN-Laboratori Nazionali del Sud, Catania (Italy); Coc, A. [Centre de Spectrometrie Nucleaire et de Spectrometrie de Masse, UMR 8609, CNRS/IN2P3 and Universite Paris Sud 11, Batiment 104, F-91405 Orsay Campus (France); Mukhamedzhanov, A. [Cyclotron Institute, Texas A and M University College Station, Texas (United States); Burjan, S. V.; Hons, Z.; Kroha, V. [Nuclear Physics Institute of ASCR Rez near Prague (Czech Republic); Hammache, F. [Institut de Physique Nucleaire, UMR-8608, CNRS/IN2P3 and Universite Paris-Sud XI, F-91406 Orsay (France)

    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.

  1. Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach

    NASA Astrophysics Data System (ADS)

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-12-01

    Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman-Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N2 flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.

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

    PubMed

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

    2010-01-01

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

  3. Pressure effect on the rate and equilibrium constants of the Diels-Alder reaction 9-chloroanthracene with tetracyanoethylene

    Microsoft Academic Search

    Vladimir D. Kiselev; Elena A. Kashaeva; Alexander I. Konovalov

    1999-01-01

    The pressure effect on the forward and backward rate constants and equilibrium constants of the Diels-Alder reaction of 9-chloroanthracene with tetracyanoethylene has been investigated in 1,2-dichloroethane up to 1000 kgcm?2 at 298.15 K. The reaction volume obtained from the pressure effect on equilibrium (?20.6 ±1.5 cm3mol?1) and as difference of activation volumes of forward (?28.5±1.5) and backward (?6.5 ± 0.5)

  4. Rate constants for aqueous-phase reactions of hydroxyl radical ({center_dot}OH) with aldehydes and ketones

    SciTech Connect

    Allen, J.M.; Allen, S.K. [Indiana State Univ., Terre Haute, IN (United States)

    1995-12-31

    A wide variety of aldehydes and ketones are formed in the troposphere by the gas-phase oxidation of hydrocarbons. These compounds are expected to readily partition into cloud, fog, and aquated aerosol drops where they can participate in a variety of aqueous-phase reactions. It has been previously demonstrated by other researchers that aqueous-phase photochemical reactions involving aromatic aldehydes and ketones may lead to the formation of hydrogen peroxide. Hydrogen peroxide is an important oxidant for S(IV) and is also an {center_dot}OH precursor. Aldehydes and ketones may also participate in other aqueous-phase reactions within atmospheric water drops including reactions with {center_dot}OH. Rate constants for reactions involving {center_dot}OH in aqueous solutions have been reported for only a limited number of tropospheric aldehydes and ketones. The authors have measured the rate constants for aqueous-phase reactions of {center_dot}OH with several tropospheric aldehydes and ketones by the technique of competition kinetics. Hydroxyl radicals were generated by continuous illumination at 313 nm of an aqueous acidified solution containing Fe(ClO{sub 4}){sub 3}, an {center_dot}OH scavenger, the aldehyde or ketone whose rate constant was to be measured, and a standard for which the rate constant for reaction with {center_dot}OH is well known. Nitrobenzene was used as the standard in all experiments. Loss of the aldehyde or ketone and the standard were monitored by HPLC. Losses attributable to direct photolysis and dark reactions were minimal.

  5. Improved Whitten?Rabinovitch Approximation for the Rice?Ramsperger?Kassel?Marcus Calculation of Unimolecular Reaction Rate Constants for Proteins

    Microsoft Academic Search

    Meiling Sun; Jeong Hee Moon; Myung Soo Kim

    2007-01-01

    The Whitten-Rabinovitch (WR) approximation used in the semi-classical calculation of the Rice- Ramsperger-Kassel-Marcus (RRKM) unimolecular reaction rate constant was improved for reliable application to protein reactions. The state sum data for the 10-mer of each amino acid calculated by the accurate Beyer-Swinehart (BS) algorithm were used to obtain the residue-specific correction functions ( w). The correction functions were obtained down

  6. The kinetic ion mobility mass spectrometer: Measurements of ion-molecule reaction rate constants at atmospheric pressure

    SciTech Connect

    Giles, K.; Grimsrud, E.P. [Montana State Univ., Bozeman, MT (United States)

    1992-08-06

    This paper discusses how the kinetic ion mobility mass spectrometer is used to measure the rate constants of ion-molecule reactions in an atmospheric pressure buffer gas. One operational mode of the instrument avoids measurement errors associated with aperture sampling of a high-pressure ionized gas. This instrument is used to study the S{sub N}2 nucleophilic displacement reactions of chloride anions with a series of alkyl bromides in nitrogen. 40 refs., 13 figs., 2 tabs.

  7. Quasiclassical trajectory scattering calculations for the OH + O ? H + O 2 reaction: Cross sections and rate constants

    Microsoft Academic Search

    M. Jorfi; P. Honvault; P. Halvick; S. Y. Lin; H. Guo

    2008-01-01

    We report quasiclassical trajectory studies of the OH+O?H+O2 reaction using a recently developed ab initio potential energy surface for the ground electronic state of HO2. The J=0 total reaction probability is in good agreement with the quantum result. Integral cross sections show no energy threshold and decrease as the collision energy increases. Rate constants have been calculated in the (1–500K)

  8. A determination of the rate constant for the reaction of HOCL with O-atoms at room temperature

    Microsoft Academic Search

    Rainer Vogt; Ralph N. Schindler

    1992-01-01

    A discharge fast flow system with mass spectrometric detection was used to determine the rate constant of the title reaction to be k(1) = (1.3 +\\/- 0.2) x 10 exp -13 cu cm\\/molecule\\/s. This experimental value is roughly a factor of 20 higher than previously recommended. It is suggested that the title reaction should be considered as a removal process

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  10. Geometry effects on the concentration and reaction rate profile in methanol production catalyst; 1: Neglecting external diffusion

    SciTech Connect

    Duan, Y.; Wu, D. (Inner Mongolia Teachers Univ., Inner Mongolia (China). Inst. for Coordination Chemistry); Earl, W.B.; Williamson, C.J. (Univ. of Canterbury, Christchurch (New Zealand). Dept. of Chemical and Process Engineering)

    1994-09-01

    In the low-pressure synthesis of methanol from carbon oxides and hydrogen over copper-based catalysts, the effect of catalyst pellet geometry has been investigated. A model for studying reaction within any sufficiently symmetrical porous catalyst particle has been also provided. Fugacity coefficients and compositions are calculated by using the Redlich-Kwong-Soave state equation, and the kinetics model announced by Villa et al. has been used for computing the reaction rates. The reaction is considered to proceed within isothermal and isobaric catalyst pellets. External diffusion has been neglected.

  11. Histidine and Its Anticodon GpUpG are Similar Metabolic Reaction Rate Enhancers: Molecular Origin of the Genetic Code

    NASA Astrophysics Data System (ADS)

    Shimizu, Mikio

    2004-02-01

    Using spectrophotometry, it was found that histidine enhances weakly but specifically various metabolic reaction rates such as pyruvate carboxylase, oxalacetate decarboxylase and glucose-6-phosphate isomerase (indicating that only one of the twenty amino acids is catalytic). Oligo-ribonucleotides having flexible dihedral angles could also be expected to be rate enhancers in these metabolic reactions. The survey by spectrophotometry showed that GpUpG, an anticodon of histidine, is also a similar rate enhancer. The formation of the reaction products in the cases of pyruvate carboxylase and oxalacetate decarboxylase was furthermore confirmed by thin-layer chromatography using 14C-labeled pyruvate and by high-performance liquid chromatography. The origin of the genetic code may thus be based on direct molecular relationships between amino acids and anticodons.

  12. Rate-promoting vibrations and coupled hydrogen-electron transfer reactions in the condensed phase: A model for enzymatic catalysis

    NASA Astrophysics Data System (ADS)

    Mincer, Joshua S.; Schwartz, Steven D.

    2004-04-01

    A model is presented for coupled hydrogen-electron transfer reactions in condensed phase in the presence of a rate promoting vibration. Large kinetic isotope effects (KIEs) are found when the hydrogen is substituted with deuterium. While these KIEs are essentially temperature independent, reaction rates do exhibit temperature dependence. These findings agree with recent experimental data for various enzyme-catalyzed reactions, such as the amine dehydrogenases and soybean lipoxygenase. Consistent with earlier results, turning off the promoting vibration results in an increased KIE. Increasing the barrier height increases the KIE, while increasing the rate of electron transfer decreases it. These results are discussed in light of other views of vibrationally enhanced tunneling in enzymes.

  13. Methods for quantifying the influences of pressure and temperature variation on metal hydride reaction rates measured under isochoric conditions

    NASA Astrophysics Data System (ADS)

    Voskuilen, Tyler G.; Pourpoint, Timothée L.

    2013-11-01

    Analysis techniques for determining gas-solid reaction rates from gas sorption measurements obtained under non-constant pressure and temperature conditions often neglect temporal variations in these quantities. Depending on the materials in question, this can lead to significant variations in the measured reaction rates. In this work, we present two new analysis techniques for comparison between various kinetic models and isochoric gas measurement data obtained under varying temperature and pressure conditions in a high pressure Sievert system. We introduce the integral pressure dependence method and the temperature dependence factor as means of correcting for experimental variations, improving model-measurement fidelity, and quantifying the effect that such variations can have on measured reaction rates. We use measurements of hydrogen absorption in LaNi5 and TiCrMn to demonstrate the effect of each of these methods and show that their use can provide quantitative improvements in interpretation of kinetics measurements.

  14. Methods for quantifying the influences of pressure and temperature variation on metal hydride reaction rates measured under isochoric conditions.

    PubMed

    Voskuilen, Tyler G; Pourpoint, Timothée L

    2013-11-01

    Analysis techniques for determining gas-solid reaction rates from gas sorption measurements obtained under non-constant pressure and temperature conditions often neglect temporal variations in these quantities. Depending on the materials in question, this can lead to significant variations in the measured reaction rates. In this work, we present two new analysis techniques for comparison between various kinetic models and isochoric gas measurement data obtained under varying temperature and pressure conditions in a high pressure Sievert system. We introduce the integral pressure dependence method and the temperature dependence factor as means of correcting for experimental variations, improving model-measurement fidelity, and quantifying the effect that such variations can have on measured reaction rates. We use measurements of hydrogen absorption in LaNi5 and TiCrMn to demonstrate the effect of each of these methods and show that their use can provide quantitative improvements in interpretation of kinetics measurements. PMID:24289432

  15. 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.

