WorldWideScience

Sample records for phase reaction rates

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

    Science.gov (United States)

    Minakata, Daisuke; Crittenden, John

    2011-04-15

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

  2. Reaction rate of hydrolysis of iodine

    International Nuclear Information System (INIS)

    Miyake, Yoshikazu; Eguchi, Wataru; Adachi, Motonari

    1979-01-01

    Absorption rates of dilute iodine vapor contained in air by aqueous mixtures of sodium hydroxide and boric acid were measured using a laminar liquid jet column absorber at 298 K. Absorption rates in this system are controlled by a series of complex reactions taking place in the liquid phase. The reaction rate constant of iodine hydrolysis in the aqueous phase was determined from the absorption rates observed under the conditions that the base-catalytic hydrolysis reaction of iodine can be considered to be irreversible and that other reactions can be neglected. The absorption rates calculated theoretically with the rate constant value obtained above were in good accordance with the whole experimental data observed for a wide range of experimental conditions. (author)

  3. Temperature dependence of muonium reaction rates in the gas phase

    International Nuclear Information System (INIS)

    Fleming, D.G.; Garner, D.M.; Mikula, R.J.; British Columbia Univ., Vancouver

    1981-01-01

    A study of the temperature dependence of reaction rates has long been an important tool in establishing reaction pathways in chemical reactions. This is particularly true for the reactions of muonium (in comparison with those of hydrogen) since a measurement of the activation energy for chemical reaction is sensitive to both the height and the position of the potential barrier in the reaction plane. For collision controlled reactions, on the other hand, the reaction rate is expected to exhibit a weak T 1 sup(/) 2 dependence characteristic of the mean collision velocity. These concepts are discussed and their effects illustrated in a comparison of the chemical and spin exchange reaction rates of muonium and hydrogen in the temperature range approx.300-approx.500 K. (orig.)

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

    Science.gov (United States)

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

    2018-05-01

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

  5. Rate of Isotope Exchange Reaction Between Tritiated Water in a Gas Phase and Water on the Surface of Piping Materials

    International Nuclear Information System (INIS)

    Nakashio, Nobuyuki; Yamaguchi, Junya; Kobayashi, Ryusuke; Nishikawa, Masabumi

    2001-01-01

    The system effect of tritium arises from the interaction of tritium in the gas phase with water on the surface of piping materials. It has been reported that the system effect can be quantified by applying the serial reactor model to the piping system and that adsorption and isotope exchange reactions play the main roles in the trapping of tritium. The isotope exchange reaction that occurs when the chemical form of tritium in the gas phase is in the molecular form, i.e., HT or T 2 , has been named isotope exchange reaction 1, and that which occurs when tritium in the gas phase is in water form, i.e., HTO or T 2 O, has been named isotope exchange reaction 2.The rate of isotope exchange reaction 2 is experimentally quantified, and the rate is observed to be about one-third of the rate of adsorption. The trapping and release behavior of tritium from the piping surface due to isotope exchange reaction 2 is also discussed. It is certified that swamping of water vapor to process gas is effective to release tritium from the surface contaminated with tritium

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

    Science.gov (United States)

    Dateo, Christopher E.; Walch, Stephen P.

    2002-01-01

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

  7. Nuclear-reaction rates in the thermonuclear runaway phase of accreting neutron stars

    International Nuclear Information System (INIS)

    Wiescher, M.; Barnard, V.; Goerres, J.; Fisker, J.L.; Martinez-Pinedo, G.; Langanke, K.; Rembges, F.; Thielemann, F.K.; Schatz, H.

    2002-01-01

    The rp-process has been suggested as the dominant nucleosynthesis process in explosive hydrogen burning at high temperature and density conditions. The process is characterized by a sequence of fast proton capture reactions and subsequent β-decays. The reaction path of the rp-process runs along the drip line up to Z∼50. Most of the charged-particle reaction rates for the reaction path are presently based on statistical Hauser-Feshbach calculations. While these rates are supposed to be reliable within a factor of two for conditions of high density in the compound nuclei, discrepancies may occur for nuclei near closed shells or near the proton drip line where the Q-values of proton capture processes are typically very small. It has been argued that the thermonuclear runaway is less sensitive to the reaction rates because of the rapid time-scale of the event. However, since these processes may operate at the same time-scale as fast mixing and convection processes, a change in reaction rates indeed may have a significant impact. In this paper we present two examples, the break-out from the hot CNO cycles, and the thermonuclear runaway in X-ray bursts itself, where changes in reaction rates have a direct impact on time-scale, energy generation and nucleosynthesis predictions for the explosive event. (orig.)

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

    Science.gov (United States)

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

    2012-07-05

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

  9. Rate of reaction of dimethylmercury with oxygen atoms in the gas phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge

    1986-01-01

    The rate constant for the reaction of atomic oxygen (O(3P)) with dimethylmercury has been measured at room temperature at a pressure of about 1 Torr using a fast flow system with electron paramagnetic resonance and mass spectrometric detection. Some reaction products were identified. The rate...

  10. Back Reaction And Local Cosmological Expansion Rate

    CERN Document Server

    Geshnizjani, G; Geshnizjani, Ghazal; Brandenberger, Robert

    2002-01-01

    We calculate the back reaction of cosmological perturbations on a general relativistic variable which measures the local expansion rate of the Universe. Specifically, we consider a cosmological model in which matter is described by a single field. We analyze back reaction both in a matter dominated Universe and in a phase of scalar field-driven chaotic inflation. In both cases, we find that the leading infrared terms contributing to the back reaction vanish when the local expansion rate is measured at a fixed value of the matter field which is used as a clock, whereas they do not appear to vanish if the expansion rate is evaluated at a fixed value of the background time. We discuss possible implications for more realistic models with a more complicated matter sector.

  11. The Phase Behavior Effect on the Reaction Engineering of Transesterification Reactions and Reactor Design for Continuous Biodiesel Production

    Science.gov (United States)

    Csernica, Stephen N.

    The demand for renewable forms of energy has increased tremendously over the past two decades. Of all the different forms of renewable energy, biodiesel, a liquid fuel, has emerged as one of the more viable possibilities. This is in large part due to the fact that biodiesel can readily be used in modern day diesel engines with nearly no engine modifications. It is commonly blended with conventional petroleum-derived diesel but it can also be used neat. As a result of the continued growth of the industry, there has been a correspondingly large increase in the scientific and technical research conducted on the subject. Much of the research has been conducted on the feasibility of using different types of feedstocks, which generally vary with respect to geographic locale, as well as different types of catalysts. Much of the work of the present study was involved with the investigation of the binary liquid-liquid nature of the system and its effects on the reaction kinetics. Initially, the development of an analytical method for the analysis of the compounds present in transesterification reaction mixtures using high performance liquid chromatography (HPLC) was developed. The use of UV(205 nm) as well as refractive index detection (RID) were shown capable to detect the various different types of components associated with transesterification reactions. Reversed-phase chromatography with isocratic elution was primarily used. Using a unique experimental apparatus enabling the simultaneous analysis of both liquid phases throughout the reaction, an experimental method was developed for measuring the reaction rate under both mass transfer control and reaction control. The transesterification reaction rate under each controlling mechanism was subsequently evaluated and compared. It was determined that the reaction rate is directly proportional to the concentration of triglycerides in the methanol phase. Furthermore, the reaction rate accelerates rapidly as the system

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

    Science.gov (United States)

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

    2015-07-01

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

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

    Science.gov (United States)

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

    2015-01-01

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

  14. Back reaction and the local cosmological expansion rate

    CERN Document Server

    Geshnizjani, G

    2002-01-01

    We calculate the back reaction of cosmological perturbations on a general relativistic variable which measures the local expansion rate of the Universe. Specifically, we consider a cosmological model in which matter is described by a single field. We analyze back reaction both in a matter-dominated Universe and in a phase of scalar field-driven chaotic inflation. In both cases, we find that the leading infrared terms contributing to the back reaction vanish when the local expansion rate is measured at a fixed value of the matter field which is used as a clock, whereas they do not appear to vanish if the expansion rate is evaluated at a fixed value of the background time. We discuss possible implications for more realistic models with a more complicated matter sector.

  15. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    Science.gov (United States)

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-02

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  16. Chemical-Reaction-Controlled Phase Separated Drops: Formation, Size Selection, and Coarsening

    Science.gov (United States)

    Wurtz, Jean David; Lee, Chiu Fan

    2018-02-01

    Phase separation under nonequilibrium conditions is exploited by biological cells to organize their cytoplasm but remains poorly understood as a physical phenomenon. Here, we study a ternary fluid model in which phase-separating molecules can be converted into soluble molecules, and vice versa, via chemical reactions. We elucidate using analytical and simulation methods how drop size, formation, and coarsening can be controlled by the chemical reaction rates, and categorize the qualitative behavior of the system into distinct regimes. Ostwald ripening arrest occurs above critical reaction rates, demonstrating that this transition belongs entirely to the nonequilibrium regime. Our model is a minimal representation of the cell cytoplasm.

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

    KAUST Repository

    Suleimanov, Yu.V.

    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+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

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

    KAUST Repository

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

    2013-01-01

    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+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  19. Effect of Five-Finger Shoes on Vertical Ground Reaction Force Loading Rates and Perceived Comfort during the Stance Phase of the Running

    Directory of Open Access Journals (Sweden)

    Seyede Zeynab Hoseini

    2016-06-01

    Full Text Available Objective:  Increased vertical ground reaction force loading rates and lack of comfort footwear in the early stance phase can increase the risk of overuse injuries. The purpose of this study was to investigate the effect of Five-finger shoes on vertical ground reaction force loading rate and perceived comfort during the stance phase of running. Methods: 15 male students (aged 24 ± 5/24 years, weight 75/8 ± 4/61 kg, height 178/6 ± 6/64 cm were selected. Subjects were asked to run over a force plate, in control shoe, five finger shoe and barefoot conditions. Loading rate using the slope of the vertical reaction force and perceived comfort were determined using a visual analogue scale. One factor repeated measures ANOVA was used to test the loading rate hypothesis and Paired t-tests was used to test the meaningfulness of perceived comfort (P<0/05. Results: The effect of shoes on loading rate was found to be not significant (P=0.1. However, comfort of control shoes increased by 10. 92% as compared to that of five-finger shoes (P=0.001.  Conclusion: The loading rate of five-finger shoes is the same as that of barefoot during running; however, as subjects did not perceive them as comfortable as regular shoes are five-finger shoes cannot be advised as a desirable choice in exercises.

  20. Thermonuclear reaction rates. III

    International Nuclear Information System (INIS)

    Harris, M.J.; Fowler, W.A.; Caughlan, G.R.; Zimmerman, B.A.

    1983-01-01

    Stellar thermonuclear reaction rates are revised and updated, adding a number of new important reaction rates. Several reactions with large negative Q-values are included, and examples of them are discussed. The importance of the decay rates for Mg-26(p,n) exp 26 Al and Al-26(n,p) exp 26 Mg for stellar studies is emphasized. 19 references

  1. Resonant thermonuclear reaction rate

    International Nuclear Information System (INIS)

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

    1986-01-01

    Basic physical principles for the resonant and nonresonant thermonuclear reaction rates are applied to find their standard representations for nuclear astrophysics. Closed-form representations for the resonant reaction rate are derived in terms of Meijer's G-function. Analytic representations of the resonant and nonresonant nuclear reaction rates are compared and the appearance of Meijer's G-function is discussed in physical terms

  2. Sn-In-Ag phase equilibria and Sn-In-(Ag)/Ag interfacial reactions

    International Nuclear Information System (INIS)

    Chen Sinnwen; Lee Wanyu; Hsu Chiaming; Yang Chingfeng; Hsu Hsinyun; Wu Hsinjay

    2011-01-01

    Research highlights: → Thermodynamic models of Sn-In and Sn-In-Ag are developed using the CALPHAD approach. → Reaction layer in the Sn-In-(Ag)/Ag couples at 100 deg. C is thinner than those at 25 deg. C, 50 deg. C, and 75 deg. C. → Reactions in the Sn-20 wt%In-2.8 wt%Ag/Ag couples are faster than those in the Sn-20 wt%In/Ag couples. - Abstract: Experimental verifications of the Sn-In and Sn-In-Ag phase equilibria have been conducted. The experimental measurements of phase equilibria and thermodynamic properties are used for thermodynamic modeling by the CALPHAD approach. The calculated results are in good agreement with experimental results. Interfacial reactions in the Sn-In-(Ag)/Ag couples have been examined. Both Ag 2 In and AgIn 2 phases are formed in the Sn-51.0 wt%In/Ag couples reacted at 100 and 150 deg. C, and only the Ag 2 In phase is formed when reacted at 25, 50 and 75 deg. C. Due to the different growth rates of different reaction phases, the reaction layer at 100 deg. C is thinner than those at 25 deg. C, 50 deg. C, and 75 deg. C. In the Sn-20.0 wt%In/Ag couples, the ζ phase is formed at 250 deg. C and ζ/AgIn 2 phases are formed at 125 deg. C. Compared with the Sn-20 wt%In/Ag couples, faster interfacial reactions are observed in the Sn-20.0 wt%In-2.8 wt%Ag/Ag couples, and minor Ag addition to Sn-20 wt%In solder increases the growth rates of the reaction phases.