  16. Astrophysical reaction rate for the neutron-generator reaction 13C(alpha,n)16O in asymptotic giant branch stars.

    PubMed

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

    2006-11-10

    The reaction 13C(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+ 6.356 MeV subthreshold resonance in (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 ((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. PMID:17155619

  17. 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. [Department of Physics, Florida State University, Tallahassee, Florida 32306 (United States); Mukhamedzhanov, A. M.; Goldberg, V. Z. [Cyclotron Institute, Texas A and M University, College Station, Texas 77843 (United States); Brown, S. [Department of Physics, Florida State University, Tallahassee, Florida 32306 (United States); Department of Physics, The University of Surrey, Guildford, Surrey (United Kingdom)

    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.

  18. Reactions of ethynyl radicals - Rate constants with CH4, C2H6, and C2D6

    NASA Technical Reports Server (NTRS)

    Laufer, A. H.

    1981-01-01

    An experiment to measure ethynyl radical reactivity with other simple molecules is described. Flash photolysis of CF3C2H, a C2H precursor, was kinetically and spectroscopically analyzed for C2H reactions with CH4, C2H6, and C2D6 and rate constants for the abstraction reaction at room temperature were determined. The experimental apparatus is described, and the acetylene feedstock purification procedures are outlined. Rate constants are provided, and additional examination of the effects of added helium showed no alterations over the pressure range 20-700 torr.

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

    SciTech Connect

    Bobrov, A. A.; Boyarinov, V. F.; Glushkov, A. E.; Glushkov, E. S.; Kompaniets, G. V.; Moroz, N. P.; Nevinitsa, V. A.; Nosov, V. I.; Smirnov, O. N.; Fomichenko, P. A.; Zimin, A. A. [National Research Centre, Kurchatov Inst., Kurchatov Sq. 1, Moscow (Russian Federation)

    2012-07-01

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

  20. 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. [Argonne National Laboratory, Argonne IL 60439 (United States); Grames, J.; Meekins, D.; Poelker, M.; Suleiman, R. [Jefferson Lab, Newport News, VA 23606 (United States); Robinson, A.; Ugalde, C., E-mail: cugalde@uchicago.edu [University of Chicago, Chicago, IL 60637 (United States); Sonnenschein, A. [Fermilab, Batavia, IL 60510 (United States)

    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.

  1. 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.

  2. Proteolysis inside the membrane is a rate-governed reaction not driven by substrate affinity

    PubMed Central

    Dickey, Seth W.; Baker, Rosanna P.; Cho, Sangwoo; Urban, Siniša

    2013-01-01

    SUMMARY Enzymatic cleavage of transmembrane anchors to release proteins from the membrane controls diverse signaling pathways and is implicated in over a dozen diseases. How catalysis works within the viscous, water-excluding, two-dimensional membrane is unknown. We developed an inducible reconstitution system to interrogate rhomboid proteolysis quantitatively within the membrane in real time. Remarkably, rhomboid proteases displayed no physiological affinity for substrates (Kd ~190 ?M, or 0.1 mol%). Instead, ~10,000-fold differences in proteolytic efficiency with substrate mutants and diverse rhomboid proteases were reflected in kcat values alone. Analysis of gate-open mutant and solvent isotope effects revealed that substrate gating, not hydrolysis, is rate limiting. Ultimately a single proteolytic event within the membrane normally takes minutes. Rhomboid intramembrane proteolysis is thus a slow, kinetically controlled reaction not driven by transmembrane protein-protein affinity. These properties are unlike those of other studied proteases or membrane proteins but strikingly reminiscent of one subset of DNA-repair enzymes, raising important mechanistic and drug-design implications. PMID:24315097

  3. Measurements of the O+ plus N2 and O+ plus O2 reaction rates from 300 to 900 K

    NASA Technical Reports Server (NTRS)

    Chen, A.; Johnsen, R.; Biondi, M. A.

    1977-01-01

    Rate coefficients for the O(+) + N2 atom transfer and O(+) + O2 charge transfer reactions are determined at thermal energies between 300 K and 900 K difference in a heated drift tube mass spectrometer apparatus. At 300 K the values K(O(+) + N2) = (1.2 plus or minus 0.1) x 10 to the negative 12 power cubic cm/sec and k(O(+) + O2) = (2.1 plus or minus 0.2) x 10 to the negative 11 power cubic cm/sec were obtained, with a 50% difference decrease in the reaction rates upon heating to 700 K. These results are in good agreement with heated flowing afterglow results, but the O(+) + O2 thermal rate coefficients are systematically lower than equivalent Maxwellian rates inferred by conversion of nonthermal drift tube and flow drift data.

  4. CF3CF=CH2 and (Z)-CF3CF=CHF: temperature dependent OH rate coefficients and global warming potentials.

    PubMed

    Papadimitriou, Vassileios C; Talukdar, Ranajit K; Portmann, R W; Ravishankara, A R; Burkholder, James B

    2008-02-14

    Rate coefficients over the temperature range 206-380 K are reported for the gas-phase reaction of OH radicals with 2,3,3,3-tetrafluoropropene (CF(3)CF=CH(2)), k(1)(T), and 1,2,3,3,3-pentafluoropropene ((Z)-CF(3)CF=CHF), k(2)(T), which are major components in proposed substitutes for HFC-134a (CF(3)CFH(2)) in mobile air-conditioning units. Rate coefficients were measured under pseudo-first-order conditions in OH using pulsed-laser photolysis to produce OH and laser-induced fluorescence to detect it. Rate coefficients were found to be independent of pressure between 25 and 600 Torr (He, N(2)). For CF(3)CF=CH(2), the rate coefficients, within the measurement uncertainty, are given by the Arrhenius expression k(1)(T)=(1.26+/-0.11) x 10(-12) exp[(-35+/-10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K)=(1.12+/-0.09) x 10(-12) cm(3) molecule(-1) s(-1). For (Z)-CF(3)CF=CHF, the rate coefficients are given by the non-Arrhenius expression k(2)(T)=(1.6+/-0.2) x 10(-18)T(2) exp[(655+/-50)/T] cm(3) molecule(-1) s(-1) where k(2)(296 K)=(1.29+/-0.06) x 10(-12) cm(3) molecule(-1) s(-1). Over the temperature range most relevant to the atmosphere, 200-300 K, the Arrhenius expression k(2)(T)=(7.30+/-0.7) x 10(-13) exp[(165+/-20)/T] cm(3) molecule(-1) s(-1) reproduces the measured rate coefficients very well and can be used in atmospheric model calculations. The quoted uncertainties in the rate coefficients are 2sigma (95% confidence interval) and include estimated systematic errors. The global warming potentials for CF(3)CF=CH(2) and (Z)-CF(3)CF=CHF were calculated to be <4.4 and <3.6, respectively, for the 100 year time horizon using infrared absorption cross sections measured in this work, and atmospheric lifetimes of 12 and 10 days that are based solely on OH reactive loss. PMID:18231683

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

    PubMed

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

    2015-06-01

    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(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. PMID:26049499

  6. 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.

  7. Measurements of Fission and Radioactive Capture Reaction Rates Inside the Fuel of the Ipen\\/MB01

    Microsoft Academic Search

    Luís Felipe L. Mura; Ulysses D'utra Bitelli; Leda C. C. B. Fanaro

    2011-01-01

    This work presents the measures of the nuclear reaction rates along the radial direction of the fuel pellet by irradiation\\u000a and posterior gamma spectrometry of a thin slice of fuel pellet of UO2 at 4.3% enrichment. From its irradiation, the rate of radioactive capture and fission had been measured as a function of\\u000a the radius of the pellet disk using

  8. Reactivity-Structure-Based Rate Estimation Rules for Alkyl Radical H Atom Shift and Alkenyl Radical Cycloaddition Reactions.

    PubMed

    Wang, Kun; Villano, Stephanie M; Dean, Anthony M

    2015-07-16

    Intramolecular H atom shift reactions of alkyl radicals and cycloaddition reactions of alkenyl radicals are two important reaction classes in hydrocarbon combustion and pyrolysis. In this work, we derive high-pressure rate estimation rules that are based on the results of electronic structure calculations at the CBS-QB3 level of theory combined with transition state theory calculations. The rules for the H atom shift reactions of alkyl radicals cover the 1,2- up to the 1,7-H shifts. The rules for the cycloaddition reactions of alkenyl radicals are for both the endo- and exo-cycloaddition and include the formation of three- to seven-member ring products. The results are in good agreement with available experiment measurements and other theoretical studies. Both types of reactions proceed via cyclic transition state structures. The impact of ring size and substituent groups on pre-exponential factors and activation energies are discussed in the context of a Benson-type structure-reactivity relationship. Similar relationships between the pre-exponential factors and the number of internal rotors lost in formation of the transition state are derived for both H-shift and cycloaddition reactions. The activation energies are found to be more complicated. The ring strain contribution to the barrier is much lower for the exo-cycloaddition reactions than it is for the other two investigated reaction systems. The ring strains for the H-shift and endo-cycloaddition are similar to one another and are comparable to that of cycloalkanes for three- to six-member rings, but are significantly lower for the larger rings. The results suggest that the 1,6-H shift and 1,7-endo-cycloaddition reactions might be faster than previous estimates. PMID:25563061

  9. 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 dioxide-iodide, (b) chlorine(III)-iodide, (c) chlorine(III)-iodine, and (d) hypoiodous and iodous acid experimentally measured, remeasured, or which were previously experimentally measured include oxidation of iodine

  10. Reaction Rates Measurement across the Pressure Vessel of Chooz-A Pwr by Self-Dosimetry Technique

    Microsoft Academic Search

    D. Beretz; C. Destouches; A. Bache

    2003-01-01

    CHOOZ-A, a French-Belgian power plant was the first PWR in operation in France; it was definitively shut down in 1991. A large feedback program has been realized during the decommissioning. In this framework, several core samples have been machined from the pressure vessel. They have been used for the determination of the attenuation of the cobalt and iron reaction rates

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

    SciTech Connect

    McAuliffe, J.J. (Univ. of Cincinnati College of Medicine, OH (United States)); Perry, S.B. (Childrens Hospital, Boston, MA (United States)); Brooks, E.E. (Univ. of Cincinnati, OH (United States)); Ingwall, J.S. (Brigham and Women's Hospital, Boston, MA (United States) Harvard Medical School, Boston, MA (United States))

    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.

  12. 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.

  13. 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.