  3. The effect of composition of mixture on rate of radiation initiation of chain reactions

    International Nuclear Information System (INIS)

    Poluehktov, V.A.; Begishev, I.R.; Podkhalyuzin, A.T.; Babkina, Eh.I.; Morozov, V.A.; Shapovalov, V.V.

    1977-01-01

    The effect of the composition of starting components on the rate of a number of chain liquid-phase reactions initiated by γ-quanta of Co 60 has been investigated at constant temperature and dosage rate. In regard to 1,1-difluoroethane chlorination, cyclohexene phosphorylation and adamantane alkylation with hexafluoropropylene reactions, abnormal effect of the reagent compositions on reaction rates has been discovered. The possible radical - starting molecule complexing reaction and molecular complexing from the starting components have been considered

  4. Microcanonical rates, gap times, and phase space dividing surfaces

    NARCIS (Netherlands)

    Ezra, Gregory S.; Waalkens, Holger; Wiggins, Stephen

    2009-01-01

    The general approach to classical unimolecular reaction rates due to Thiele is revisited in light of recent advances in the phase space formulation of transition state theory for multidimensional systems. Key concepts, such as the phase space dividing surface separating reactants from products, the

  5. Charged-particle thermonuclear reaction rates: II. Tables and graphs of reaction rates and probability density functions

    International Nuclear Information System (INIS)

    Iliadis, C.; Longland, R.; Champagne, A.E.; Coc, A.; Fitzgerald, R.

    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 issue (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 μ and σ 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 issue (Paper III). In the fourth paper of this issue (Paper IV) we compare our new reaction rates to previous results.

  6. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed

    2014-01-01

    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

  7. Dynamic phase transition in diffusion-limited reactions

    International Nuclear Information System (INIS)

    Tauber, U.C.

    2002-01-01

    Many non-equilibrium systems display dynamic phase transitions from active to absorbing states, where fluctuations cease entirely. Based on a field theory representation of the master equation, the critical behavior can be analyzed by means of the renormalization group. The resulting universality classes for single-species systems are reviewed here. Generically, the critical exponents are those of directed percolation (Reggeon field theory), with critical dimension d c = 4. Yet local particle number parity conservation in even-offspring branching and annihilating random walks implies an inactive phase (emerging below d c = 4/3) that is characterized by the power laws of the pair annihilation reaction, and leads to different critical exponents at the transition. For local processes without memory, the pair contact process with diffusion represents the only other non-trivial universality class. The consistent treatment of restricted site occupations and quenched random reaction rates are important open issues (Author)

  8. What Is a Reaction Rate?

    Science.gov (United States)

    Schmitz, Guy

    2005-01-01

    The definition of reaction rate is derived and demonstrations are made for the care to be taken while using the term. Reaction rate can be in terms of a reaction property, the extent of reaction and thus it is possible to give a definition applicable in open and closed systems.

  9. Neutrino-nucleus reaction rates based on the relativistic quasiparticle random phase approximation

    International Nuclear Information System (INIS)

    Paar, N.; Vretenar, D.; Marketin, T.; Ring, P.

    2008-01-01

    Neutrino-nucleus cross sections are described in a novel theoretical framework where the weak interaction of leptons with hadrons is expressed in the standard current-current form, the nuclear ground state is described in the relativistic Hartree-Bogoliubov model, and the relevant transitions to excited states are calculated in the relativistic quasiparticle random phase approximation. The model is employed in studies of neutrino-nucleus reactions in several test cases

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

    Science.gov (United States)

    Motagamwala, Ali Hussain; Dumesic, James A.

    2016-01-01

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

  11. A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

    Science.gov (United States)

    Shaw, Jacob T.; Lidster, Richard T.; Cryer, Danny R.; Ramirez, Noelia; Whiting, Fiona C.; Boustead, Graham A.; Whalley, Lisa K.; Ingham, Trevor; Rickard, Andrew R.; Dunmore, Rachel E.; Heard, Dwayne E.; Lewis, Ally C.; Carpenter, Lucy J.; Hamilton, Jacqui F.; Dillon, Terry J.

    2018-03-01

    Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k = 5.7 (±0.3) × 10-11 cm3 molecule-1 s-1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T = 323 (±10) K.

  12. A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

    Directory of Open Access Journals (Sweden)

    J. T. Shaw

    2018-03-01

    Full Text Available Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k =  5.7 (±0.3  ×  10−11 cm3 molecule−1 s−1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10 K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T =  323 (±10 K.

  13. Applications of Reaction Rate

    Science.gov (United States)

    Cunningham, Kevin

    2007-01-01

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

  14. Effect of alteration phase formation on the glass dissolution rate

    International Nuclear Information System (INIS)

    Ebert, W.L.

    1997-01-01

    The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests

  15. Effect of alteration phase formation on the glass dissolution rate

    Energy Technology Data Exchange (ETDEWEB)

    Ebert, W L [Argonne National Laboratory, Chemical Technology Div. (United States)

    1997-07-01

    The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests.

  16. Reaction rate of propene pyrolysis.

    Science.gov (United States)

    Han, Peipei; Su, Kehe; Liu, Yan; Wang, Yanli; Wang, Xin; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

    2011-10-01

    The reaction rate of propene pyrolysis was investigated based on the elementary reactions proposed in Qu et al., J Comput Chem 2009, 31, 1421. The overall reaction rate was developed with the steady-state approximation and the rate constants of the elementary reactions were determined with the variational transition state theory. For the elementary reaction having transition state, the vibrational frequencies of the selected points along the minimum energy path were calculated with density functional theory at B3PW91/6-311G(d,p) level and the energies were improved with the accurate model chemistry method G3(MP2). For the elementary reaction without transition state, the frequencies were calculated with CASSCF/6-311G(d,p) and the energies were refined with the multireference configuration interaction method MRCISD/6-311G(d,p). The rate constants were evaluated within 200-2000 K and the fitted three-parameter expressions were obtained. The results are consistent with those in the literatures in most cases. For the overall rate, it was found that the logarithm of the rate and the reciprocal temperature have excellent linear relationship above 400 K, predicting that the rate follows a typical first-order law at high temperatures of 800-2000 K, which is also consistent with the experiments. The apparent activation energy in 800-2000 K is 317.3 kJ/mol from the potential energy surface of zero Kelvin. This value is comparable with the energy barriers, 365.4 and 403.7 kJ/mol, of the rate control steps. However, the apparent activation energy, 215.7 kJ/mol, developed with the Gibbs free energy surface at 1200 K is consistent with the most recent experimental result 201.9 ± 0.6 kJ/mol. Copyright © 2011 Wiley Periodicals, Inc.

  17. Reactions homogenes en phase gazeuse dans les lits fluidises

    Science.gov (United States)

    Laviolette, Jean-Philippe

    This thesis presents a study on homogeneous gas-phase reactions in fluidized beds. The main objective is to develop new tools to model and characterize homogeneous gas-phase reactions in this type of reactor. In the first part of this work, the non-premixed combustion of C 1 to C4 n-alkanes with air was investigated inside a bubbling fluidized bed of inert sand particles at intermediate temperatures: 923 K ≤ TB ≤ 1123 K. For ethane, propane and n-butane, combustion occurred mainly in the freeboard region at bed temperatures below T1 = 923 K. On the other hand, complete conversion occurred within 0.2 m of the injector at: T2 = 1073 K. For methane, the measured values of T1 and T2 were significantly higher at 1023 K and above 1123 K, respectively. The fluidized bed combustion was accurately modeled with first-order global kinetics and two one-phase PFR models in series: one PFR to model the region close to the injector and another to represent the main fluidized bed body. The measured global reaction rates for C2 to C4 n-alkanes were characterized by a uniform Arrhenius expression, while the global reaction rate for methane was significantly slower. Reactions in the injector region either led to significant conversion in that zone or an autoignition delay inside the main fluidized bed body. The conversion in the injector region increased with rising fluidized bed temperature and decreased with increasing jet velocity. To account for the promoting and inhibiting effects, an analogy was made with the concept of induction time: the PFR length (bi) of the injector region was correlated to the fluidized bed temperature and jet velocity using an Arrhenius expression. In the second part of this work, propane combustion experiments were conducted in the freeboard of a fluidized bed of sand particles at temperatures between 818 K and 923 K and at superficial gas velocity twice the minimum fluidization velocity. The freeboard region was characterized by simultaneous

  18. Temperature effects on lithium-nitrogen reaction rates

    International Nuclear Information System (INIS)

    Ijams, W.J.; Kazimi, M.S.

    1985-08-01

    A series of experiments have been run with the aim of measuring the reaction rate of lithium and nitrogen over a wide spectrum of lithium pool temperatures. In these experiments, pure nitrogen was blown at a controlled flow rate over a preheated lithium pool. The pool had a surface area of approximately 4 cm 2 and a total volume of approximately 6 cm 3 . The system pressure varied from 0 to 4 psig. The reaction rate was very small - approximately 0.002 to 0.003 g Li min cm 2 for lithium temperatures below 500 0 C. Above 500 0 C the reaction rate began to increase sharply, and reached a maximum of approximately 0.80 g Li min cm 2 above 700 0 C. It dropped off beyond 1000 0 C and seemed to approach zero at 1150 0 C. The maximum reaction rate observed in these forced convection experiments was higher by 60% than those previously observed in experiments where the nitrogen flowed to the reaction site by means of natural convection. During a reaction, a hard nitride layer built up on the surface of the lithium pool - its effect on the reaction rate was observed. The effect of the nitrogen flow rate on the reaction rate was also observed

  19. Kinetic aspects of the embedded clusters: Reaction - Rate Theory

    International Nuclear Information System (INIS)

    Despa, F.; Apostol, M.

    1995-07-01

    The main stages of the cluster growth process are reviewed using Reaction - Rate Theory. The precipitation stage is shown as a relaxation of the solute towards a cluster state characterized by a higher stability. The kinetic of the late stage of phase separation, the coarsening process, is analyzed by an off-centre diffusion mechanism. The theoretical results are compared to the experimental ones. (author). 37 refs, 6 figs

  20. Measurement of inertial confinement fusion reaction rate

    International Nuclear Information System (INIS)

    Peng Xiaoshi; Wang Feng; Tang Daorun; Liu Shenye; Huang Tianxuan; Liu Yonggang; Xu Tao; Chen Ming; Mei Yu

    2011-01-01

    Fusion reaction rate is an important parameter for measuring compression during the implosion in inertial confinement fusion experiment. We have developed a system for fusion reaction history measurement with high temporal resolution. The system is composed of plastic scintillator and nose cone, optical system and streak camera. We have applied this system on the SG-III prototype for fusion reaction rate measuring. For the first time, fusion reaction rate history have been measured for deuterium-tritium filled targets with neutrons yields about 10 10 . We have analyzed possible influence factor during fusion reaction rate measuring. It indicates that the instrument measures fusion reaction bang time at temporal resolutions as low as 30 ps.(authors)

  1. Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

    NARCIS (Netherlands)

    Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

    2001-01-01

    Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

  2. Representing Rate Equations for Enzyme-Catalyzed Reactions

    Science.gov (United States)

    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…

  3. Cross-section and reaction rates for some reactions involved in explosive nucleosynthesis

    International Nuclear Information System (INIS)

    Cheng, C.W.