  14. Optimal reconstruction of concentrations, gradients and reaction rates from particle distributions.

    PubMed

    Fernàndez-Garcia, D; Sanchez-Vila, X

    2011-03-01

    Random walk particle tracking methodologies to simulate solute transport of conservative species constitute an attractive alternative for their computational efficiency and absence of numerical dispersion. Yet, problems stemming from the reconstruction of concentrations from particle distributions have typically prevented its use in reactive transport problems. The numerical problem mainly arises from the need to first reconstruct the concentrations of species/components from a discrete number of particles, which is an error prone process, and then computing a spatial functional of the concentrations and/or its derivatives (either spatial or temporal). Errors are then propagated, so that common strategies to reconstruct this functional require an unfeasible amount of particles when dealing with nonlinear reactive transport problems. In this context, this article presents a methodology to directly reconstruct this functional based on kernel density estimators. The methodology mitigates the error propagation in the evaluation of the functional by avoiding the prior estimation of the actual concentrations of species. The multivariate kernel associated with the corresponding functional depends on the size of the support volume, which defines the area over which a given particle can influence the functional. The shape of the kernel functions and the size of the support volume determines the degree of smoothing, which is optimized to obtain the best unbiased predictor of the functional using an iterative plug-in support volume selector. We applied the methodology to directly reconstruct the reaction rates of a precipitation/dissolution problem involving the mixing of two different waters carrying two aqueous species in chemical equilibrium and moving through a randomly heterogeneous porous medium. PMID:20627365

  15. Optimal reconstruction of concentrations, gradients and reaction rates from particle distributions

    NASA Astrophysics Data System (ADS)

    Fernàndez-Garcia, D.; Sanchez-Vila, X.

    2011-03-01

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

  16. 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.

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

    Microsoft Academic Search

    David A. Benson; Mark M. Meerschaert

    2008-01-01

    Chemical reactions may be simulated without regard to local concentrations by applying simple probabilistic rules of particle interaction and combination. The forward reaction A + B? C is coded by calculating the probability that any A and B particles will occupy the same volume over some time interval. This becomes a convolution of the location densities of the two particles.

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

    Microsoft Academic Search

    David A. Benson; Mark M. Meerschaert

    2008-01-01

    Chemical reactions may be simulated without regard to local concentrations by applying simple probabilistic rules of particle interaction and combination. The forward reaction A + B-> C is coded by calculating the probability that any A and B particles will occupy the same volume over some time interval. This becomes a convolution of the location densities of the two particles.

  19. Inter-and intraspecific variation in excited-state triplet energy transfer rates in reaction centers of photosynthetic bacteria.

    SciTech Connect

    Laible, P. D.; Morris, Z. S.; Thurnauer, M. C.; Schiffer, M.; Hanson, D. K.

    2003-08-01

    In protein-cofactor reaction center (RC) complexes of purple photosynthetic bacteria, the major role of the bound carotenoid (C) is to quench the triplet state formed on the primary electron donor (P) before its sensitization of the excited singlet state of molecular oxygen from its ground triplet state. This triplet energy is transferred from P to C via the bacteriochlorophyll monomer B{sub B}. Using time-resolved electron paramagnetic resonance (TREPR), we have examined the temperature dependence of the rates of this triplet energy transfer reaction in the RC of three wild-type species of purple nonsulfur bacteria. Species-specific differences in the rate of transfer were observed. Wild-type Rhodobacter capsulatus RCs were less efficient at the triplet transfer reaction than Rhodobacter sphaeroides RCs, but were more efficient than Rhodospirillum rubrum RCs. In addition, RCs from three mutant strains of R. capsulatus carrying substitutions of amino acids near P and B{sub B} were examined. Two of the mutant RCs showed decreased triplet transfer rates compared with wild-type RCs, whereas one of the mutant RCs demonstrated a slight increase in triplet transfer rate at low temperatures. The results show that site-specific changes within the RC of R. capsulatus can mimic interspecies differences in the rates of triplet energy transfer. This application of TREPR was instrumental in defining critical energetic and coupling factors that dictate the efficiency of this photoprotective process.

  20. 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...

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

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

    The pressure dependence of the absolute rate constant for the reaction of the hydroxyl radical with acetylene, important in both atmospheric and combustion chemistry, is determined for temperatures between 228 and 413 K. The flash photolysis-resonance fluorescence technique was employed at five temperatures over wide ranges of pressure and acetylene concentrations, with the OH produced by water photolysis and hydroxyl resonance fluorescent photons measured by multiscaling techniques. Results indicate that, except at the lowest temperature, the bimolecular rate constant for the reaction depends strongly on total pressure, with the pressure effect becoming more pronounced with increasing temperature. At limiting high pressures, the rate constant is found to be equal to 6.83 + or - 1.19 x 10 to the -12th exp (-646 + or - 47/T) cu cm/molecule per sec, where T is the temperature. Results thus demonstrate the importance of environmental conditions in theoretical studies of atmospheric and combustion product compositions

  2. 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.

  3. Rate Coefficients for the Gas-Phase Reactions of Hydroxyl Radicals with a Series of Methoxylated Aromatic Compounds.

    PubMed

    Lauraguais, Amélie; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Coeur, Cécile

    2015-06-18

    Rate coefficients for the reactions of hydroxyl radicals (OH) with a series of oxygenated aromatics (two methoxybenzene and five methoxyphenol isomers) have been obtained using the relative kinetic method in 1080 and 480 L photoreactors at the University of Wuppertal, Germany. The experiments were realized at 295 ± 2 K and 1 bar total pressure of synthetic air using in situ Fourier transform infrared spectroscopy for the chemical analysis. The following rate coefficients (in units of cm(3)?molecule(-1)?s(-1)) were determined: methoxybenzene (anisole), (2.08 ± 0.21) × 10(-11); 1-methoxy-2-methylbenzene, (4.56 ± 0.50) × 10(-11); 2-methoxyphenol (guaiacol), (5.40 ± 0.72) × 10(-11); 3-methoxyphenol, (6.93 ± 0.67) × 10(-11); 4-methoxyphenol, (5.66 ± 0.55) × 10(-11); 2-methoxy-4-methylphenol, (7.51 ± 0.68) × 10(-11); 2,3-dimethoxyphenol, (7.49 ± 0.81) × 10(-11); and 2,6-dimethoxyphenol (syringol), (8.10 ± 0.98) × 10(-11). The rate coefficients for the reactions of OH with 2,3-dimethoxyphenol and 1-methoxy-2-methylbenzene are first time measurements. The rate coefficients determined in this work are compared with previous determinations reported in the literature and also with the values estimated using a structure-activity relationship method. A comparison is performed between the OH rate coefficients obtained for methoxylated aromatics with those of other substituted aromatics in order to understand the influence of the type, number, and position of the different substituents on the reactivity of aromatics toward OH. In addition, a comparison is made between the OH and Cl rate coefficients for the compounds. The principal atmospheric sink of these methoxylated aromatic compounds during daytime is their reaction with OH radicals. The corresponding lifetimes for reaction with OH radicals and Cl atoms are 2-8 and 11-50 h, respectively. PMID:25989938

  4. Organic photochemistry. 20. A method for estimating gas-phase rate constants for reactions of hydroxyl radicals with organic compounds from their relative rates of reaction with hydrogen peroxide under photolysis in 1,1,2-trichlorotrifluoroethane solution

    SciTech Connect

    Dilling, W.L.; Gonsior, S.J.; Boggs, G.U.; Mendoza, C.G.

    1988-12-01

    The reaction with hydroxyl radicals appears to be the major transformation route for many organic compounds in the atmosphere. To avoid the difficulties of measuring the rate constants for these reactions in the gas phase for some compounds, we have developed a solution-phase system for measuring relative rates. This system involves photolysis of continuously extracted 90% hydrogen peroxide into 1,1,2-trichlorotrifluoroethane solution, which contains two or more organic compounds, one of which serves as a reference standard whose gas-phase rate constant is known. Reasonable correlations (r/sup 2/ = 0.84, 0.87) were obtained between the relative solution-phase rates and the absolute gas-phase rate constants, which varied over 4 orders of magnitude for n-hexane, 2,2,4-trimethylpentane, cyclohexane, 1,1,1,-trichloroethane, cyclohexene, trichloroethene, tetra-chloroethene, ethyl acetate, toluene, n-propylbenzene, o-xylene, p-isopropyltoluene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, biphenyl, naphthalene, hexafluorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, anisole, and nitrobenzene. This method allows estimations of the gas-phase rate constants to within 1 order of magnitude or better.

  5. Measuring Rate Constants for Reactions of the Simplest Criegee Intermediate (CH2OO) by Monitoring the OH Radical

    NASA Astrophysics Data System (ADS)

    liu, Y.; Bayes, K. D.; Sander, S. P.

    2013-12-01

    While generating the CH2OO molecule by reacting CH2I with O2, significant amounts of the OH radical were observed by laser induced fluorescence (LIF). At least two different processes formed OH; a fast process was probably due to a reaction of vibrationally hot CH2I radicals. The second process appeared to be associated with the decay of the CH2OO molecule. The addition of molecules known to react with CH2OO increased the observed decay rates of the OH signal. Using the OH signals as a proxy for the CH2OO concentration, the rate constant for the reaction of hexafluoroacetone with CH2OO was determined to be (3.33 × 0.27) x 10-11 cm3 molecule-1 s-1, in good agreement with the value measured by Taatjes et al.1 The rate constant for the reaction of SO2 with CH2OO, (3.53 × 0.29) x 10-11 cm3 molecule-1 s-1, showed no pressure dependence over the range of 50 to 200 Torr and was in agreement with the value at 4 Torr reported by Welz et al.2 This lack of a pressure dependence shows that SO2 + CH2OO is almost certainly a two-body reaction forming SO3 + CH2O and not a three-body stabilization.

  6. The effect of nuclear reaction rates and convective mixing on the evolution of a 6M{sub ?} star

    SciTech Connect

    Halabi, Ghina M., E-mail: gfm01@aub.edu.lb [American University of Beirut, Department of Physics, P.O. Box 11-0236, Riad El-Solh, Beirut (Lebanon)

    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.

  7. A model SN2 reaction ‘on water’ does not show rate enhancement

    NASA Astrophysics Data System (ADS)

    Nelson, Katherine V.; Benjamin, Ilan

    2011-05-01

    Molecular dynamics calculations of the benchmark nucleophilic substitution reaction (SN2) Cl- + CH3Cl are carried out at the water liquid/vapor interface. The reaction free energy profile and the activation free energy are determined as a function of the reactants' location normal to the surface. The activation free energy remains almost constant relative to that in bulk water, despite the fact that the barrier is expected to significantly decrease as the reaction is carried out near the vapor phase. We show that this is due to the combined effects of a clustering of water molecules around the nucleophile and a relatively weak hydration of the transition state.