    1979-03-01

    Total proton-induced and alpha-induced reaction cross sections have been determined for the 24 Mg(α,n), 25 Mg(p,n), 26 Mg(p,n), 27 Al(p,n), 28 Si(α,n), 42 Ca(p,γ), 42 Ca(α,n) and 44 Ca(p,n) reactions from energies near threshold (except the exothermic (p,γ) reaction) to about 3 to 4 MeV above threshold. The product nuclei are all positron emitters with half-lives ranging from about 3 sec to about 4 hours. From the measured cross sections reaction rates have been calculated in the temperature range 1 9 9 =1, at which the discrepancy is large. Included also are analytic forms for (p,n), (α,n), and (p,γ) reactions which can be used to describe the reaction rate within the temperature range 1 9 <=6 and which agree with the experimental rates at the discrete temperatures where the reaction rates have been calculated

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

    Science.gov (United States)

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

    2014-06-01

    Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Liquid and Gas Phase Chemistry of Hypergolic Reactions between MMH and NTO or RFNA

    Science.gov (United States)

    Black, Ariel

    Hypergolic systems rely on fuel and oxidizer propellant combinations that spontaneously ignite upon contact. Monomethylhydrazine (MMH) fuel and nitrogen tetroxide (NTO) - based oxidizers embody the state of the art for hypergolic propellants, although the health and safety hazards associated with these propellants demand investigation into less-toxic, high performance alternatives. In order to replicate the combustion characteristics of these highly reactive propellants, a detailed understanding of the full reaction process is necessary. Current reaction mechanisms and hypergolic ignition models generally assume that gas-phase chemistry dominates the interaction since the liquid-phase reactions occur on the order of microseconds. However, condensed-phase reactions produce intermediates integral to gas-phase initiation and development. Additional insight into the physical and chemical processes that dictate this liquid-phase chemistry is therefore essential. Concurrently, further examination of the gas-phase reactions leading to and immediately following ignition is also needed. A method devoted to the determination of the liquid phase hypergolic reaction mechanism and kinematic rate parameters for MMH-NTO and MMH-red fuming nitric acid (RFNA) is presented in this study. MMH-RFNA reaction chemistry is better understood and documented in literature than MMH-NTO and is examined for comparison and validation. Drop on pool experiments at a range of temperatures were initially undertaken using MMH and RFNA and then modified to accommodate the high vapor pressure of NTO. Using a temperature and atmosphere controlled droplet contact chamber, the liquid phases of MMH-RFNA and MMH-NTO were studied by capturing impacts at frame rates from 100,000 to 500,000 fps. This footage allowed for the identification of time delays between droplet contact and initial gas formation, enabling calibration of the Arrhenius pre-exponential factors and activation energies for a global, one

  6. Rates of Thermonuclear Reactions in Dense Plasmas

    International Nuclear Information System (INIS)

    Tsytovich, V.N.; Bornatici, M.

    2000-01-01

    The problem of plasma screening of thermonuclear reactions has attracted considerable scientific interest ever since Salpeter's seminal paper, but it is still faced with controversial statements and without any definite conclusion. It is of relevant importance to thermonuclear reactions in dense astrophysical plasmas, for which charge screening can substantially affect the reaction rates. Whereas Salpeter and a number of subsequent investigations have dealt with static screening, Carraro, Schafer, and Koonin have drawn attention to the fact that plasma screening of thermonuclear reactions is an essentially dynamic effect. In addressing the issue of collective plasma effects on the thermonuclear reaction rates, the first critical overview of most of the work carried out so far is presented and the validity of the test particle approach is assessed. In contrast to previous investigations, we base our description on the kinetic equation for nonequilibrium plasmas, which accounts for the effects on the rates of thermonuclear reactions of both plasma fluctuations and screening and allows one to analyze explicitly the effects of the fluctuations on the reaction rates. Such a kinetic formulation is more general than both Salpeter's approach and the recently developed statistical approaches and makes it possible to obtain a more comprehensive understanding of the problem. A noticeable result of the fluctuation approach is that the static screening, which affects both the interaction and the self-energy of the reacting nuclei, does not affect the reaction rates, in contrast with the results obtained so far. Instead, a reduction of the thermonuclear reaction rates is obtained as a result of the effect of plasma fluctuations related to the free self-energy of the reacting nuclei. A simple physical explanation of the slowing down of the reaction rates is given, and the relation to the dynamically screened test particle approach is discussed. Corrections to the reaction rates

  7. Typewriting rate as a function of reaction time.

    Science.gov (United States)

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

    1977-12-01

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

  8. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

    DEFF Research Database (Denmark)

    Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

    2001-01-01

    The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the inc......The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase...... in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4â10......-10 mol FeS2/gâs are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate...

  9. Spent fuel reaction - the behavior of the ε-phase over 3.1 years

    International Nuclear Information System (INIS)

    Finn, P.A.; Hoh, J.C.; Wolf, S.F.

    1996-01-01

    The release fractions of the five elements in the ε-phase ( 99 Tc, 97 Mo, Ru, Rh, and Pd) as well as that of 238 U are reported for the reaction of two oxide fuels (ATM-103 and ATM-106) in unsaturated tests under oxidizing conditions. The 99 Tc release fractions provide a lower limit for the magnitude of the spent fuel reaction. The 99 Tc release fractions indicate that a surface reaction might be the rate controlling mechanism for fuel reaction under unsaturated conditions and the oxidant is possibly H 2 O 2 , a product of alpha radiolysis of water

  10. Effect of the Gouy phase on the coherent phase control of chemical reactions.

    Science.gov (United States)

    Gordon, Robert J; Barge, Vishal J

    2007-11-28

    We show how the spatial phase of a focused laser beam may be used as a tool for controlling the branching ratio of a chemical reaction. Guoy discovered [Acad. Sci., Paris, C. R. 110, 1250 (1890)] that when an electromagnetic wave passes through a focus its phase increases by pi. In a coherent control scheme involving the absorption of n photons of frequency omega(m) and m photons of frequency omega(n), the overall phase shift produced by the Gouy phase is (n-m)pi. At any given point in space, this phase shift is identical for all reaction products. Nevertheless, if the yields for different reaction channels have different intensity dependencies, the Gouy phase produces a net phase lag between the products that varies with the axial coordinate of the laser focus. We obtain here analytical and numerical values of this phase as the laser focus is scanned across the diameter of the molecular beam, taking into account the Rayleigh range and astigmatism of the laser beam and saturation of the transition. We also show that the modulation depth of the interference pattern may be increased by optimizing the relative intensities of the two fields.

  11. Coupled enzyme reactions performed in heterogeneous reaction media: experiments and modeling for glucose oxidase and horseradish peroxidase in a PEG/citrate aqueous two-phase system.

    Science.gov (United States)

    Aumiller, William M; Davis, Bradley W; Hashemian, Negar; Maranas, Costas; Armaou, Antonios; Keating, Christine D

    2014-03-06

    The intracellular environment in which biological reactions occur is crowded with macromolecules and subdivided into microenvironments that differ in both physical properties and chemical composition. The work described here combines experimental and computational model systems to help understand the consequences of this heterogeneous reaction media on the outcome of coupled enzyme reactions. Our experimental model system for solution heterogeneity is a biphasic polyethylene glycol (PEG)/sodium citrate aqueous mixture that provides coexisting PEG-rich and citrate-rich phases. Reaction kinetics for the coupled enzyme reaction between glucose oxidase (GOX) and horseradish peroxidase (HRP) were measured in the PEG/citrate aqueous two-phase system (ATPS). Enzyme kinetics differed between the two phases, particularly for the HRP. Both enzymes, as well as the substrates glucose and H2O2, partitioned to the citrate-rich phase; however, the Amplex Red substrate necessary to complete the sequential reaction partitioned strongly to the PEG-rich phase. Reactions in ATPS were quantitatively described by a mathematical model that incorporated measured partitioning and kinetic parameters. The model was then extended to new reaction conditions, i.e., higher enzyme concentration. Both experimental and computational results suggest mass transfer across the interface is vital to maintain the observed rate of product formation, which may be a means of metabolic regulation in vivo. Although outcomes for a specific system will depend on the particulars of the enzyme reactions and the microenvironments, this work demonstrates how coupled enzymatic reactions in complex, heterogeneous media can be understood in terms of a mathematical model.

  12. Effect of excited states on thermonuclear reaction rates

    International Nuclear Information System (INIS)

    Sargood, D.G.

    1983-01-01

    Values of the ratio of the thermonuclear reaction rate of a reaction, with target nuclei in a thermal distribution of energy states, to the reaction rate with all target nuclei in their ground states are tabulated for neutron, proton and α-particle induced reactions on the naturally occurring nuclei from 20 Ne to 70 Zn, at temperatures of 1, 2, 3.5 and 5x10 9 K. The ratios are determined from reaction rates based on statistical model cross sections

  13. A Kinetic Study of the Gas-Phase Reaction of OH with Br2

    Science.gov (United States)

    Bryukov, Mikhail G.; Dellinger, Barry; Knyazev, Vadim D.

    2011-01-01

    An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297 – 766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A non-linear least-squares fit with two floating parameters of the temperature dependent k1(T) data set using an equation of the form k1(T) = ATn yields the recommended expression k1(T) = 1.85×10−9T − 0.66 cm3 molecule−1 s−1 for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated using quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH···Br2 complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled using the RRKM method on the basis of the calculated PES. PMID:16854030

  14. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Failor, R.A.

    1989-01-01

    Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

  15. Non-equilibrium reaction rates in chemical kinetic equations

    Science.gov (United States)

    Gorbachev, Yuriy

    2018-05-01

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

  16. Effect of nuclear reaction rates on primordial abundances

    International Nuclear Information System (INIS)

    Mishra, Abhishek; Basu, D.N.

    2011-01-01

    The theoretical predictions of the primordial abundances of elements in the big-bang nucleosynthesis (BBN) are dominated by uncertainties in the input nuclear reaction rates. The effect of modifying these reaction rates on light element abundance yields in BBN by replacing the thirty-five reaction rates out of the existing eighty-eight has been investigated. Also the study have been taken of these yields as functions of evolution time or temperature. Here it has been found that using these new reaction rates results in only a little increase in helium mass fraction over that obtained previously in BBN calculations. This allows insights into the role of the nuclear reaction rates in the setting of the neutron-to-proton ratio during the BBN epoch. We observe that most of these nuclear reactions have minimal effect on the standard BBN abundance yields of 6 Li and 7 Li

  17. Gas-phase reaction rate constants for atmospheric pressure ionization in ion-mobility spectrometry

    International Nuclear Information System (INIS)

    Vandiver, V.J.

    1987-01-01

    Ion-mobility spectrometry (IMS) is an instrumental technique in which gaseous ions are formed from neutral molecules by proton and charge transfer from reactant ions through collisional ionization. An abbreviated rate theory has been proposed for atmospheric pressure ionization (API) in IMS, but supporting experimental measurements have not been reported. The objectives of this thesis were (1) assessment of existing API rate theory using positive and negative product ions in IMS, (2) measurement of API equilibria and kinetics for binary mixtures, and (3) investigating of cross-ionizations with multiple-product ions in API reactions. Although IMS measurements and predictions from rate theory were comparable, shapes and slopes of response curves for both proton transfer and electron capture were not described exactly by existing theory. In particular, terms that are needed for calculation of absolute rate constants were unsuitable in the existing theory. These included recombination coefficients,initial number of reactant ions, and opposing ion densities

  18. Reactions between Ti3Al-Nb and mixed second phases

    International Nuclear Information System (INIS)

    Bowden, D.M.; Sastry, S.M.L.; Smith, P.R.

    1989-01-01

    In engineered multiphase materials, the interfacial characteristics that develop between individual phases during high-temperature exposure can play a significant role in determining mechanical behavior. In titanium alloys containing silicon carbide and boron fibers, rule-of-mixtures strength values are not realized, primarily because of the chemical reactions that occur between the matrix alloys and these phases. Previous investigations of the reaction between titanium alloys and boron have shown that a uniform reaction layer of the phase TiB 2 is formed, followed by growth of TiB needles. The primary mechanism of this reaction was observed to be the one-way diffusion of boron into titanium. The use of a B 4 C coating on the boron (B 4 C/B) as a diffusion barrier was found to significantly slow the reaction between the titanium and boron. Certain alloy additions to titanium, such as aluminum, vanadium, and molybdenum, can increase the chemical compatibility of these two phases. For the case of SiC, the reaction zone is formed by the interdiffusion of silicon and carbon atoms with titanium. X-ray diffraction studies have shown the reaction components to include TiC, Ti 5 Si 3 , and TiSi 2 . In the present study, the reactions between a Ti 3 Al alloy and both B 4 C/B and SiC have been examined. Reaction models are proposed to describe the development of the chemical interaction zone formed between these phases

  19. Monotectic four-phase reaction in Al-Bi-Zn alloys

    Energy Technology Data Exchange (ETDEWEB)

    Groebner, J. [Clausthal University of Technology, Institute of Metallurgy, Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld (Germany); Mirkovic, D. [Clausthal University of Technology, Institute of Metallurgy, Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld (Germany); Schmid-Fetzer, R. [Clausthal University of Technology, Institute of Metallurgy, Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld (Germany)]. E-mail: schmid-fetzer@tu-clausthal.de

    2005-06-15

    Thermodynamic phase diagram calculations were used for the systematic search for a monotectic four-phase reaction in ternary Al-alloys. Systems with intermetallic phases and also the elements Cd and Hg were excluded in the present search. The ternary Al-Bi-Zn is a rare occasion where such a reaction, L' = L' + (Al)' + (Zn), actually occurs. Experimental work could be focused on key samples in that system and involved DSC for thermal analysis and calorimetry, and also metallographic analysis using SEM/EDX. Experimental results verify the existence of the monotectic reaction and were also used for a quantitative thermodynamic modeling of Al-Bi-Zn. Solidification paths and microstructures of Al-Bi-Zn alloys are shown to be rather complex. Using thermodynamic calculations, these rich details involving up to three invariant reactions and unexpected monovariant reaction types can be clearly revealed and understood.

  20. Thermonuclear reaction rates in a deuterium-tritium plasma

    International Nuclear Information System (INIS)

    Beckman, L.