  8. Measuring the 16O(?, ?)20Ne Reaction Rate with the Dragon Recoil Separator at Triumf

    NASA Astrophysics Data System (ADS)

    Hager, U.; Greife, U.; Buchmann, L.; Davids, B.; Fallis, J.; Hutcheon, D.; Ottewell, D.; Reeve, S.; Rojas, A.; Ruiz, C.; Sjue, S. K. L.; Erikson, L.; Carmona-Gallardo, M.; Vockenhuber, C.; Brown, J. R.; Irvine, D.

    2013-03-01

    The DRAGON recoil separator facility at TRIUMF measures radiative ? and proton capture reactions of astrophysical importance in inverse kinematics. This is done employing radioactive and stable ion beams produced and accelerated using the ISAC (Isotope Separator and ACcelerator) facility in conjunction with the DRAGON windowless gas target. Over the last few years, the DRAGON collaboration has embarked on a programme to measure a variety of reactions considered vital to the understanding of various astrophysical scenarios. An overview of DRAGON's separation, beam suppression, and detection capabilities will be given. In addition, examples of recent reaction cross section measurements will be discussed, such as the 16O(?, ?)20Ne reaction, which plays an important part in the He and Ne burning in massive stars.

  9. Absolute and relative rate constants for the reactions of OH and Cl with Pentanols

    E-print Network

    Boyer, Edmond

    , 2]. They are emitted by grassland and agricultural vegetation and have long been used as industrial; reactions with other oxidants such as ozone and nitrate radicals being of minor importance. Sunlight

  10. High-pressure rate rules for alkyl + O2 reactions. 1. The dissociation, concerted elimination, and isomerization channels of the alkyl peroxy radical.

    PubMed

    Villano, Stephanie M; Huynh, Lam K; Carstensen, Hans-Heinrich; Dean, Anthony M

    2011-11-24

    The reactions of alkyl peroxy radicals (RO(2)) play a central role in the low-temperature oxidation of hydrocarbons. In this work, we present high-pressure rate estimation rules for the dissociation, concerted elimination, and isomerization reactions of RO(2). These rate rules are derived from a systematic investigation of sets of reactions within a given reaction class using electronic structure calculations performed at the CBS-QB3 level of theory. The rate constants for the dissociation reactions are obtained from calculated equilibrium constants and a literature review of experimental rate constants for the reverse association reactions. For the concerted elimination and isomerization channels, rate constants are calculated using canonical transition state theory. To determine if the high-pressure rate expressions from this work can directly be used in ignition models, we use the QRRK/MSC method to calculate apparent pressure and temperature dependent rate constants for representative reactions of small, medium, and large alkyl radicals with O(2). A comparison of concentration versus time profiles obtained using either the pressure dependent rate constants or the corresponding high-pressure values reveals that under most conditions relevant to combustion/ignition problems, the high-pressure rate rules can be used directly to describe the reactions of RO(2). PMID:22003961

  11. THE EFFECTS OF THERMONUCLEAR REACTION RATE VARIATIONS ON {sup 26}Al PRODUCTION IN MASSIVE STARS: A SENSITIVITY STUDY

    SciTech Connect

    Iliadis, Christian; Champagne, Art [Department of Physics and Astronomy, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3255 (United States); Chieffi, Alessandro [Istituto Nazionale di Astrofisica-Istituto di Astrofisica Spaziale e Fisica Cosmica, Via Fosso del Cavaliere, I-00133 Roma (Italy); Limongi, Marco, E-mail: iliadis@unc.edu, E-mail: aec@tunl.duke.edu, E-mail: alessandro.chieffi@iasf-roma.inaf.it, E-mail: marco@oa-roma.inaf.it [Istituto Nazionale di Astrofisica-Osservatorio Astronomico di Roma, Via Frascati 33, I-00040 Monteporzio Catone (Italy)

    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.

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

    Microsoft Academic Search

    D. A. Benson; M. M. Meerschaert

    2008-01-01

    We extend the advantages of Lagrangian random walk particle tracking (RWPT) methods that have long been used to simulate advection and dispersion in highly heterogeneous media. By formulating dissolution as a random, independent decay process, the classical continuum rate law is recovered. A novel formulation of the random precipitation process requires a consideration of the probability that two nearby particles

  13. Measurement of the proton production rate of the 23Na(?,p)26Mg reaction relevant for Galactic 26Al

    NASA Astrophysics Data System (ADS)

    Almaraz-Calderon, S.; Albers, M.; Hoffman, C. R.; Jiang, C. L.; Rehm, K. E.; Ugalde, C.; Bertone, P. F.; Alcorta, M.; Deibel, C. M.; Marley, S. T.

    2014-09-01

    The observation of 26Al in the galactic interstellar medium via its 1809-keV gamma ray confirmed that active nucleosynthesis takes place in the Galaxy. The 23Na(?,p)26Mg reaction directly influences the production of 26Al in convective C/Ne burning shell of massive presupernova stars. We have performed a direct measurement of the 23Na(?,p)26Mg reaction cross section at astrophysically important energies. The rate of proton production via this mechanism was found to be much higher than theoretical estimates. This change in the cross section will strongly affect the production of 26Al in massive stars and the contribution to proton production from the 23Na(?,p)26Mg reaction should now be correctly incorporated into the astrophysical models. The observation of 26Al in the galactic interstellar medium via its 1809-keV gamma ray confirmed that active nucleosynthesis takes place in the Galaxy. The 23Na(?,p)26Mg reaction directly influences the production of 26Al in convective C/Ne burning shell of massive presupernova stars. We have performed a direct measurement of the 23Na(?,p)26Mg reaction cross section at astrophysically important energies. The rate of proton production via this mechanism was found to be much higher than theoretical estimates. This change in the cross section will strongly affect the production of 26Al in massive stars and the contribution to proton production from the 23Na(?,p)26Mg reaction should now be correctly incorporated into the astrophysical models. This work is supported by the U.S. DOE Office of Nuclear Physics under Contract No. DE-AC02-06CH11357.

  14. 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

  15. 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.

  16. 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.

  17. Reply to 'Comments on upscaling geochemical reaction rates usingpore-scale network modeling' by Peter C. Lichtner and Qinjun Kang

    SciTech Connect

    Li, Li; Peters, Catherine A.; Celia, Michael A.

    2006-05-03

    Our paper "Upscaling geochemical reaction rates usingpore-scale network modeling" presents a novel application of pore-scalenetwork modeling to upscale mineral dissolution and precipitationreaction rates from the pore scale to the continuum scale, anddemonstrates the methodology by analyzing the scaling behavior ofanorthite and kaolinite reaction kinetics under conditions related to CO2sequestration. We conclude that under highly acidic conditions relevantto CO2 sequestration, the traditional continuum-based methodology may notcapture the spatial variation in concentrations from pore to pore, andscaling tools may be important in correctly modeling reactive transportprocesses in such systems. This work addresses the important butdifficult question of scaling mineral dissolution and precipitationreaction kinetics, which is often ignored in fields such as geochemistry,water resources, and contaminant hydrology. Although scaling of physicalprocesses has been studied for almost three decades, very few studieshave examined the scaling issues related to chemical processes, despitetheir importance in governing the transport and fate of contaminants insubsurface systems.

  18. Why HOC+ is detectable in interstellar clouds: the rate of the reaction between HOC+ and H2

    NASA Technical Reports Server (NTRS)

    Herbst, E.; Woon, D. E.

    1996-01-01

    The recent confirmation by Ziurys and Apponi of the detection of HOC+ toward Sgr B2 (OH), and their identification of the ion in Orion-KL and several other sources show that HOC+ is far more abundant than predicted by previous ion-molecule models. In these models, the reaction HOC(+) + H2 --> HCO(+) + H2 is assumed to rapidly destroy HOC+, based on the results of a prior calculation. We have recalculated the rate of this reaction as a function of temperature using a new ab initio potential surface and a phase space approach to the dynamics which includes tunneling. The newly calculated rate is small (< or = 1 x 10(-10) cm3 s-1) at temperatures under 100 K.

  19. Experimental determination of the rate constant of the reaction between C2H5O2 and OH radicals

    NASA Astrophysics Data System (ADS)

    Faragó, Eszter P.; Schoemaecker, Coralie; Viskolcz, Béla; Fittschen, Christa

    2015-01-01

    The rate constant of the reaction has been measured at T = 296 K using laser photolysis coupled to CRDS and LIF. C2H5O2 was generated from the reaction of Cl-atoms with C2H6 at 55 Torr O2, whereby Cl-atoms were generated by 248 nm photolysis of (COCl)2. OH radicals were generated simultaneously by photolysing H2O2. The initial Cl-concentration (and hence C2H5O2) was determined in separate experiments by replacing C2H6 by CH3OH and thus conversion of Cl-atoms to HO2. The time-resolved OH decay was detected in excess of C2H5O2. A fast rate constant of k = (1.2 ± 0.3) × 10-10 cm3 s-1 was determined.

  20. A Model of Exchange-Rate Determination with Policy Reaction: Evidence From Monthly Data

    Microsoft Academic Search

    William Branson

    1983-01-01

    During the 1970s an extensive theoretical literature has developed analyzing market determination of freely floating exchange rates. At the same time, there has been extensive and continuous intervention in the market by central banks. Exchange rates have not been floating freely; they have been managed, or manipulated, by central banks. However, most of the description of exchange rate policy, as

  1. A Model of Exchange-Rate Determination with Policy Reaction: Evidence from Monthly Data

    Microsoft Academic Search

    William H. Branson

    1983-01-01

    During the 1970s an extensive theoretical literature has developed analyzing market determination of freely floating exchange rates. At the same time, there has been extensive and continuous intervention in the market by central banks. Exchange rates have not been floating freely;they have been managed, or manipulated, by central banks. However, most of the description of exchange rate policy, as actually

  2. A reaction rate constant for avocado sunblotch viroid and its complementary DNA with application to viroid detection.

    PubMed

    Allen, R N

    1982-01-01

    Molecular hybridization between avocado sunblotch viroid and its complementary DNA (cDNA) proceeds as if it were a bimolecular chemical reaction with a rate constant of 0.21 liters per nanomole of nucleotide per day. Computer simulations show the minimum incubation times required to detect the viroid with cDNA probes of varying sensitivity with respect to viroid concentration, and estimate the concentration of one of the reactants when the other is known. PMID:6896865

  3. A Reaction Rate Constant for Avocado Sunblotch Viroid and Its Complementary DNA with Application to Viroid Detection

    Microsoft Academic Search

    Robert Norman Allen

    1982-01-01

    Summary Molecular hybridization between avocado sunblotch viroid and its complementary DNA (cDNA) proceeds as if it were a bimolecular chemical reaction with a rate constant of 0.21 liters per nanomole of nucleotide per day. Computer simulations show the minimum incubation times required to detect the viroid with cDNA probes of varying sensitivity with respect to viroid concentration, and estimate the

  4. A comparative study of reaction rate, species, and vibration-dissociation coupling models for an AOTV flowfield 

    E-print Network

    Bobskill, Glenn James

    1988-01-01

    , species, and vibrational coupling models at three different AOTV trajectory points. A comparative study of the CVD, CVDV, CVDV-Preferential, and Park-Like vibrational coupling models combined with three reaction rate sets were used to determine... the best modeling combinations. The conclusions obtained were that the results from the CVD model were considered to be incorrect due to the model's inability to compensate for the effects that dissociation and recombination have on vibration...

  5. Application of the re-circulating tracer well test method to determine nitrate reaction rates in shallow unconfined aquifers.

    PubMed

    Burbery, Lee F; Flintoft, Mark J; Close, Murray E

    2013-02-01

    Five re-circulating tracer well tests (RCTWTs) have been conducted in a variety of aquifer settings, at four sites across New Zealand. The tests constitute the first practical assessment of the two-well RCTWT methodology described by Burbery and Wang (Journal of Hydrology, 2010; 382:163-173) and were aimed at evaluating nitrate reaction rates in situ. The performance of the RCTWTs differed significantly at the different sites. The RCTWT method performed well when it was applied to determine potential nitrate reaction rates in anoxic, electro-chemically reductive, nitrate-free aquifers of volcanic lithology, on the North Island, New Zealand. Regional groundwater flow was not fast-flowing in this setting. An effective first-order nitrate reaction rate in the region of 0.09 d(-1) to 0.26 d(-1) was determined from two RCTWTs applied at one site where a reaction rate of 0.37 d(-1) had previously been estimated from a push-pull test. The RCTWT method performed poorly, however, in a fast-flowing, nitrate-impacted fluvio-glacial gravel aquifer that was examined on the South Island, New Zealand. This setting was more akin to the hypothetical physiochemical problem described by Burbery and Wang (2010). Although aerobic conditions were identified as the primary reason for failure to measure any nitrate reaction in the gravel aquifer, failure to establish significant interflow in the re-circulation cell due to the heterogeneous nature of the aquifer structure, and natural variability exhibited in nitrate contaminant levels of the ambient groundwater further contributed to the poor performance of the test. Our findings suggest that in practice, environmental conditions are more complex than assumed by the RCTWT methodology, which compromises the practicability of the method as one for determining attenuation rates in groundwater based on tracing ambient contaminant levels. Although limited, there appears to be a scope for RCTWTs to provide useful information on potential attenuation rates when reactants are supplemented to the aquifer system under examination. PMID:23261905

  6. Measuring Rate Constants for Reactions of the Simplest Criegee Intermediate CH_2OO by Monitoring the OH Radical

    NASA Astrophysics Data System (ADS)

    Liu, Yingdi; Bayes, Kyle D.; Sander, Stanley P.

    2014-06-01

    Criegee radicals are important atmospheric intermediates formed from ozonolysis of alkenes. It potentially contributes to the atmospheric oxidation cycle mainly by generating OH radicals through unimolecular decomposition. In this work, we focus on studying the unimolecular decomposition reaction of the smallest Criegee intermediate (CH2OO), which was generated by reacting CH2I with O2. While generating the CH2OO molecule by reacting CH2I with O2, significant amounts of the OH radical were observed by laser-induced fluorescence. The addition of molecules known to react with CH2OO increased the observed decay rates of the OH signal. Using the OH signals as a proxy for the CH2OO concentration, the rate constant for the reaction of hexafluoroacetone with CH2OO was determined. The rate constant for the reaction of SO2 with CH2OO showed no pressure dependence over the range of 50 to 200 Torr. This work provides the direct experimental evidence for the unimolecular decomposition of CH2OO, and possible mechanisms of CH2OO have been investigated by this multidimensional study.

  7. 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

  8. 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, E-mail: yni@ustc.edu.cn [CAS Key Laboratory of Mechanical Behavior and Design of Materials, and Department of Modern Mechanics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Song, Yicheng [Department of Mechanics and Shanghai Key Laboratory of Mechanics in Energy Engineering, Shanghai University, Shanghai 200444 (China)

    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.

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

    E-print Network

    Hu, Qinhong "Max"

    bonding of arsenate to iron, compared to sulfate to iron, leads to an enrichment of surface layer arse arsenate­iron complexes preventing protonation at low pH and repelling hydroxyls at high pH. The stronger- nate­iron complex sites, inhibiting the dissolution of jarosite with time. The secondary reaction

  10. On the relationship between structure and reaction rate in olefin ring-closing metathesis.

    PubMed

    Ashworth, Ian W; Carboni, Davide; Hillier, Ian H; Nelson, David J; Percy, Jonathan M; Rinaudo, Giuseppe; Vincent, Mark A

    2010-10-14

    In the RCM reactions of a series of simple ?,?-dienes, the relative order of reactivity has been unambiguously determined showing that cyclohexene forms faster than cyclopentene or cycloheptene. 1,5-Hexadiene inhibits the RCM of 1,7-octadiene; 1,5-hexadiene cannot progress to the RCM product (cyclobutene) but forms an unexpectedly stable cyclic ?(2)-complex. PMID:20820538

  11. Women’s Self-Disclosure of HIV Infection: Rates, Reasons, and Reactions

    Microsoft Academic Search

    Jane M. Simoni; Hyacinth R. C. Mason; Gary Marks; Monica S. Ruiz; Deborah Reed; Jean L. Richardson

    1995-01-01

    A survey of 65 ethnically diverse women at 2 outpatient HIV clinics revealed relatively low rates of disclosure of HIV-positive serostatus to extended family members, somewhat higher rates for immediate family members, and highest rates for lovers and friends. Spanish-speaking Latinas were less likely to disclose their serostatus or to discuss HIV-related worries with others than English-speaking Latinas, African Americans,

  12. Kinetic and rheological measurements of the effects of inert 2-, 3- and 4-bromobenzoate ions on the cationic micellar-mediated rate of piperidinolysis of ionized phenyl salicylate.

    PubMed

    Yusof, Nor Saadah M; Niyaz Khan, M

    2011-05-01

    The effects of the concentration of inert organic salts, [MX], (MX=2-, 3- and 4-BrBzNa with BrBzNa=BrC(6)H(4)CO(2)Na) on the rate of piperidinolysis of ionized phenyl salicylate (PS(-)) have been rationalized in terms of pseudophase micellar (PM) coupled with an empirical equation. The appearance of induction concentration in the plots of k(obs) versus [MX] (where k(obs) is pseudo-first-order rate constants for the reaction of piperidine (Pip) with PS(-)) is attributed to the occurrence of two or more than two independent ion exchange processes between different counterions at the cationic micellar surface. The derived kinetic equation, in terms of PM model coupled with an empirical equation, gives empirical parameters F(X/S) and K(X/S) whose magnitudes lead to the calculation of usual ion exchange constant K(X)(Br) (=K(X)/K(Br) with K(X) and K(Br) representing cationic micellar binding constants of counterions X(-) and Br(-), respectively). The value of F(X/S) measures the fraction of S(-) (=PS(-)) ions transferred from the cationic micellar pseudophase to the aqueous phase by the optimum value of [MX] due to ion exchange X(-)/S(-). Similarly, the value of K(X/S) measures the ability of X(-) ions to expel S(-) ions from cationic micellar pseudophase to aqueous phase through ion exchange X(-)/S(-). This rather new technique gives the respective values of K(X)(Br) as 8.8±0.3, 71±6 and 62±5 for X(-)=2-, 3- and 4-BrBz(-). Rheological measurements reveal the shear thinning behavior of all the surfactant solutions at 15mM CTABr (cetyltrimethylammonium bromide) indicating indirectly the presence of rodlike micelles. The plots of shear viscosity (?) at a constant shear rate (?), i.e. ?(?), versus [MX] at 15 mM CTABr exhibit maxima for MX=3-BrBzNa and 4-BrBzNa while for MX=2-BrBzNa, the viscosity maximum appears to be missing. Such viscosity maxima are generally formed in surfactant solutions containing long stiff and flexible rodlike micelles with entangled and branched/multiconnected networks. Thus, 15 mM CTABr solutions at different [MX] contain long stiff and flexible rodlike micelles for MX=3- and 4-BrBzNa and short rodlike micelles for MX=2-BrBzNa. PMID:21333302

  13. Influence of mastication rate on dynamic flavour release analysed by combined model mouth/proton transfer reaction-mass spectrometry

    NASA Astrophysics Data System (ADS)

    van Ruth, Saskia M.; Buhr, Katja

    2004-12-01

    The influence of mastication rate on the dynamic release of seven volatile flavour compounds from sunflower oil was evaluated by combined model mouth/proton transfer reaction-mass spectrometry (PTR-MS). Air/oil partition coefficients were measured by static headspace gas chromatography. The dynamic release of the seven volatile flavour compounds from sunflower oil was significantly affected by the compounds' hydrophobicity and the mastication rate employed in the model mouth. The more hydrophobic compounds were released at a higher rate than their hydrophilic counterparts. Increase in mastication rate increased the maximum concentration measured by 36% on average, and the time to reach this maximum by 35% on average. Mastication affected particularly the release of the hydrophilic compounds. The maximum concentration of the compounds correlated significantly with the compounds' air/oil partition coefficients. The initial release rates over the first 15 s were affected by the type of compound, but not by the mastication rate. During the course of release, the proportions of the hydrophilic compounds to the overall flavour mixture in air decreased. The contribution of the hydrophobic compounds increased. Higher mastication rates, however, increased the proportions of the hydrophilic compounds and decreased those of the hydrophobic compounds.

  14. 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.

  15. Iodine atom production rates by electron impact versus post discharge reactions for pulsed COIL

    NASA Astrophysics Data System (ADS)

    Napartovich, A. P.; Kochetov, I. V.; Vagin, N. P.; Yuryshev, N. N.

    2009-02-01

    Pulsed discharge is effective means to achieve high-peak lasing in COIL. Numerical model is developed for simulation of pulsed discharge in gas stream from the singlet oxygen generator mixed with CF3I. The model comprises a system of kinetic equations for neutral and charged species, electric circuit equation, and gas thermal balance equation. Sources of iodine atoms under discharge and post-discharge conditions are analyzed. The dominant source in the discharge is electron-impact dissociation of CF3I molecules. In post-discharge phase chemical reactions are identified giving notable input into I production. Deformation of laser pulse waveform observed experimentally is explained by influence of these reactions.