    1978-12-01

    In a deuterium-tritium plasma six thermonuclear reactions take place between the deuterons, tritons and the 3 He-particles formed in about half of the d-d-reactions. The rate constants for these six reactions have been calculated from the latest evaluations of the reaction cross sections which were available. In some cases, notably the reactions t+t, t+ 3 He and 3 He+ 3 He, the number of published cross section measurements is small, and the uncertainty in the calculated rate constants consequently large. Analytical expressions for the rate constants as functions of the plasma temperature have been set up. (author)

  1. Efficient Computation of Transition State Resonances and Reaction Rates from a Quantum Normal Form

    NARCIS (Netherlands)

    Schubert, Roman; Waalkens, Holger; Wiggins, Stephen

    2006-01-01

    A quantum version of a recent formulation of transition state theory in phase space is presented. The theory developed provides an algorithm to compute quantum reaction rates and the associated Gamov-Siegert resonances with very high accuracy. The algorithm is especially efficient for

  2. Global minimum profile error (GMPE) - a least-squares-based approach for extracting macroscopic rate coefficients for complex gas-phase chemical reactions.

    Science.gov (United States)

    Duong, Minh V; Nguyen, Hieu T; Mai, Tam V-T; Huynh, Lam K

    2018-01-03

    Master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) has shown to be a powerful framework for modeling kinetic and dynamic behaviors of a complex gas-phase chemical system on a complicated multiple-species and multiple-channel potential energy surface (PES) for a wide range of temperatures and pressures. Derived from the ME time-resolved species profiles, the macroscopic or phenomenological rate coefficients are essential for many reaction engineering applications including those in combustion and atmospheric chemistry. Therefore, in this study, a least-squares-based approach named Global Minimum Profile Error (GMPE) was proposed and implemented in the MultiSpecies-MultiChannel (MSMC) code (Int. J. Chem. Kinet., 2015, 47, 564) to extract macroscopic rate coefficients for such a complicated system. The capability and limitations of the new approach were discussed in several well-defined test cases.

  3. Application of microwave irradiation to organic liquid phase reactions

    International Nuclear Information System (INIS)

    Huang Kun; Liu Hua; Ji Xuelin

    1994-01-01

    Microwave irradiation has been used in organic liquid phase reactions to significantly reduce the reaction time and improve the yield. The proposed mechanism, the development of techniques and reactions, such as Diels-Alder, ene, rearrangement reactions etc., are discussed

  4. Improved predictions of nuclear reaction rates with the TALYS reaction code for astrophysical applications

    International Nuclear Information System (INIS)

    Goriely, S.; Hilaire, S.; Koning, A.J

    2008-01-01

    Context. Nuclear reaction rates of astrophysical applications are traditionally determined on the basis of Hauser-Feshbach reaction codes. These codes adopt a number of approximations that have never been tested, such as a simplified width fluctuation correction, the neglect of delayed or multiple-particle emission during the electromagnetic decay cascade, or the absence of the pre-equilibrium contribution at increasing incident energies. Aims. The reaction code TALYS has been recently updated to estimate the Maxwellian-averaged reaction rates that are of astrophysical relevance. These new developments enable the reaction rates to be calculated with increased accuracy and reliability and the approximations of previous codes to be investigated. Methods. The TALYS predictions for the thermonuclear rates of relevance to astrophysics are detailed and compared with those derived by widely-used codes for the same nuclear ingredients. Results. It is shown that TALYS predictions may differ significantly from those of previous codes, in particular for nuclei for which no or little nuclear data is available. The pre-equilibrium process is shown to influence the astrophysics rates of exotic neutron-rich nuclei significantly. For the first time, the Maxwellian- averaged (n, 2n) reaction rate is calculated for all nuclei and its competition with the radiative capture rate is discussed. Conclusions. The TALYS code provides a new tool to estimate all nuclear reaction rates of relevance to astrophysics with improved accuracy and reliability. (authors)

  5. Estimation of the rate of volcanism on Venus from reaction rate measurements

    Science.gov (United States)

    Fegley, Bruce, Jr.; Prinn, Ronald G.

    1989-01-01

    Laboratory rate data for the reaction between SO2 and calcite to form anhydrite are presented. If this reaction rate represents the SO2 reaction rate on Venus, then all SO2 in the Venusian atmosphere will disappear in 1.9 Myr unless volcanism replenishes the lost SO2. The required volcanism rate, which depends on the sulfur content of the erupted material, is in the range 0.4-11 cu km of magma erupted per year. The Venus surface composition at the Venera 13, 14, and Vega 2 landing sites implies a volcanism rate of about 1 cu km/yr. This geochemically estimated rate can be used to determine if either (or neither) of two discordant geophysically estimated rates is correct. It also suggests that Venus may be less volcanically active than the earth.

  6. Nickel group cluster anion reactions with carbon monoxide: Rate coefficients and chemisorption efficiency

    Science.gov (United States)

    Hintz, Paul A.; Ervin, Kent M.

    1994-04-01

    Reactions of Ni-n(n=3-10), Pd-n(n=3-8), and Pt-n(n=3-7) with CO are studied in a flow tube reactor. Bimolecular rate coefficients are measured for the association reaction of CO adsorbing on the cluster surface. The rate coefficients range from about 10% of the collision rate for the trimer anions to near the collision rate for clusters larger than four atoms. The maximum number of CO molecules that bind to each cluster is determined. Whereas the saturation limits for nickel are typical for an 18 electron transition metal, the limits for platinum are lower, reflecting the electron deficient structures observed in condensed phase chemistry. The CO saturated palladium clusters represent the first examples of saturated binary palladium carbonyl compounds. Comparisons are made to similar studies on metal cation and neutral clusters and also to surface scattering studies of nickel group metals.

  7. Phase Equilibria of the Sn-Ni-Si Ternary System and Interfacial Reactions in Sn-(Cu)/Ni-Si Couples

    Science.gov (United States)

    Fang, Gu; Chen, Chih-chi

    2015-07-01

    Interfacial reactions in Sn/Ni-4.5 wt.%Si and Sn-Cu/Ni-4.5 wt.%Si couples at 250°C, and Sn-Ni-Si ternary phase equilibria at 250°C were investigated in this study. Ni-Si alloys, which are nonmagnetic, can be regarded as a diffusion barrier layer material in flip chip packaging. Solder/Ni-4.5 wt.%Si interfacial reactions are crucial to the reliability of soldered joints. Phase equilibria information is essential for development of solder/Ni-Si materials. No ternary compound is present in the Sn-Ni-Si ternary system at 250°C. Extended solubility of Si in the phases Ni3Sn2 and Ni3Sn is 3.8 and 6.1 at.%, respectively. As more Si dissolves in these phases their lattice constants decrease. No noticeable ternary solubility is observed for the other intermetallics. Interfacial reactions in solder/Ni-4.5 wt.%Si are similar to those for solder/Ni. Si does not alter the reaction phases. No Si solubility in the reaction phases was detected, although rates of growth of the reaction phases were reduced. Because the alloy Ni-4.5 wt.%Si reacts more slowly with solders than pure Ni, the Ni-4.5 wt.%Si alloy could be a potential new diffusion barrier layer material for flip chip packaging.

  8. Charged-particle thermonuclear reaction rates: IV. Comparison to previous work

    International Nuclear Information System (INIS)

    Iliadis, C.; Longland, R.; Champagne, A.E.; Coc, A.

    2010-01-01

    We compare our Monte Carlo reaction rates (see Paper II of this issue) 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 issue), and (ii) newly available nuclear physics information (see Paper III of this issue).

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

    Science.gov (United States)

    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.

  10. MEMS Lubrication by In-Situ Tribochemical Reactions From the Vapor Phase.

    Energy Technology Data Exchange (ETDEWEB)

    Dugger, Michael Thomas; Asay, David B.; Kim, Seong H.

    2008-01-01

    Vapor Phase Lubrication (VPL) of silicon surfaces with pentanol has been demonstrated. Two potential show stoppers with respect to application of this approach to real MEMS devices have been investigated. Water vapor was found to reduce the effectiveness of VPL with alcohol for a given alcohol concentration, but the basic reaction mechanism observed in water-free environments is still active, and devices operated much longer in mixed alcohol and water vapor environments than with chemisorbed monolayer lubricants alone. Complex MEMS gear trains were successfully lubricated with alcohol vapors, resulting in a factor of 104 improvement in operating life without failure. Complex devices could be made to fail if operated at much higher frequencies than previously used, and there is some evidence that the observed failure is due to accumulation of reaction products at deeply buried interfaces. However, if hypothetical reaction mechanisms involving heated surfaces are valid, then the failures observed at high frequency may not be relevant to operation at normal frequencies. Therefore, this work demonstrates that VPL is a viable approach for complex MEMS devices in conventional packages. Further study of the VPL reaction mechanisms are recommended so that the vapor composition may be optimized for low friction and for different substrate materials with potential application to conventionally fabricated, metal alloy parts in weapons systems. Reaction kinetics should be studied to define effective lubrication regimes as a function of the partial pressure of the vapor phase constituent, interfacial shear rate, substrate composition, and temperature.

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

    Science.gov (United States)

    Woon, D. E.; Herbst, E.

    1997-01-01

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

  12. The Pictet-Spengler reaction in solid-phase combinatorial chemistry

    DEFF Research Database (Denmark)

    Nielsen, Thomas E; Diness, Frederik; Meldal, Morten

    2003-01-01

    The Pictet-Spengler reaction is an important reaction for the generation of tetrahydro-beta-carbolines and tetrahydroisoquinoline ring systems, which exhibit a range of biological and pharmacological properties. This review covers the solid-phase Pictet-Spengler reaction, as employed in solid...

  13. Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K.

    Science.gov (United States)

    Richters, Stefanie; Herrmann, Hartmut; Berndt, Torsten

    2015-05-07

    The rate coefficients of the reaction of ozone with the four atmospherically relevant sesquiterpenes β-caryophyllene, α-humulene, α-cedrene and isolongifolene were investigated at 295 ± 2 K and atmospheric pressure by at least two independent experimental investigations for each reaction. Relative rate experiments were carried out in a flow tube using two different experimental approaches with GC-MS detection (RR 1) and PTR-MS analysis (RR 2) as the analytical techniques. Absolute rate coefficients were determined in a stopped-flow experiment following the ozone depletion by means of UV spectroscopy. The average rate coefficients from the combined investigations representing the mean values of the different experimental methods are (unit: cm(3) molecule(-1) s(-1)): k(O3+β-caryophyllene) = (1.1 ± 0.3) × 10(-14) (methods: RR 1, RR 2, absolute), k(O3+α-humulene) = (1.2 ± 0.3) × 10(-14) (RR 1, RR 2), k(O3+α-cedrene) = (1.7 ± 0.5) × 10(-16) (RR 2, absolute) and k(O3+isolongifolene) = (1.1 ± 0.5) × 10(-17) (RR 2, absolute). The high ozonolysis rate coefficients for β-caryophyllene and α-humulene agree well with the results by Shu and Atkinson (Int. J. Chem. Kinet., 1994, 26) and lead to short atmospheric lifetimes of about two minutes with respect to the ozone reaction. The relatively small rate coefficients for α-cedrene and isolongifolene differ from the available literature values by a factor of about 2.5-6. Possible reasons for the deviations are discussed. Finally, calibrated sesquiterpene FT-IR spectra were recorded for the first time.

  14. APUAMA: a software tool for reaction rate calculations.

    Science.gov (United States)

    Euclides, Henrique O; P Barreto, Patricia R

    2017-06-01

    APUAMA is a free software designed to determine the reaction rate and thermodynamic properties of chemical species of a reagent system. With data from electronic structure calculations, the APUAMA determine the rate constant with tunneling correction, such as Wigner, Eckart and small curvature, and also, include the rovibrational level of diatomic molecules. The results are presented in the form of Arrhenius-Kooij form, for the reaction rate, and the thermodynamic properties are written down in the polynomial form. The word APUAMA means "fast" in Tupi-Guarani Brazilian language, then the code calculates the reaction rate on a simple and intuitive graphic interface, the form fast and practical. As program output, there are several ASCII files with tabulated information for rate constant, rovibrational levels, energy barriers and enthalpy of reaction, Arrhenius-Kooij coefficient, and also, the option to the User save all graphics in BMP format.

  15. Improved predictions of nuclear reaction rates for astrophysics applications with the TALYS reaction code

    International Nuclear Information System (INIS)

    Goriely, S.; Hilaire, S.; Koning, A.J.

    2008-01-01

    Nuclear reaction rates for astrophysics applications are traditionally determined on the basis of Hauser-Feshbach reaction codes, like MOST. These codes use simplified schemes to calculate the capture reaction cross section on a given target nucleus, not only in its ground state but also on the different thermally populated states of the stellar plasma at a given temperature. Such schemes include a number of approximations that have never been tested, such as an approximate width fluctuation correction, the neglect of delayed particle emission during the electromagnetic decay cascade or the absence of the pre-equilibrium contribution at increasing incident energies. New developments have been brought to the reaction code TALYS to estimate the Maxwellian-averaged reaction rates of astrophysics relevance. These new developments give us the possibility to calculate with an improved accuracy the reaction cross sections and the corresponding astrophysics rates. The TALYS predictions for the thermonuclear rates of astrophysics relevance are presented and compared with those obtained with the MOST code on the basis of the same nuclear ingredients for nuclear structure properties, optical model potential, nuclear level densities and γ-ray strength. It is shown that, in particular, the pre-equilibrium process significantly influences the astrophysics rates of exotic neutron-rich nuclei. The reciprocity theorem traditionally used in astrophysics to determine photo-rates is also shown no to be valid for exotic nuclei. The predictions obtained with different nuclear inputs are also analyzed to provide an estimate of the theoretical uncertainties still affecting the reaction rate prediction far away from the experimentally known regions. (authors)

  16. Photochemical reactions of triplet benzophenone and anthraquinone molecules with amines in the gas phase

    International Nuclear Information System (INIS)

    Zalesskaya, G.A.; Sambor, E.G.; Belyi, N.N.

    2004-01-01

    The intermolecular photoinduced reactions between triplet ketone molecules and aliphatic amines and pyridine are studied by the quenching of delayed fluorescence of anthraquinone and benzophenone vapors by diethylamine, dibutylamine, cyclohexylamine, triethylamine, and pyridine. In the temperature range 423-573 K, the delayed fluorescence quenching rate constants k q are estimated from changes in the decay rate constant and the intensity of delayed fluorescence upon increasing pressure of bath gases. It is ascertained that, in the gas phase, the mixtures under study exhibit both a negative and a positive dependence of k q on temperature, which indicates that some photoinduced reactions do not have activation barriers. The rate constant k q is shown to increase with decreasing ionization potential of the electron donors. This points to the importance of interactions with charge transfer in the photoreaction of triplet ketone molecules with aliphatic amines and pyridine in the gas phase. The relationship between k q and the change in the free energy ΔG upon the photoinduced intermolecular electron transfer, which is the primary stage of the photochemical reaction, is studied. It is shown that the dependence k q (ΔG) for the donor-acceptor pairs under study is described well by the Marcus equation, in which the average vibrational energies of the donor and acceptor are taken into account for the estimate of ΔG

  17. Charged particle induced thermonuclear reaction rates: a compilation for astrophysics

    International Nuclear Information System (INIS)

    Grama, C.

    1999-01-01

    We report on the results of the European network NACRE (Nuclear Astrophysics Compilation of REaction rates). The principal reason for setting up the NACRE network has been the necessity of building up a well-documented and detailed compilation of rates for charged-particle induced reactions on stable targets up to Si and on unstable nuclei of special significance in astrophysics. This work is meant to supersede the only existing compilation of reaction rates issued by Fowler and collaborators. The main goal of NACRE network was the transparency in the procedure of calculating the rates. More specifically this compilation aims at: 1. updating the experimental and theoretical data; 2. distinctly identifying the sources of the data used in rate calculation; 3. evaluating the uncertainties and errors; 4. providing numerically integrated reaction rates; 5. providing reverse reaction rates and analytical approximations of the adopted rates. The cross section data and/or resonance parameters for a total of 86 charged-particle induced reactions are given and the corresponding reaction rates are calculated and given in tabular form. Uncertainties are analyzed and realistic upper and lower bounds of the rates are determined. The compilation is concerned with the reaction rates that are large enough for the target lifetimes shorter than the age of the Universe, taken equal to 15 x 10 9 y. The reaction rates are provided for temperatures lower than T = 10 10 K. In parallel with the rate compilation a cross section data base has been created and located at the site http://pntpm.ulb.ac.be/nacre..htm. (authors)

  18. The path to improved reaction rates for astrophysics

    International Nuclear Information System (INIS)

    Rauscher, T.

    2011-01-01

    This review focuses on nuclear reactions in astrophysics and, more specifically, on reactions with light ions (nucleons and α particles) proceeding via the strong interaction. It is intended to present the basic definitions essential for studies in nuclear astrophysics, to point out the differences between nuclear reactions taking place in stars and in a terrestrial laboratory, and to illustrate some of the challenges to be faced in theoretical and experimental studies of those reactions. The discussion revolves around the relevant quantities for astrophysics, which are the astrophysical reaction rates. The sensitivity of the reaction rates to the uncertainties in the prediction of various nuclear properties is explored and some guidelines for experimentalists are also provided. (author)

  19. Identification of liquid-phase decomposition species and reactions for guanidinium azotetrazolate

    International Nuclear Information System (INIS)

    Kumbhakarna, Neeraj R.; Shah, Kaushal J.; Chowdhury, Arindrajit; Thynell, Stefan T.

    2014-01-01

    Highlights: • Guanidinium azotetrazolate (GzT) is a high-nitrogen energetic material. • FTIR spectroscopy and ToFMS spectrometry were used for species identification. • Quantum mechanics was used to identify transition states and decomposition pathways. • Important reactions in the GzT liquid-phase decomposition process were identified. • Initiation of decomposition occurs via ring opening, releasing N 2 . - Abstract: The objective of this work is to analyze the decomposition of guanidinium azotetrazolate (GzT) in the liquid phase by using a combined experimental and computational approach. The experimental part involves the use of Fourier transform infrared (FTIR) spectroscopy to acquire the spectral transmittance of the evolved gas-phase species from rapid thermolysis, as well as to acquire spectral transmittance of the condensate and residue formed from the decomposition. Time-of-flight mass spectrometry (ToFMS) is also used to acquire mass spectra of the evolved gas-phase species. Sub-milligram samples of GzT were heated at rates of about 2000 K/s to a set temperature (553–573 K) where decomposition occurred under isothermal conditions. N 2 , NH 3 , HCN, guanidine and melamine were identified as products of decomposition. The computational approach is based on using quantum mechanics for confirming the identity of the species observed in experiments and for identifying elementary chemical reactions that formed these species. In these ab initio techniques, various levels of theory and basis sets were used. Based on the calculated enthalpy and free energy values of various molecular structures, important reaction pathways were identified. Initiation of decomposition of GzT occurs via ring opening to release N 2

  20. Raman Spectral Determination of Chemical Reaction Rate Characteristics

    Science.gov (United States)

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

    2017-09-01

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

  1. Chemical changes in groundwater and their reaction rates

    International Nuclear Information System (INIS)

    Talma, A.S.

    1981-01-01

    The evolution of the major ion concentrations of groundwater (Na, K, Ca, Mg, HCO 3 , SO 4 , Cl and NO 3 ) can be described as the consequence of a number of competing chemical reactions. With the aid of the naturally occuring radioactive and stable isotopes some of these reactions can be separated, identified and followed in space and time. In some field studies, especialy of artesian water, the rates of reactions can be estimated. A number of processes observed in South African sandstones aquifers are discussed and the variable reaction rates demonstrated. Reactions that can be identified include carbonate solution, chemical weathering, salt leaching, cation exchange and redox processes

  2. Reaction Order Ambiguity in Integrated Rate Plots

    Science.gov (United States)

    Lee, Joe

    2008-01-01

    Integrated rate plots are frequently used in reaction kinetics to determine orders of reactions. It is often emphasised, when using this methodology in practice, that it is necessary to monitor the reaction to a substantial fraction of completion for these plots to yield unambiguous orders. The present article gives a theoretical and statistical…

  3. Effective dynamics along given reaction coordinates, and reaction rate theory.

    Science.gov (United States)

    Zhang, Wei; Hartmann, Carsten; Schütte, Christof

    2016-12-22

    In molecular dynamics and related fields one considers dynamical descriptions of complex systems in full (atomic) detail. In order to reduce the overwhelming complexity of realistic systems (high dimension, large timescale spread, limited computational resources) the projection of the full dynamics onto some reaction coordinates is examined in order to extract statistical information like free energies or reaction rates. In this context, the effective dynamics that is induced by the full dynamics on the reaction coordinate space has attracted considerable attention in the literature. In this article, we contribute to this discussion: we first show that if we start with an ergodic diffusion process whose invariant measure is unique then these properties are inherited by the effective dynamics. Then, we give equations for the effective dynamics, discuss whether the dominant timescales and reaction rates inferred from the effective dynamics are accurate approximations of such quantities for the full dynamics, and compare our findings to results from approaches like Mori-Zwanzig, averaging, or homogenization. Finally, by discussing the algorithmic realization of the effective dynamics, we demonstrate that recent algorithmic techniques like the "equation-free" approach and the "heterogeneous multiscale method" can be seen as special cases of our approach.

  4. Laboratory investigations of the alpha-pinene/ozone gas-phase reaction

    International Nuclear Information System (INIS)

    Benner, C.L.

    1985-01-01

    In order to provide more insight into terpene photooxidation or ozonolysis reaction mechanisms, a radiotracer technique was developed. This technique was applied to an investigation of the 14 C-alpha-pinene/ozone reaction. In the first phase of the research, the carbon distribution at the conclusion of the ozonolysis reaction was determined by separating carbon-14-labelled gaseous products from labelled aerosols, and counting each phase by liquid scintillation methods. The resulting carbon balance was 38% to 60% filtered aerosols, 6% to 20% gas phase compounds, and 11% to 29% products absorbed on the reaction chamber walls. Recoveries of the alpha-pinene carbon-14 ranging from 79% to 97% were achieved using this method. The alpha-pinene concentrations in these experiments were close to ambient (1 part per billion), yet the carbon balance was similar to that observed at much higher concentrations (>1 part per million). In the second phase of the alpha-pinene study, both gas and aerosol products of the ozonolysis reaction were collected on cartridges impregnated with 2,4-dinitrophenylhydrazine, then analyzed by HPLC. In the final experiments, alpha-pinene aerosol was reacted with a silylating agent to improve the detection of organic acids and alcohols. The gas chromatographic/mass spectrometric analysis of the silylated aerosol products showed evidence of dimer/polymer formation occurring in the ozonolysis reaction

  5. Rates for some reactions involving 42Ca and 44Ca

    International Nuclear Information System (INIS)

    Cheng, C.W.; King, J.D.

    1980-01-01

    Ground-state reaction rates have been deduced from recent cross section measurements for the 42 CA(α, n) 45 Ti, 42 Ca(p, γ) 43 Sc, and 44 Ca(p, n) 44 Sc reactions. Comparison of these rates with those calculated from a statistical model of nuclear reactions. (Woosley et al) shows good agreement for the first two, but the 44 Ca(p, n) rate is more than a factor of 2 less than the theoretical prediction. Stellar reaction rates have been derived from the ground-state rates by multiplying the ground-state rates by the ratio of stellar to ground-state rates given by the statistical model. Both ground-state and stellar rates have been represented by analytic functions of the temperature. The role of these reactions in the approach to quasi-equilibrium during explosive silicon burning is discussed

  6. Synthesis of Zr-Si-O-N phases by carbonitriding reaction. Characterization of crystalline phases using the Rietveld method

    Directory of Open Access Journals (Sweden)

    Mazzoni A.D.

    2001-01-01

    Full Text Available Zirconium compounds are of great interest for ceramic application due to their excellent thermal and mechanical properties. Zirconium phases of the system Zr-O-C-N were obtained using carbonitriding reactions of zircon mineral (ZrO2.SiO2, under different reaction conditions. The reaction products were studied by X-ray diffraction (XRD using the Rietveld method. Silicon was employed as internal standard. Zirconium compounds formed were m-ZrO2 (monoclinic, beta"-zirconium oxynitride and a cubic Zr(C,N,O phase whose lattice parameter a o depends on the composition. The crystallite sizes of the three zirconium phases were determined also by XRD. The minority phases present are the ones of the Si-O-N-C system. The reaction conditions employed allows to obtain reaction products with low or without silicon content.

  7. Simplified method of ''push-pull'' test data analysis for determining in situ reaction rate coefficients

    International Nuclear Information System (INIS)

    Haggerty, R.; Schroth, M.H.; Istok, J.D.