  16. 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.

  17. MultiDimensional Simulations of Fluorocarbon Plasmas with Ion Energy Resolved Surface Reaction Rates

    Microsoft Academic Search

    Ning Zhou; Vladimir Kolobov; Vladimir Kudriavtsev

    2001-01-01

    The commercial CFD-ACE+ software has been extended to account for ion energy dependent surface reactions. The ion energy distribution function and the mean ion energy at a biased wafer were obtained using the Riley sheath model extended by the NASA group (Bose et al., J. Appl. Phys. v.87, 7176(2000)). The plasma chemistry model (by P. Ho et al., SAND2001-1292) consisting

  18. Fundamental Kinetic Modeling: ab initio rate constant calculations of elementary reactions 

    E-print Network

    Jenks, Richard Lee

    1998-01-01

    . The following discussion follows that of Benson (1976). Group Additivity Group additivity is a simple way to estimate the heat capacity, entropy and standard heat of formation for chemical species in a reaction. Each molecule is broken up into groups... method. The table containing the values of the fee-radical group are available as well. If these properties are required at temperatures other than 298 K, heat capacity data at several temperatures are given, and equations (7) and (8) are used...

  19. Overall rate constant measurements of the reactions of alkene-derived hydroxyalkylperoxy radicals with nitric oxide

    E-print Network

    Elrod, Matthew J.

    with nitric oxide Angela M. Miller, Laurence Y. Yeung, Annastassja C. Kiep and Matthew J. Elrod* Department ! R CHðOHÞ CHðO2Þ R0 ð2Þ which is generally followed by reaction with nitric oxide: R CHðOHÞ CHðO2Þ R0 derived from the OH-initiated oxidation of several atmospherically abundant alkenes--ethene, propene, 1

  20. Rate constant for the reaction of OH with HO/sub 2/

    SciTech Connect

    Lii, R.R.; Gorse, R.A. Jr.; Sauer, M.C. Jr.; Gordon, S.

    1980-01-01

    Spectrophotometric observation of both HO/sub 2/ and OH in pulse-irradiated Ar-H/sub 2/O-O/sub 2/ systems leads to a value of k/sub 1/ = (0.99 +- 0.12) x 10/sup -10/ cm/sup 3/ molecule/sup -1/s/sup -1/ at 308 K for the reaction OH + HO/sub 2/ ..-->.. H/sub 2/O + O/sub 2/.

  1. Rate constant for the reaction of OH with HO/sub 2/

    SciTech Connect

    Ruey-Rong Lii; Gorse, R.A. Jr.; Sauer, M.C. Jr.; Gordon, S.

    1980-04-17

    Spectrophotometric observation of both HO/sub 2/ and OH in pulse-irradiated Ar-H/sub 2/O-O/sub 2/ systems leads to a value of k/sub 1/ = (0.99 +- 0.12) x 10/sup -10/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 308 K for the reaction OH + HO/sub 2/ ..-->.. H/sub 2/O + O/sub 2/.

  2. 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.

  3. 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.

  4. Large-scale prediction of the parity distribution in the nuclear level density and application to astrophysical reaction rates

    E-print Network

    D. Mocelj; T. Rauscher; G. Martinez-Pinedo; K. Langanke; L. Pacearescu; A. Faessler; F. -K. Thielemann; Y. Alhassid

    2007-04-26

    A generalized method to calculate the excitation-energy dependent parity ratio in the nuclear level density is presented, using the assumption of Poisson distributed independent quasi particles combined with BCS occupation numbers. It is found that it is crucial to employ a sufficiently large model space to allow excitations both from low-lying shells and to higher shells beyond a single major shell. Parity ratios are only found to equilibrate above at least 5-10 MeV of excitation energy. Furthermore, an overshooting effect close to major shells is found where the parity opposite to the ground state parity may dominate across a range of several MeV before the parity ratio finally equilibrates. The method is suited for large-scale calculations as needed, for example, in astrophysical applications. Parity distributions were computed for all nuclei from the proton dripline to the neutron dripline and from Ne up to Bi. These results were then used to recalculate astrophysical reaction rates in a Hauser-Feshbach statistical model. Although certain transitions can be considerably enhanced or suppressed, the impact on astrophysically relevant reactions remains limited, mainly due to the thermal population of target states in stellar reaction rates.

  5. Large-scale prediction of the parity distribution in the nuclear level density and application to astrophysical reaction rates

    SciTech Connect

    Mocelj, D.; Rauscher, T.; Thielemann, F.-K. [Departement fuer Physik und Astronomie, Universitaet Basel, Basel (Switzerland); Martinez-Pinedo, G. [GSI Darmstadt, Darmstadt (Germany); Langanke, K. [GSI Darmstadt, Darmstadt (Germany); Institut fuer Kernphysik, Technische Universitaet Darmstadt, Darmstadt (Germany); Pacearescu, L.; Faessler, A. [Institut fuer Theoretische Physik, Universitaet Tuebingen, Tuebingen (Germany); Alhassid, Y. [Center for Theoretical Physics, Sloane Physics Laboratory, Yale University, New Haven, Connecticut 06520 (United States)

    2007-04-15

    A generalized method to calculate the excitation-energy dependent parity ratio in the nuclear level density is presented, using the assumption of Poisson distributed independent quasi particles combined with BCS occupation numbers. It is found that it is crucial to employ a sufficiently large model space to allow excitations both from low-lying shells and to higher shells beyond a single major shell. Parity ratios are only found to equilibrate above at least 5-10 MeV of excitation energy. Furthermore, an overshooting effect close to major shells is found where the parity opposite to the ground state parity may dominate across a range of several MeV before the parity ratio finally equilibrates. The method is suited for large-scale calculations as needed, for example, in astrophysical applications. Parity distributions were computed for all nuclei from the proton dripline to the neutron dripline and from Ne up to Bi. These results were then used to recalculate astrophysical reaction rates in a Hauser-Feshbach statistical model. Although certain transitions can be considerably enhanced or suppressed, the impact on astrophysically relevant reactions remains limited, mainly due to the thermal population of target states in stellar reaction rates.

  6. Kinetics of FeS precipitation: Part 1. Competing reaction mechanisms

    NASA Astrophysics Data System (ADS)

    Rickard, David

    1995-11-01

    The kinetics of the fast precipitation reaction between aqueous iron (II) and dissolved sulfide at 25°C can be interpreted in terms of two competing reactions. The first may be represented by Fe 2+ + H2S ? FeS(s) + 2 H+ This can be described by an observed rate law - d[aH 2S]/dt = k11[aH 2S] where k' 1, is the observed first order rate constant with a value of 90 ± 10 s -1, [ cH 2S] is the concentration of dissolved H 2S in moles per liter, and t is time in seconds. The rate law is consistent with an Eigen-Wilkins model of the process in which the rate is described by d[FeS]/dt = - d[ aH2S]/dt = k1[ aFe2+][aH 2S], where aH 2S and aFe 2+ are the formally dimensionless hydrogen sulfide and Fe(II) activities which are represented on a moles·liter -1 scale for experimental and practical convenience. The logarithm of k1, the theoretical Eigen-Wilkins reaction rate constant, has a value of 7 ± 1 liters·mole -1·s -1. The second reaction may be represented by Fe 2 + 2HS - ? Fe(HS) 2(s) The rate of this reaction may be described by an observed rate law of the form - d[aHS -]/ dt = k21[aHS -] 2 where [ aHS -] is the formally dimensionless bisulfide activity which is represented on a moles·liter -1 scale for experimental convenience. The observed second order rate constant, k' 2, has a value of 1.3 × 10 7 liters·mole -1·s -1 at 25°C. The result is consistent with an Eigen-Wilkins model of the process in which k21[aFe 2+][aHS -] 2 where aFe 2+ is the dissolved Fe(II) activity and the logarithm of k2, the Eigen-Wilkins reaction rate constant, has a value of 12.5 ± 1 liters 2·mole -2·s -1. The theoretical interpretation of both reactions suggests that the rates are direct functions of the ion activity products of the iron sulfide precipitates. The second stage of the reaction involves the condensation of Fe(SH) 2 to FeS with the release of dissolved sulfide back to solution: Fe(SH) 2( s)?FeS( s)+H 2S This reaction is relatively slow and results in a sinusoidal form superimposed on the Stage 1 concentration-time curve. Overall, the rate of removal of total dissolved sulfide from solution by these processes can be empirically modeled by - d[ ?S]/ dt= ko[ ?S] and [ ?S] - [ ?S] o = e- ko1 where [?S] is the concentration of total dissolved sulfide at any time, [?S] 0 is the concentration of total dissolved sulfide at t = 0, and k0 is a pseudo first order rate constant of 15 s -1 where [?Fe 2+], the total dissolved iron(II) concentration, is between 10 -3 and 10 -4 M. Theoretically, the rates of both reactions are directly proportional to [ aFe 2+]. A good approximation for the rate of removal of total dissolved sulfide by the iron(II) (bi)sulfide precipitation processes in most environments can, therefore, be obtained by using a value for k 0of15 × 10 -4/[ ?Fe2+] . Application of the rate laws to natural systems suggests that the relative dominance of the two competing pathways is pH and ?S dependent and independent of ?Fe 2+. In environments with ppm or greater ?S concentrations (?10 -3 M), the rate of sulfide removal is two magnitudes greater in neutral to alkaline systems than in systems with pH < 7. The bisulfide pathway resulting in the formation of Fe(SH) 2 dominates and the H 2S pathway only dominates in acidic environments. The results suggest that, in these relatively sulfide-rich environments, a standing concentration of Fe(SH) 2 will be present and may constitute an important component in further reactions, such as pyrite formation. In contrast, in sulfide-poor systems with ?S concentrations at the sub-ppm (<10 -3 M) level, the rate is greater in neutral to acidic conditions and the H 2S pathway, involving the direct formation of FeS, dominates in all environments with pH < 8.

  7. Aroxyl-radical-scavenging rate increases remarkably under the coexistence of ?-tocopherol and ubiquinol-10 (or vitamin C): finding of synergistic effect on the reaction rate.