    1998-01-01

    The single-well, ''''push-pull'''' test method is useful for obtaining information on a wide variety of aquifer physical, chemical, and microbiological characteristics. A push-pull test consists of the pulse-type injection of a prepared test solution into a single monitoring well followed by the extraction of the test solution/ground water mixture from the same well. The test solution contains a conservative tracer and one or more reactants selected to investigate a particular process. During the extraction phase, the concentrations of tracer, reactants, and possible reaction products are measured to obtain breakthrough curves for all solutes. This paper presents a simplified method of data analysis that can be used to estimate a first-order reaction rate coefficient from these breakthrough curves. Rate coefficients are obtained by fitting a regression line to a plot of normalized concentrations versus elapsed time, requiring no knowledge of aquifer porosity, dispersivity, or hydraulic conductivity. A semi-analytical solution to the advective-dispersion equation is derived and used in a sensitivity analysis to evaluate the ability of the simplified method to estimate reaction rate coefficients in simulated push-pull tests in a homogeneous, confined aquifer with a fully-penetrating injection/extraction well and varying porosity, dispersivity, test duration, and reaction rate. A numerical flow and transport code (SUTRA) is used to evaluate the ability of the simplified method to estimate reaction rate coefficients in simulated push-pull tests in a heterogeneous, unconfined aquifer with a partially penetrating well. In all cases the simplified method provides accurate estimates of reaction rate coefficients; estimation errors ranged from 0.1 to 8.9% with most errors less than 5%

  8. An improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions

    CERN Document Server

    Kraft, M

    2003-01-01

    We propose an improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions. By combining forward and reverse reaction rates, a significant gain in computational efficiency is achieved. Two modifications of modelling the temperature dependence (with and without conservation of enthalpy) are introduced and studied quantitatively. The algorithm is tested for the combustion of n-heptane, which is a reference fuel component for internal combustion engines. The convergence of the algorithm is studied by a series of numerical experiments and the computational cost of the stochastic algorithm is compared with the DAE code DASSL. If less accuracy is needed the stochastic algorithm is faster on short simulation time intervals. The new stochastic algorithm is significantly faster than the original direct simulation algorithm in all cases considered.

  9. Restrictive liquid-phase diffusion and reaction in bidispersed catalysts

    International Nuclear Information System (INIS)

    Lee, S.Y.; Seader, J.D.; Tsai, C.H.; Massoth, F.E.

    1991-01-01

    In this paper, the effect of bidispersed pore-size distribution on liquid-phase diffusion and reaction in NiMo/Al 2 O 3 catalysts is investigated by applying two bidispersed-pore-structure models, the random-pore model and a globular-structure model, to extensive experimental data, which were obtained from sorptive diffusion measurements at ambient conditions and catalytic reaction rate measurements on nitrogen-containing compounds. Transport of the molecules in the catalysts was found to be controlled by micropore diffusion, in accordance with the random-pore model, rather than macropore diffusion as predicted by the globular-structure model. A qualitative criterion for micropore-diffusion control is proposed: relatively small macroporosity and high catalyst pellet density. Since most hydrotreating catalysts have high density, diffusion in these types of catalysts may be controlled by micropore diffusion. Accordingly, it is believed in this case that increasing the size of micropores may be more effective to reduce intraparticle diffusion resistance than incorporating macropores alone

  10. A numerical evaluation of prediction accuracy of CO2 absorber model for various reaction rate coefficients

    Directory of Open Access Journals (Sweden)

    Shim S.M.

    2012-01-01

    Full Text Available The performance of the CO2 absorber column using mono-ethanolamine (MEA solution as chemical solvent are predicted by a One-Dimensional (1-D rate based model in the present study. 1-D Mass and heat balance equations of vapor and liquid phase are coupled with interfacial mass transfer model and vapor-liquid equilibrium model. The two-film theory is used to estimate the mass transfer between the vapor and liquid film. Chemical reactions in MEA-CO2-H2O system are considered to predict the equilibrium pressure of CO2 in the MEA solution. The mathematical and reaction kinetics models used in this work are calculated by using in-house code. The numerical results are validated in the comparison of simulation results with experimental and simulation data given in the literature. The performance of CO2 absorber column is evaluated by the 1-D rate based model using various reaction rate coefficients suggested by various researchers. When the rate of liquid to gas mass flow rate is about 8.3, 6.6, 4.5 and 3.1, the error of CO2 loading and the CO2 removal efficiency using the reaction rate coefficients of Aboudheir et al. is within about 4.9 % and 5.2 %, respectively. Therefore, the reaction rate coefficient suggested by Aboudheir et al. among the various reaction rate coefficients used in this study is appropriate to predict the performance of CO2 absorber column using MEA solution. [Acknowledgement. This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF, funded by the Ministry of Education, Science and Technology (2011-0017220].

  11. Effects of oxygen supply condition and specific biofilm interfacial area on phenol removal rate in a three-phase fluidized bed reactor

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, A.; Meutia, A. A.; Osawa, M.; Arai, M.; Tsuneda, S. [Waseda Univ., Dept. of Chemical Engineering, Tokyo (Japan)

    2000-02-01

    A theoretical and experimental evaluation of the effects of superficial gas velocity, oxygen concentration in the gas phase, and specific biofilm interfacial area on the volumetric removal rate of phenol is described. The reaction rate was found to follow first order reaction kinetics with respect to oxygen, and zero-order reaction kinetics with respect to phenol. A semi-theoretical equation was developed which is capable of predicting the volumetric removal rate and is used to explain the overall removal rate of phenol. Biological reaction as the rate-controlling step and oxygen absorption are both explicable by this equation. 14 refs., 5 figs.

  12. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  13. Phenomenon of quantum low temperature limit of chemical reaction rates

    International Nuclear Information System (INIS)

    Gol'danskij, V.I.

    1975-01-01

    The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerisation, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerisation reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau 0 ) required to add one new link to the polymer chain of formaldehyde during its polymerisation by radiation and during postpolymerisation and to establish that below 80K the increase of tau 0 slows down and that at T approximately equal to 10-4K the time tau 0 reaches a plateau (tau 0 approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life)

  14. Phenomenon of quantum low temperature limit of chemical reaction rates

    Energy Technology Data Exchange (ETDEWEB)

    Gol' danskii, V I [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

    1975-12-01

    The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life).

  15. Reaction rate of 24Mg(p,γ)25Al

    International Nuclear Information System (INIS)

    Powell, D.C.; Iliadis, C.; Champagne, A.E.; Grossmann, C.A.; Hale, S.E.; Hansper, V.Y.; McLean, L.K.

    1999-01-01

    The proton-capture reaction on 24 Mg has been investigated in the bombarding energy range of E p =0.2-1.7 MeV. Resonance properties (strengths, branching ratios and lifetimes) of low-energy resonances have been measured. From the experimental results, accurate proton partial widths, γ-ray partial widths and total widths (Γ p , Γ γ , and Γ) have been deduced. The present experimental information establishes the 24 Mg+p reaction rates over the temperature range T=0.02-2.0 GK with statistical uncertainties of 5% to 21%. Our recommended reaction rates deviate from previous estimates by 18% to 45%. Based on our results, we can rule out the recent suggestion that the total width of the E R =223 keV resonance has a significant influence on the reaction rates. We also discuss several effects that might give rise to systematic uncertainties in the reaction rates. The astrophysical implications for hydrogen burning of 24 Mg at low stellar temperatures are presented

  16. Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

    DEFF Research Database (Denmark)

    Musko, Nikolai; Jensen, Anker Degn; Baiker, Alfons

    2012-01-01

    Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were...... cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved...... performed using a 5wt% Pd on activated carbon in custom-designed high pressure autoclaves at 323K. The Cubic-Plus-Association (CPA) equation of state was employed to model the phase behaviour of the experimentally studied systems. CPA binary interaction parameters were estimated based on the experimental...

  17. General properties of astrophysical reaction rates in explosive nucleosynthesis

    International Nuclear Information System (INIS)

    Rauscher, Thomas

    2013-01-01

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

  18. Accurate and approximate thermal rate constants for polyatomic chemical reactions

    International Nuclear Information System (INIS)

    Nyman, Gunnar

    2007-01-01

    In favourable cases it is possible to calculate thermal rate constants for polyatomic reactions to high accuracy from first principles. Here, we discuss the use of flux correlation functions combined with the multi-configurational time-dependent Hartree (MCTDH) approach to efficiently calculate cumulative reaction probabilities and thermal rate constants for polyatomic chemical reactions. Three isotopic variants of the H 2 + CH 3 → CH 4 + H reaction are used to illustrate the theory. There is good agreement with experimental results although the experimental rates generally are larger than the calculated ones, which are believed to be at least as accurate as the experimental rates. Approximations allowing evaluation of the thermal rate constant above 400 K are treated. It is also noted that for the treated reactions, transition state theory (TST) gives accurate rate constants above 500 K. TST theory also gives accurate results for kinetic isotope effects in cases where the mass of the transfered atom is unchanged. Due to neglect of tunnelling, TST however fails below 400 K if the mass of the transferred atom changes between the isotopic reactions

  19. Exchange reaction between hydrogen and deuterium. II - Proposal for an heterogeneous initiation mechanism of gaseous phase reactions

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, Chantal; Gaillard-Cusin, Francoise; James, Henri [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of experimental data related to evolution period exhibited by H/sub 2/-D/sub 2/ exchange process requires to take into account the variation against time of every atomic species -adsorbed or not- implied in the reaction mechanism. The formation of first chain carriers involves: - chemisorption of either gaseous reactant on the surface active centres (..sigma..), e.g.: ..sigma.. + 1/2 H/sub 2/ reversible ..sigma..H; - consecutive generation of atomic species through hetero-homogeneous transfer between chemisorbed species (..sigma..H) and gaseous molecules: ..sigma..H+H/sub 2/..--> sigma..+H/sub 2/+H/sup 0/, ..sigma..H+D/sub 2/..--> sigma..+HD+D/sup 0/. Therefore, it can be shown that the heterogeneous initiation process of a gas phase reaction identifies to a chain linear mechanism. Such an heterogeneous sequence conditions the further proceeding of the homogeneous chain reaction; both evolutions being kinematically connected. Rate constant of hydrogen adsorption on silica glass: ksub(a1) approximately 10/sup 14/ exp(-47/RT)Isup(0,5).molesup(-0,5).S/sup -1/ has been evaluated.

  20. Rates of the main thermonuclear reactions

    International Nuclear Information System (INIS)

    Abramovich, S.N.; Guzhovskii, B.Ya.; Dunaeva, S.A.; Fomushkin, E.F.

    1992-01-01

    The data on the cross sections of main thermonuclear reactions have been estimated with an account of the latest experimental results in a form of S-factor spline presentation. Based on this estimation, the reates of these reactions in 0.0001-1 MeV temperature range in the supposition of Maxwell distribution of relative velocities have been computed. The Maxwell-Boltzmann averaged -factors were calculated according to the table values of the reaction rates. Then the -factors were approximated with the 3 order spline-function. The necessity of the account of electron shielding and intramolecular movement at low temperatures is discussed (orig.)

  1. Probing the rate-determining region of the potential energy surface for a prototypical ion-molecule reaction.

    Science.gov (United States)

    Xie, Changjian; Liu, Xinguo; Sweeny, Brendan C; Miller, Thomas M; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A; Guo, Hua

    2018-03-13

    We report a joint experimental-theoretical study of the F -  + HCl → HF + Cl - reaction kinetics. The experimental measurement of the rate coefficient at several temperatures was made using the selected ion flow tube method. Theoretical rate coefficients are calculated using the quasi-classical trajectory method on a newly developed global potential energy surface, obtained by fitting a large number of high-level ab initio points with augmentation of long-range electrostatic terms. In addition to good agreement between experiment and theory, analyses suggest that the ion-molecule reaction rate is significantly affected by shorter-range interactions, in addition to the traditionally recognized ion-dipole and ion-induced dipole terms. Furthermore, the statistical nature of the reaction is assessed by comparing the measured and calculated HF product vibrational state distributions to that predicted by the phase space theory.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  2. Preparation of molybdenum borides by combustion synthesis involving solid-phase displacement reactions

    International Nuclear Information System (INIS)

    Yeh, C.L.; Hsu, W.S.

    2008-01-01

    Preparation of molybdenum borides of five different phases in the Mo-B binary system (including Mo 2 B, MoB, MoB 2 , Mo 2 B 5 , and MoB 4 ) was performed by self-propagating high-temperature synthesis (SHS) with two kinds of the reactant samples. When elemental powder compacts with an exact stoichiometry corresponding to the boride phase were employed, self-sustaining reaction was only achieved in the sample with Mo:B = 1:1 and nearly single-phase MoB was yielded. Therefore, the other four boride compounds were prepared from the reactant compacts composed of MoO 3 , Mo, and B powders, within which the displacement reaction of MoO 3 with boron was involved in combustion synthesis. Experimental evidence shows that the extent of displacement reaction in the overall reaction has a significant impact on sustainability of the synthesis reaction, combustion temperature, reaction front velocity, and composition of the end product. An increase in the solid-phase displacement reaction taking place during the SHS process contributes more heat flux to the synthesis reaction, thus resulting in the increase of combustion temperature and enhancement of the reaction front velocity. Based upon the XRD analysis, formation of Mo 2 B, MoB 2 , and Mo 2 B 5 as the dominant boride phase in the end product was successful through the SHS reaction with powder compacts under appropriate stoichiometries between MoO 3 , Mo, and B. However, a poor conversion was observed in the synthesis of MoB 4 . The powder compact prepared for the production of MoB 4 yielded mostly Mo 2 B 5

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

    Science.gov (United States)

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

    2012-01-14

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

  4. Rate constant for reaction of atomic hydrogen with germane

    Science.gov (United States)

    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.

  5. A review of reaction rates in high temperature air

    Science.gov (United States)

    Park, Chul

    1989-01-01

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

  6. High-precision (p,t) reactions to determine reaction rates of explosive stellar processes

    NARCIS (Netherlands)

    Matić, Andrija

    2007-01-01

    The aim of my study was to investigate the nuclear structure of 22Mg and 26Si. These two nuclei play a significant role in stellar reaction processes at high temperatures. On base of the obtained nuclear structure we calculated the stellar reaction rates for the following reactions: 18Ne(α,p)21Na,

  7. Reaction-rate formula in out of equilibrium quantum field theory

    OpenAIRE

    Niegawa, A.; Okano, K.; Ozaki, H.

    1999-01-01

    A complete derivation, from first principles, of the reaction-rate formula for a generic reaction taking place in an out of equilibrium quantum-field system is given. It is shown that the formula involves no finite-volume correction. Each term of the reaction-rate formula represents a set of physical processes that contribute to the reaction under consideration.

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

    Science.gov (United States)

    Ji, Y.; Shen, C.

    2014-03-01

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

  9. Systematic Search for Chemical Reactions in Gas Phase Contributing to Methanol Formation in Interstellar Space.

    Science.gov (United States)

    Gamez-Garcia, Victoria G; Galano, Annia

    2017-10-05

    A massive search for chemical routes leading to methanol formation in gas phase has been conducted using computational chemistry, at the CBS-QB3 level of theory. The calculations were performed at five different temperatures (100, 80, 50, 20, and 10 K) and at three pressures (0.1, 0.01, and 0.001 atm) for each temperature. The search was focused on identifying reactions with the necessary features to be viable in the interstellar medium (ISM). A searching strategy was applied to that purpose, which allowed to reduce an initial set of 678 possible reactions to a subset of 11 chemical routes that are recommended, for the first time, as potential candidates for contributing to methanol formation in the gas phase of the ISM. They are all barrier-less, and thus they are expected to take place at collision rates. Hopefully, including these reactions in the currently available models, for the gas-phase methanol formation in the ISM, would help improving the predicted fractional abundance of this molecule in dark clouds. Further investigations, especially those dealing with grain chemistry and electronic excited states, would be crucial to get a complete picture of the methanol formation in the ISM.

  10. 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.

    Science.gov (United States)

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

    2013-06-06

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

  11. Cross sections and thermonuclear reaction rates of proton-induced reactions on 37Cl

    International Nuclear Information System (INIS)

    Weber, R.O.; Tingwell, C.I.W.; Mitchell, L.W.; Sevior, M.E.; Sargood, D.G.

    1984-01-01

    The yields of γ-rays from the reactions of 37 Cl(p,γ) 38 Ar and 37 Cl(p,αγ) 34 S have been measured as a of bombarding energy over the ranges 0.65 - 2.15 MeV and 1.25 -2.15 MeV respectively, and the yield of neutrons from 37 Cl(p,n) 37 Ar from threshold to 2.50 MeV. The results are compared with global statistical-model calculations and thermonuclear reaction rates are calculated for the temperature range 5 x 10 8 - 10 10 K. The significance of these thermonuclear reaction rates for stellar nucleosynthesis calculations is discussed

  12. Charged-particle induced thermonuclear reaction rates: a compilation for astrophysics

    International Nuclear Information System (INIS)

    Grama, Cornelia; Angulo, C.; Arnould, M.

    2000-01-01

    The rapidly growing wealth of nuclear data becomes less and less easily accessible to the astrophysics community. Mastering this volume of information and making it available in an accurate and usable form for incorporation into stellar evolution or nucleosynthesis models become urgent goals of prime necessity. we report on the results of the European network NACRE (Nuclear Astrophysics Compilation of REaction rates). The principal motivation for the setting-up of the NACRE network has been the necessity of building up a well-documented and detailed compilation of rates for charged-particle induced reactions on stable targets up to Si and on unstable nuclei of special significance in astrophysics. This work is meant to supersede the only existing compilation of reaction rates issued by Fowler and collaborators. The cross section data and/or resonance parameters for a total of 86 charged-particle induced reactions are given and the corresponding reaction rates are calculated and given in tabular form. When cross section data are not available in the whole needed range of energies, the theoretical predictions obtained in the framework of the Hauser-Feshbach model is used. Uncertainties are analyzed and realistic upper and lower bounds of the rates are determined. Reverse reaction rates and analytical approximations of the adopted rates are also provided. (authors)

  13. Charged-particle induced thermonuclear reaction rates: a compilation for astrophysics

    International Nuclear Information System (INIS)

    Grama, Cornelia

    1999-01-01

    The rapidly growing wealth of nuclear data becomes less and less easily accessible to the astrophysics community. Mastering this volume of information and making it available in an accurate and usable form for incorporation into stellar evolution or nucleosynthesis models become urgent goals of prime necessity. We report on the results of the European network NACRE (Nuclear Astrophysics Compilation of REaction rates). The principal motivation for the setting-up of the NACRE network has been the necessity of building up a well-documented and detailed compilation of rates for charged -particle induced reactions on stable targets up to Si and on unstable nuclei of special significance in astrophysics. This work is meant to supersede the only existing compilation of reaction rates issued by Fowler and collaborators. The cross section data and/or resonance parameters for a total of 86 charged-particle induced reactions are given and the corresponding reaction rates are calculated and given in tabular form. When cross section data are not available in the whole needed range of energies the theoretical predictions obtained in the framework of the Hauser-Feshbach model are used. Uncertainties are analyzed and realistic upper and lower bounds of the rates are determined. Reverse reaction rates and analytical approximations of the adopted rates are also provided. (author)

  14. Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications

    Science.gov (United States)

    Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.

    2018-03-01

    An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

  15. BAYESIAN ESTIMATION OF THERMONUCLEAR REACTION RATES

    Energy Technology Data Exchange (ETDEWEB)

    Iliadis, C.; Anderson, K. S. [Department of Physics and Astronomy, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3255 (United States); Coc, A. [Centre de Sciences Nucléaires et de Sciences de la Matière (CSNSM), CNRS/IN2P3, Univ. Paris-Sud, Université Paris–Saclay, Bâtiment 104, F-91405 Orsay Campus (France); Timmes, F. X.; Starrfield, S., E-mail: iliadis@unc.edu [School of Earth and Space Exploration, Arizona State University, Tempe, AZ 85287-1504 (United States)

    2016-11-01

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

  16. The relationship between phase and heart rate

    International Nuclear Information System (INIS)

    Underwood, S.R.; Walton, S.; Brown, N.J.G.; Laming, P.J.; Ell, P.J.; Emanuel, R.W.; Swanton, R.H.

    1984-01-01

    The Fourier phase image is used in rest and stress radionuclide angiocardiography to assess the timing of ventricular wall motion in a regional fashion, and areas of high phase are taken to reprensent areas of delayed contraction. However, phase increases with heart rate and this can make interpretation difficult. This study investigates the relationship between phase and heart rate. A heterogenous group of 43 subjects was studied by ECG-gated equilibrium radionuclide angiocardiography, all of the subjects having normal extent of left ventricular wall motion as judged by normal ejection fraction and normal amplitude image. Mean left ventricular phase correlated well with mean time of end systole (r=0.92), but there was no correlation with time of end diastole.Thus phase reflects the time of end systole as a proportion of cycle length and should be linearly related to heart rate provided the duration of systole is unchanged. In 28 normal subjects mean left ventricular phase correlated linearly with resting rate (r=0.91), and when exercised the relationship was maintained up to 90 beats per minute. Above this rate the increases were less marked as the duration of systole shortened. The same was true in 4 subjects paced at different rates. Mean resting heart rate in the normal subjects was 70 beats per minute and correcting phase linearly to rate 70 did not change mean left ventricular phase but did decrease the standard deviation from 18 degree to 12 degree. It is concluded that correcting phase for heart rate below 90 beats per minute will increase the sensitivity of the phase image to abnormalities of the timing of ventricular contraction. This correction should be appropriate in resting, isometric exercise, and cold pressor studies but because of the higher heart rates involved will not be appropriate for bicycle exercise. (Author)

  17. Enhancement of D-T reaction rate due to D-T contact

    International Nuclear Information System (INIS)

    Hitoki, Shigehisa; Ogasawara, Masatada; Aono, Osamu.

    1979-09-01

    The reaction rate that is appropriate for magnetized nonuniform plasma is numerically calculated to investigate the enhancement of the D-T reaction rate. Spatial separation of the guiding center distributions of D and T enhances the reaction rate. Cases of several guiding center configurations are investigated. The largest enhancement is obtained, when both guiding center distributions are delta-functions which are separated by a length that corresponds to the Gamow peak energy. As compared with the case of no separation of D and T, the maximum enhancing factors obtained are 2.3 for total reaction rate and 1.6 for local reaction rate. Cases of the guiding center distributions with finite widths are also investigated. (author)

  18. C-terminal peptide extension via gas-phase ion/ion reactions

    Science.gov (United States)

    Peng, Zhou; McLuckey, Scott A.

    2015-01-01

    The formation of peptide bonds is of great importance from both a biological standpoint and in routine organic synthesis. Recent work from our group demonstrated the synthesis of peptides in the gas-phase via ion/ion reactions with sulfo-NHS reagents, which resulted in conjugation of individual amino acids or small peptides to the N-terminus of an existing ‘anchor’ peptide. Here, we demonstrate a complementary approach resulting in the C-terminal extension of peptides. Individual amino acids or short peptides can be prepared as reagents by incorporating gas phase-labile protecting groups to the reactive C-terminus and then converting the N-terminal amino groups to the active ketenimine reagent. Gas-phase ion/ion reactions between the anionic reagents and doubly protonated “anchor” peptide cations results in extension of the “anchor” peptide with new amide bond formation at the C-terminus. We have demonstrated that ion/ion reactions can be used as a fast, controlled, and efficient means for C-terminal peptide extension in the gas phase. PMID:26640400

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Science.gov (United States)

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

    2016-07-13

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

  1. A global model for SF6 plasmas coupling reaction kinetics in the gas phase and on the surface of the reactor walls

    International Nuclear Information System (INIS)

    Kokkoris, George; Panagiotopoulos, Apostolos; Gogolides, Evangelos; Goodyear, Andy; Cooke, Mike

    2009-01-01

    Gas phase and reactor wall-surface kinetics are coupled in a global model for SF 6 plasmas. A complete set of gas phase and surface reactions is formulated. The rate coefficients of the electron impact reactions are based on pertinent cross section data from the literature, which are integrated over a Druyvesteyn electron energy distribution function. The rate coefficients of the surface reactions are adjustable parameters and are calculated by fitting the model to experimental data from an inductively coupled plasma reactor, i.e. F atom density and pressure change after the ignition of the discharge. The model predicts that SF 6 , F, F 2 and SF 4 are the dominant neutral species while SF 5 + and F - are the dominant ions. The fit sheds light on the interaction between the gas phase and the reactor walls. A loss mechanism for SF x radicals by deposition of a fluoro-sulfur film on the reactor walls is needed to predict the experimental data. It is found that there is a net production of SF 5 , F 2 and SF 6 , and a net consumption of F, SF 3 and SF 4 on the reactor walls. Surface reactions as well as reactions between neutral species in the gas phase are found to be important sources and sinks of the neutral species.

  2. Mars Ascent Vehicle Reaction Control System, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — During this Phase I NASA program, Valley Tech Systems (VTS) will develop an innovative solid Reaction Control System (RCS) architecture concept design that can...

  3. Rate coefficients for hydrogen abstraction reaction of pinonaldehyde

    Indian Academy of Sciences (India)

    The H abstraction reaction from the –CHO group was found to be the most dominant reaction channelamong all the possible reaction pathways and its corresponding rate coefficient at 300 K is kEckart's unsymmetrical= 3.86 ×10-10 cm3 molecule-1 s-1. Whereas the channel with immediate lower activation energy is the ...

  4. Elementary steps and reaction pathways in the aqueous phase alkylation of phenol with ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Eckstein, Sebastian; Hintermeier, Peter H.; Olarte, Mariefel V.; Liu, Yue; Baráth, Eszter; Lercher, Johannes A.

    2017-08-01

    The hydronium ion normalized reaction rate in aqueous phase alkylation of phenol with ethanol on H-MFI zeolites increases with decreasing concentration of acid sites. Higher rates are caused by higher concentrations of phenol in the zeolite pores, as the concentration of hydronium ions generated by zeolite Brønsted acid sites decreases. Considering the different concentrations of reacting species it is shown that the intrinsic rate constant for alkylation is independent of the concentration of hydronium ions in the zeolite pores. Alkylation at the aromatic ring of phenol and of toluene as well as O-alkylation of phenol have the same activation energy, 104 ± 5 kJ/mol. This is energetic barrier to form the ethyl carbenium ion from ethanol associated to the hydronium ion. Thus, in both the reaction pathways the catalyst involves a carbenium ion, which forms a bond to a nucleophilic oxygen (ether formation) or carbon (alkylation).