    PubMed

    Mukai, Kazuo; Ouchi, Aya; Nakaya, Saori; Nagaoka, Shin-ichi

    2013-07-18

    Measurements of aroxyl radical (ArO(•))-scavenging rate constants (ks(AOH)) of antioxidants (AOHs) (?-tocopherol (?-TocH), ubiquinol-10 (UQ10H2), and sodium ascorbate (Na(+)AsH(-))) were performed in 2-propanol/water (2-PrOH/H2O, 5/1, v/v) solution using stopped-flow spectrophotometry. ks(AOH) values were measured not only for each AOH but also for the mixtures of two AOHs ((i) ?-TocH and UQ10H2 and (ii) ?-TocH and Na(+)AsH(-)). A notable synergistic effect that the ks(AOH) values increase 1.6, 2.5, and 6.8 times for ?-TocH, UQ10H2, and Na(+)AsH(-), respectively, was observed for the solutions including two kinds of AOHs. Furthermore, measurements of the regeneration rates of ?-tocopheroxyl radical (?-Toc(•)) to ?-TocH by UQ10H2 and Na(+)AsH(-) were performed in 2-PrOH/H2O using double-mixing stopped-flow spectrophotometry. Second-order rate constants (kr) obtained for UQ10H2 and Na(+)AsH(-) were 2.01 × 10(5) and 1.19 × 10(6) M(-1) s(-1), respectively. In fact, UV-vis absorption of ?-Toc(•) (?max = 428 nm), which had been produced by reaction of ?-TocH with ArO(•), disappeared under the existence of UQ10H2 or Na(+)AsH(-) due to the above fast regeneration reaction. The result indicates that the prooxidant effect of ?-Toc(•) is suppressed by the coexistence of UQ10H2 or Na(+)AsH(-). As ?-TocH, UQ10H2, and ascorbate monoanion (AsH(-)) coexist in relatively high concentrations in plasma, blood, and various tissues, the above synergistic effect, that is, the increase of the free-radical-scavenging rate and suppression of the prooxidant reaction, may function in biological systems. PMID:23777398

  8. 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.

  9. Finite Element Analysis of the Time-Dependent Smoluchowski Equation for Acetylcholinesterase Reaction Rate Calculations

    PubMed Central

    Cheng, Yuhui; Suen, Jason K.; Zhang, Deqiang; Bond, Stephen D.; Zhang, Yongjie; Song, Yuhua; Baker, Nathan A.; Bajaj, Chandrajit L.; Holst, Michael J.; McCammon, J. Andrew

    2007-01-01

    This article describes the numerical solution of the time-dependent Smoluchowski equation to study diffusion in biomolecular systems. Specifically, finite element methods have been developed to calculate ligand binding rate constants for large biomolecules. The resulting software has been validated and applied to the mouse acetylcholinesterase (mAChE) monomer and several tetramers. Rates for inhibitor binding to mAChE were calculated at various ionic strengths with several different time steps. Calculated rates show very good agreement with experimental and theoretical steady-state studies. Furthermore, these finite element methods require significantly fewer computational resources than existing particle-based Brownian dynamics methods and are robust for complicated geometries. The key finding of biological importance is that the rate accelerations of the monomeric and tetrameric mAChE that result from electrostatic steering are preserved under the non-steady-state conditions that are expected to occur in physiological circumstances. PMID:17307827

  10. 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.

  11. The Influence of Uncertainties in the 15O(alpha,gamma)19Ne Reaction Rate on Models of Type I X-Ray Bursts

    E-print Network

    Barry Davids; Richard H. Cyburt; Jordi José; Subramanian Mythili

    2011-04-14

    We present a Monte Carlo calculation of the astrophysical rate of the 15O(alpha,gamma)19Ne reaction based on an evaluation of published experimental data. By considering the likelihood distributions of individual resonance parameters derived from measurements, estimates of upper and lower limits on the reaction rate at the 99.73% confidence level are derived in addition to the recommended, median value. These three reaction rates are used as input for three separate calculations of Type I x-ray bursts using spherically symmetric, hydrodynamic simulations of an accreting neutron star. In this way the influence of the 15O(alpha,gamma)19Ne reaction rate on the peak luminosity, recurrence time, and associated nucleosynthesis in models of Type I x-ray bursts is studied. Contrary to previous findings, no substantial effect on any of these quantities is observed in a sequence of four bursts when varying the reaction rate between its lower and upper limits. Rather, the differences in these quantities are comparable to the burst-to-burst variations with a fixed reaction rate, indicating that uncertainties in the 15O(alpha,gamma)19Ne reaction rate do not strongly affect the predictions of this Type I x-ray burst model.

  12. THE INFLUENCE OF UNCERTAINTIES IN THE {sup 15}O({alpha}, {gamma}){sup 19}Ne REACTION RATE ON MODELS OF TYPE I X-RAY BURSTS

    SciTech Connect

    Davids, Barry [TRIUMF, Vancouver, BC V6T 2A3 (Canada); Cyburt, Richard H. [Joint Institute for Nuclear Astrophysics and National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI (United States); Jose, Jordi [Departament de Fisica i Enginyeria Nuclear, Universitat Politecnica de Catalunya and Institut d'Estudis Espacials de Catalunya, Barcelona (Spain); Mythili, Subramanian [Physics Department, George Mason University, Fairfax, VA (United States)

    2011-07-01

    We present a Monte Carlo calculation of the astrophysical rate of the {sup 15}O({alpha}, {gamma}){sup 19}Ne reaction based on an evaluation of published experimental data. By considering the likelihood distributions of individual resonance parameters derived from measurements, estimates of upper and lower limits on the reaction rate at the 99.73% confidence level are derived in addition to the recommended, median value. These three reaction rates are used as input for three separate calculations of Type I X-ray bursts (XRBs) using spherically symmetric, hydrodynamic simulations of an accreting neutron star. In this way the influence of the {sup 15}O({alpha}, {gamma}){sup 19}Ne reaction rate on the peak luminosity, recurrence time, and associated nucleosynthesis in models of Type I XRBs is studied. Contrary to previous findings, no substantial effect on any of these quantities is observed in a sequence of four bursts when varying the reaction rate between its lower and upper limits. Rather, the differences in these quantities are comparable to the burst-to-burst variations with a fixed reaction rate, indicating that uncertainties in the {sup 15}O({alpha}, {gamma}){sup 19}Ne reaction rate do not strongly affect the predictions of this Type I XRB model.

  13. Communication: Transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields.

    PubMed

    Craven, Galen T; Bartsch, Thomas; Hernandez, Rigoberto

    2014-07-28

    When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product--for example, an energy barrier--becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, "Persistence of transition state structure in chemical reactions driven by fields oscillating in time," Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically expensive simulation of the long-time dynamics of a large ensemble of trajectories. PMID:25084872

  14. Communication: Transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields

    NASA Astrophysics Data System (ADS)

    Craven, Galen T.; Bartsch, Thomas; Hernandez, Rigoberto

    2014-07-01

    When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product—for example, an energy barrier—becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, "Persistence of transition state structure in chemical reactions driven by fields oscillating in time," Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically expensive simulation of the long-time dynamics of a large ensemble of trajectories.

  15. Rate enhanced olefin cross-metathesis reactions: the copper iodide effect.

    PubMed

    Voigtritter, Karl; Ghorai, Subir; Lipshutz, Bruce H

    2011-06-01

    Copper iodide has been shown to be an effective cocatalyst for the olefin cross-metathesis reaction. In particular, it has both a catalyst stabilizing effect due to iodide ion, as well as copper(I)-based phosphine-scavenging properties that apply to use of the Grubbs-2 catalyst. A variety of Michael acceptors and olefinic partners can be cross-coupled under mild conditions in refluxing diethyl ether that avoid chlorinated solvents. This effect has also been applied to chemistry in water at room temperature using the new surfactant TPGS-750-M. PMID:21528868

  16. 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).

  17. 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. [I.N.F.N. Laboratori Nazionali del Sud, via Santa Sofia 62, Catania (Italy); Lamia, L.; Spitaleri, C. [Dipartimento di Fisica e Astronomia, Universitá degli Studi di Catania (Italy)

    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.

  18. On the introduction of 17O+p reaction rates evaluated through the THM in AGB nucleosynthesis calculations

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    The rates for the 17O(p,??14N, 17O(p,?)18F and 18O(p,?)15N 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.

  19. 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.

  20. Rates of dissolved oxygen-induced polymerization reactions of phenol and o-cresol on activated carbon

    SciTech Connect

    Abuzaid, N.S.; Nakhla, G.F. [King Fahd Univ. of Petroleum & Minerals, Dhahran (Saudi Arabia)

    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.

  1. 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.

  2. Calculations of Maxwellian-averaged cross sections and astrophysical reaction rates using the ENDF/B-VII.0, JEFF-3.1, JENDL-3.3, and ENDF/B-VI.8 evaluated nuclear reaction data libraries

    SciTech Connect

    Pritychenko, B., E-mail: pritychenko@bnl.go [National Nuclear Data Center, Brookhaven National Laboratory, Upton, NY 11973-5000 (United States); Mughaghab, S.F.; Sonzogni, A.A. [National Nuclear Data Center, Brookhaven National Laboratory, Upton, NY 11973-5000 (United States)

    2010-11-15

    We have calculated the Maxwellian-averaged cross sections and astrophysical reaction rates of the stellar nucleosynthesis reactions (n, {gamma}), (n, fission), (n, p), (n, {alpha}), and (n, 2n) using the ENDF/B-VII.0, JEFF-3.1, JENDL-3.3, and ENDF/B-VI.8 evaluated nuclear reaction data libraries. These four major nuclear reaction libraries were processed under the same conditions for Maxwellian temperatures (kT) ranging from 1 keV to 1 MeV. We compare our current calculations of the s-process nucleosynthesis nuclei with previous data sets and discuss the differences between them and the implications for nuclear astrophysics.

  3. Stellar reaction rate for (22)Mg + p -> (23)Al from the asymptotic normalization coefficient in the mirror nuclear system (22)Ne + n -> (23)Ne 

    E-print Network

    Al-Abdullah, T.; Carstoiu, F.; Chen, X.; Clark, H. L.; Fu, C.; Gagliardi, Carl A.; Lui, Y. -W; Mukhamedzhanov, A.; Tabacaru, G.; Tokimoto, Y.; Trache, L.; Tribble, Robert E.

    2010-01-01

    The production of (22)Na in ONe novae can be influenced by the (22)Mg(p,gamma)(23)Al reaction. To investigate this reaction rate at stellar energies, we have determined the asymptotic normalization coefficient (ANC) for (22)Mg + p -> (23)Al through...

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

    E-print Network

    Jesudason, Christopher G

    2011-01-01

    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 ...

  5. Determination of rate constants for the reaction between methyldiethanolamine and carbon dioxide 

    E-print Network

    Brabson, Charles Meade

    1985-01-01

    . These impurities are removed in a process called gas sweetening. While many processes could theoretically be used to purify natural gas, the most economical results are obtained by absorbing the impurities into liquids. In the natural gas industry, aqueous..., and energy costs available during that period. However, the energy and inflation problems of the 1970'. s and 1980's have had a significant impact on gas sweetening technology. As natural gas prices increased, and the production rates from sweet gas fields...

  6. Quantum instanton calculation of rate constant for CH4 + OH ? CH3 + H2O reaction: Torsional anharmonicity and kinetic isotope effect

    NASA Astrophysics Data System (ADS)

    Wang, Wenji; Zhao, Yi

    2012-12-01

    Thermal rate constants for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The results reveal that the quantum effect is remarkable for the reaction at both low and high temperatures, and the obtained rates are in good agreement with experimental measurements at high temperatures. Compared to the harmonic approximation, the torsional anharmonic effect of the internal rotation has a little influence on the rates at low temperatures, however, it enhances the rate by about 20% at 1000 K. In addition, the free energy barriers for the isotopic reactions and the temperature dependence of kinetic isotope effects are also investigated. Generally speaking, for the title reaction, the replacement of OH with OD will reduce the free energy barrier, while substituting D for H (connected to C) will increase the free energy barrier.

  7. Rate coefficients and kinetic isotope effects of the X + CH[subscript 4] ? CH[subscript 3] + HX (X = H, D, Mu) reactions from ring polymer molecular dynamics

    E-print Network

    Li, Yongle

    The thermal rate coefficients and kinetic isotope effects have been calculated using ring polymer molecular dynamics (RPMD) for the prototypical reactions between methane and several hydrogen isotopes (H, D, and Mu). The ...

  8. 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.

  9. 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.

  10. Pulsed laser photolysis and quantum chemical-statistical rate study of the reaction of the ethynyl radical with water vapor

    NASA Astrophysics Data System (ADS)

    Carl, Shaun A.; Minh Thi Nguyen, Hue; Elsamra, Rehab M. I.; Tho Nguyen, Minh; Peeters, Jozef

    2005-03-01

    The rate coefficient of the gas-phase reaction C2H+H2O?products has been experimentally determined over the temperature range 500-825K using a pulsed laser photolysis-chemiluminescence (PLP-CL) technique. Ethynyl radicals (C2H) were generated by pulsed 193nm photolysis of C2H2 in the presence of H2O vapor and buffer gas N2 at 15Torr. The relative concentration of C2H radicals was monitored as a function of time using a CH * chemiluminescence method. The rate constant determinations for C2H+H2O were k1(550K)=(2.3±1.3)×10-13cm3s-1, k1(770cm3s-1, and k1(825cm3s-1. The error in the only other measurement of this rate constant is also discussed. We have also characterized the reaction theoretically using quantum chemical computations. The relevant portion of the potential energy surface of C2H3O in its doublet electronic ground state has been investigated using density functional theory B3LYP /6-311++G(3df,2p) and molecular orbital computations at the unrestricted coupled-cluster level of theory that incorporates all single and double excitations plus perturbative corrections for the triple excitations, along with the 6-311++G(3df,2p) basis set [(U)CCSD(T)/6-311++G(3df,2p)] and using UCCSD(T )/6-31G(d,p) optimized geometries. Five isomers, six dissociation products, and sixteen transition structures were characterized. The results confirm that the hydrogen abstraction producing C2H2+OH is the most facile reaction channel. For this channel, refined computations using (U)CCSD(T)/6-311++G(3df,2p)//(U)CCSD(T)/6-311++G(d,p) and complete-active-space second-order perturbation theory/complete-active-space self-consistent-field theory (CASPT2/CASSCF) [B. O. Roos, Adv. Chem. Phys. 69, 399 (1987)] using the contracted atomic natural orbitals basis set (ANO-L) [J. Almlöf and P. R. Taylor, J. Chem. Phys.86, 4070 (1987)] were performed, yielding zero-point energy-corrected potential energy barriers of 17kJmol-1 and 15kJmol-1, respectively. Transition-state theory rate constant calculations, based on the UCCSD(T) and CASPT2/CASSCF computations that also include H-atom tunneling and a hindered internal rotation, are in perfect agreement with the experimental values. Considering both our experimental and theoretical determinations, the rate constant can best be expressed, in modified Arrhenius form as k1(T)=(2.2±0.1)×10-21T3.05exp[-(376±100)/T]cm3s-1 for the range 300-2000K. Thus, at temperatures above 1500K, reaction of C2H with H2O is predicted to be one of the dominant C2H reactions in hydrocarbon combustion.

  11. RATE CONSTANT FOR THE REACTION OF NO2 WITH SULFUR(IV) OVER THE PH RANGE 5.3-13 (JOURNAL VERSION)

    EPA Science Inventory

    Rate constants have been determined for the reactions of NO2 with SO3(2-) and HSO3(1-) in aqueous solutions. The rate constant increases from about 1.2 x 10 to the 7th power /M-sec near pH 5 to 2.9 x 10 to the 7th power /M-sec at pH 13. The reaction appears to involve the formati...

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

    PubMed

    Radulovi?, Vladimir; Štancar, Žiga; Snoj, Luka; Trkov, Andrej

    2014-02-01

    The calculation of axial neutron flux distributions with the MCNP code at the JSI TRIGA Mark II reactor has been validated with experimental measurements of the (197)Au(n,?)(198)Au reaction rate. The calculated absolute reaction rate values, scaled according to the reactor power and corrected for the flux redistribution effect, are in good agreement with the experimental results. The effect of different cross-section libraries on the calculations has been investigated and shown to be minor. PMID:24316530

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  14. Determination of rate constants for the reactions of H, OH and eaq with indole-3-acetic acid and other plant hormones

    Microsoft Academic Search

    R. S. Shetiya; K. N. Rao; J. Shankar

    1972-01-01

    In the radiolysis of aqueous solutions of indole, indole-3-acetic acid, indole-3-propionic acid, 1-naphthylacetic acid and phenylacetic acid, the absolute rate constants of their reactions with H and OH have been determined by competition kinetics using 2-propanol as the competitor. Hydrated electron reaction rate constants have been determined for indoie, indole-3-acetic acid and indole-3-propionic acid at pH = 11 using the

  15. Evaluation of reactivity of pesticides with ozone in water using the energies of frontier molecular orbitals

    Microsoft Academic Search

    Jian-ying Hu; Takeshi Morita; Yasumoto Magara; Takako Aizawa

    2000-01-01

    The rate constants of ozone with four groups of pesticides (4 phenolic-, 8 organonitrogen-, 8 phenoxyalkylacitic-, and 4 heterocyclic N-pesticides) were determined under controlled conditions at a pH of 7.5, ionic strength of ca 10?3 M, and 100 ?M NaHCO3. The rate constant for BPMC was first determined from a pseudo-first order reaction model, the rate constants for the other pesticides

  16. FORMALISM FOR INCLUSION OF MEASURED REACTION CROSS SECTIONS IN STELLAR RATES INCLUDING UNCERTAINTIES AND ITS APPLICATION TO NEUTRON CAPTURE IN THE s-PROCESS

    SciTech Connect

    Rauscher, Thomas [Department of Physics, University of Basel, CH-4056 Basel (Switzerland)

    2012-08-10

    A general formalism to include experimental reaction cross sections into calculations of stellar rates is presented. It also allows us to assess the maximally possible reduction of uncertainties in the stellar rates by experiments. As an example for the application of the procedure, stellar neutron capture reactivities from KADoNiS v0.3 are revised and the remaining uncertainties shown. Many of the uncertainties in the stellar rates are larger than those obtained experimentally. This has important consequences for s-process models and the interpretation of meteoritic data because it allows the rates of some reactions to vary within a larger range than previously assumed.

  17. Effects of network dissolution changes on pore-to-core up-scaled reaction rates for kaolinite and anorthite reactions under acidic conditions

    E-print Network

    New York at Stoney Brook, State University of

    and anorthite reactions under acidic conditions Daesang Kim1 and W. Brent Lindquist2 * 1 King Abdullah the predictions of a continuum model. Specifically, we6 modeled anorthite and kaolinite reactions under acidic flow conditions during which the7 anorthite reactions remain far from equilibrium (dissolution only

  18. A study of rates of reaction of some substituted diphenyldiazomethanes and benzoic acid 

    E-print Network

    Gilby, Ralph Fredrick

    1954-01-01

    -nitrodiphenyIdiazomethane, benzoyl chloride - pre? pared from benzoic acid (Mallinckrodt Chemical Works) and thionyl (20). I. M. Seilbron, "Dictionary of Organic Compounds", Oxford Uni? versity Press, New York, K.Y., 1938, Vol. IU, p. 188. (21). I. M... of the benzoic acid (Mallinckrodt Chemical Works) used in this study were as follows: Analytical Reagent, Primary Standard, assay 99*95 to 100.05# benzoic acid. This material was dried at 100? C. for two hours before use. 22 EXPERIMENTAL The rates...

  19. Endothermic decompositions of inorganic monocrystalline thin plates. II. Displacement rate modulation of the reaction front

    NASA Astrophysics Data System (ADS)

    Bertrand, G.; Comperat, M.; Lallemant, M.

    1980-09-01

    Copper sulfate pentahydrate dehydration into trihydrate was investigated using monocrystalline platelets with (110) crystallographic orientation. Temperature and pressure conditions were selected so as to obtain elliptical trihydrate domains. The study deals with the evolution, vs time, of elliptical domain dimensions and the evolution, vs water vapor pressure, of the {D}/{d} ratio of ellipse axes and on the other hand of the interface displacement rate along a given direction. The phenomena observed are not basically different from those yielded by the overall kinetic study of the solid sample. Their magnitude, however, is modulated depending on displacement direction. The results are analyzed within the scope of our study of endothermic decomposition of solids.

  20. Tired and True: Message in a bottle--Analyzing reaction rates using gas pressure sensors

    NSDL National Science Digital Library

    Dan Vincent

    2009-03-01

    One of the many ways to engage students in science is by using probes or computerized devices that respond in real time to changes. In the following learning cycle lesson, an after-school science and mathematics club consisting of about 20 students uses a computerized pressure sensor to evaluate the rates at which effervescent tablets (such as Alka-Seltzer) dissolve. By using the data-collection devices, students were able to see, in real time, the variables that affected the pressure in the bottle. They were also able to apply the "message in the bottle" to effervescent rockets.