  5. Charged-particle thermonuclear reaction rates: I. Monte Carlo method and statistical distributions

    International Nuclear Information System (INIS)

    Longland, R.; Iliadis, C.; Champagne, A.E.; Newton, J.R.; Ugalde, C.; Coc, A.; Fitzgerald, R.

    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 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 μ and σ. 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 issue (Paper II). The nuclear physics input used to derive our reaction rates is presented in the third paper of this issue (Paper III). In the fourth paper of this issue (Paper IV) we compare our new reaction rates to previous results.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Y., E-mail: yji@spaceweather.ac.cn [State Key Laboratory of Space Weather, Center for Space Science and Applied Research, Chinese Academy of Sciences, Beijing 100190 (China); College of Earth Science, University of Chinese Academy of Sciences, Beijing 100049 (China); Shen, C. [State Key Laboratory of Space Weather, Center for Space Science and Applied Research, Chinese Academy of Sciences, Beijing 100190 (China)

    2014-03-15

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

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

    Science.gov (United States)

    Liebermeister, Wolfram; Uhlendorf, Jannis; Klipp, Edda

    2010-06-15

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

  8. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  9. Astrophysical Nuclear Reaction Rates in the Dense Metallic Environments

    Science.gov (United States)

    Kilic, Ali Ihsan

    2017-09-01

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

  10. Modeling non-adiabatic photoexcited reaction dynamics in condensed phases

    International Nuclear Information System (INIS)

    Coker, D.F.

    2003-01-01

    Reactions of photoexcited molecules, ions, and radicals in condensed phase environments involve non-adiabatic dynamics over coupled electronic surfaces. We focus on how local environmental symmetries can effect non-adiabatic coupling between excited electronic states and thus influence, in a possibly controllable way, the outcome of photo-excited reactions. Semi-classical and mixed quantum-classical non-adiabatic molecular dynamics methods, together with semi-empirical excited state potentials are used to probe the dynamical mixing of electronic states in different environments from molecular clusters, to simple liquids and solids, and photo-excited reactions in complex reaction environments such as zeolites

  11. Diffusion-controlled reaction. V. Effect of concentration-dependent diffusion coefficient on reaction rate in graft polymerization

    International Nuclear Information System (INIS)

    Imre, K.; Odian, G.

    1979-01-01

    The effect of diffusion on radiation-initiated graft polymerization has been studied with emphasis on the single- and two-penetrant cases. When the physical properties of the penetrants are similar, the two-penetrant problems can be reduced to the single-penetrant problem by redefining the characteristic parameters of the system. The diffusion-free graft polymerization rate is assumed to be proportional to the upsilon power of the monomer concentration respectively, and, in which the proportionality constant a = k/sub p/R/sub i//sup w//k/sub t//sup z/, where k/sub p/ and k/sub t/ are the propagation and termination rate constants, respectively, and R/sub i/ is the initiation rate. The values of upsilon, w, and z depend on the particular reaction system. The results of earlier work were generalized by allowing a non-Fickian diffusion rate which predicts an essentially exponential dependence on the monomer concentration of the diffusion coefficient, D = D 0 [exp(deltaC/M)], where M is the saturation concentration. A reaction system is characterized by the three dimensionless parameters, upsilon, delta, and A = (L/2)[aM/sup (upsilon--1)//D 0 ]/sup 1/2/, where L is the polymer film thickness. Graft polymerization tends to become diffusion controlled as A increases. Larger values of delta and ν cause a reaction system to behave closer to the diffusion-free regime. Transition from diffusion-free to diffusion-controlled reaction involves changes in the dependence of the reaction rate on film thickness, initiation rate, and monomer concentration. Although the diffusion-free rate is w order in initiation rate, upsilon order in monomer, and independent of film thickness, the diffusion-controlled rate is w/2 order in initiator rate and inverse first-order in film thickness. Dependence of the diffusion-controlled rate on monomer is dependent in a complex manner on the diffusional characteristics of the reaction system. 11 figures, 4 tables

  12. Rate coefficient for the reaction N + NO

    Science.gov (United States)

    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.

  13. Proton-transfer reactions in ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.; Schmidt, R.; Schuster, R.

    1985-01-01

    Ion-molecule reactions play an important role in various radiolytic processes, e.g. gas-pulse radiolysis, environmental research. For a discussion of mechanisms rate coefficients have to be assessed. Here gas-phase rate coefficients of ion-(polar) molecule reactions are calculated using the ideas of interaction potentials, reactive cross-sections and distribution functions of the translational energies of both the reactants (ions I, molecules M). The starting point of our approach, directed especially to gas-phase proton-transfer reactions, is the idea that the rate coefficient k can be calculated as an ion-molecule capture-rate coefficient multiplied by a 'steric factor' representing the probability for proton transfer. Mutual capture of the reaction partners within a possible reaction zone is caused by the physical interaction between an ion and a polar molecule. A model is discussed. Results are presented. (author)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Meisel, Zachary

    2008-10-01

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

  16. Thermonuclear reaction rate of 17O(p,γ)18F

    International Nuclear Information System (INIS)

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

    2005-01-01

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

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

    Science.gov (United States)

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

    2015-02-01

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

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

    Science.gov (United States)

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

    2015-08-14

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

  19. An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sidebottom, H.W.; Donlon, M.

    1991-01-01

    combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways...

  20. Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

    Science.gov (United States)

    Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

    2017-07-01

    Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract GRAPHICAL ABSTRACT TEXT HERE] -->.

  1. Rates of chemical reaction and atmospheric heating during core debris expulsion from a pressurized vessel

    International Nuclear Information System (INIS)

    Powers, D.A.; Tarbell, W.W.; Brockman, J.E.; Pilch, M.

    1986-01-01

    Core debris may be expelled from a pressurized reactor vessel during a severe nuclear reactor accident. Experimental studies of core debris expulsion from pressurized vessels have established that the expelled material can be lofted into the atmosphere of the reactor containment as particulate 0.4 to 2 mm in diameter. These particles will vigorously react with steam and oxygen in the containment atmosphere. Data on such reactions during tests with 80 kg of expelled melt will be reported. A model of the reaction rates based on gas phase mass transport will be described and shown to account for atmospheric heating and aerosol generation observed in the tests

  2. Hydrogen isotope exchange reaction rates in tritium, hydrogen and deuterium mixed gases

    International Nuclear Information System (INIS)

    Uda, Tatsuhiko

    1992-01-01

    Hydrogen isotope exchange reaction rates in H 2 +T 2 , D 2 +T 2 and H 2 +D 2 +T 2 mixed gases, as induced by tritium decay and beta radiation, were experimentally measured by laser Raman spectrometry. Initially a glass cell was filled with T 2 gas to a pressure of 30-40 kPa, and an equivalent partial pressure of H 2 and/or D 2 was added. The first-order hydrogen isotope exchange reaction rates were 5.54x10 -2 h -1 for H 2 +T 2 mixed gas and 4.76x10 -2 h -1 for D 2 +T 2 . The actual HT producing rate was nearly equivalent to the rate of DT, but the reverse reaction rate of HT was faster than that of DT. The exchange reaction rates between H, D and T showed the isotope effect, HD>HT>DT. The hydrogen isotope exchange reaction rates observed were about twenty times larger than ion formation rates by beta radiation. This result suggests that a free radical chain reaction in hydrogen isotopes is occurring. (orig.)

  3. The crystallization kinetic model of nano-CaCO3 in CO2-ammonia-phosphogypsum three-phase reaction system

    Science.gov (United States)

    Liu, Hao; Lan, Peiqiang; Lu, Shangqing; Wu, Sufang

    2018-06-01

    Phosphogypsum (PG) as a low-cost calcium resource was used to prepare nano-CaCO3 in a three-phase system by reactions. Based on the population balance equation, nano-CaCO3 crystal nucleation and growth model in the gas (CO2)-liquid (NH3·H2O)-solid (CaSO4) three-phase system was established. The crystallization kinetic model of nano-CaCO3 in CO2-NH3·H2O-CaSO4 reactions system was experimental developed over an optimized temperature range of 20-40 °C and CO2 flow rate range of 138-251 ml/min as rCaCO3 =kn 32 πM2γ3/3R3ρ2T3 (C -C∗)0.8/[ ln (C /C∗) ]3 + πρ/3M kg3 kn(C -C∗) 2t3 , where nano-CaCO3 nucleation rate constant was kn = 6.24 ×1019 exp(-15940/RT) and nano-CaCO3 growth rate constant was kg = 0.79 exp(-47650/RT) respectively. Research indicated that nucleation rates and growth rates both increased with the increasing of temperature and CO32- ion concentration. And crystal growth was dependent on temperature more than that of nucleation process because the activation energy of CaCO3 growth was bigger than that of CaCO3 nucleation. Decreasing the reaction temperature and CO2 flow rate was more beneficial for producing nano-size CaCO3 because of the lower CaCO3 growth rates. The deduced kinetic equation could briefly predict the average particle sizes of nano-CaCO3.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hufnagel, Todd C.

    2014-06-09

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

  5. Relationship among reaction rate, release rate and efficiency of nanomachine-based targeted drug delivery.

    Science.gov (United States)

    Zhao, Qingying; Li, Min; Luo, Jun

    2017-12-04

    In nanomachine applications towards targeted drug delivery, drug molecules released by nanomachines propagate and chemically react with tumor cells in aqueous environment. If the nanomachines release drug molecules faster than the tumor cells react, it will result in loss and waste of drug molecules. It is a potential issue associated with the relationship among reaction rate, release rate and efficiency. This paper aims to investigate the relationship among reaction rate, release rate and efficiency based on two drug reception models. We expect to pave a way for designing a control method of drug release. We adopted two analytical methods that one is drug reception process based on collision with tumors and another is based on Michaelis Menten enzymatic kinetics. To evaluate the analytical formulations, we used the well-known simulation framework N3Sim to establish simulations. The analytical results of the relationship among reaction rate, release rate and efficiency is obtained, which match well with the numerical simulation results in a 3-D environment. Based upon two drug reception models, the results of this paper would be beneficial for designing a control method of nanomahine-based drug release.

  6. Radical Reactions in the Gas Phase: Recent Development and Application in Biomolecules

    Directory of Open Access Journals (Sweden)

    Yang Gao

    2014-01-01

    Full Text Available This review summarizes recent literature describing the use of gas phase radical reactions for structural characterization of complex biomolecules other than peptides. Specifically, chemical derivatization, in-source chemical reaction, and gas phase ion/ion reactions have been demonstrated as effective ways to generate radical precursor ions that yield structural informative fragments complementary to those from conventional collision-induced dissociation (CID. Radical driven dissociation has been applied to a variety of biomolecules including peptides, nucleic acids, carbohydrates, and phospholipids. The majority of the molecules discussed in this review see limited fragmentation from conventional CID, and the gas phase radical reactions open up completely new dissociation channels for these molecules and therefore yield high fidelity confirmation of the structures of the target molecules. Due to the extensively studied peptide fragmentation, this review focuses only on nonpeptide biomolecules such as nucleic acids, carbohydrates, and phospholipids.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

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

    2007-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Cyburt, R. H.; Keek, L.; Schatz, H. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Amthor, A. M. [Department of Physics and Astronomy, Bucknell University, Lewisburg, PA 17837 (United States); Heger, A.; Meisel, Z.; Smith, K. [Joint Institute for Nuclear Astrophysics (JINA), Michigan State University, East Lansing, MI 48824 (United States); Johnson, E. [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States)

    2016-10-20

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

  10. Solid-phase vibrational redox reactions in coordinated oxides

    International Nuclear Information System (INIS)

    Kostikova, G.P.; Korol'kov, D.V.; Kostikov, Yu.P.

    1996-01-01

    The properties of multicomponent oxides (YBa 2 Cu 3 O 7-x , etc.), incorporating different valency forms of each of two (or more) different elements have been compared with the properties of the known chemical systems, where vibrational (periodic) redox-reactions are realized a fortiori. The essence of the new theoretical concept suggested consists in the following: high-T c superconductivity of the complex oxides and similar compounds originates from vibrational redox reaction proceeding in solid phase and involving different valency atoms of every element

  11. Experimental determination of reaction rates of water. Hydrogen exchange of tritium with hydrophobic catalysts

    International Nuclear Information System (INIS)

    Bixel, J.C.; Hartzell, B.W.; Park, W.K.

    1976-01-01

    This study was undertaken to obtain data needed for further development of a process for the enrichment and removal of tritium from the water associated with light-water reactors, fuel-reprocessing plants, and tritium-handling laboratories. The approach is based on the use of antiwetting, hydrophobic catalysts which permit the chemical exchange reactions between liquid water and gaseous hydrogen in direct contact, thus eliminating problems of catalyst deactivation and the complexity of reactor design normally associated with current catalytic-detritiation techniques involving gas-phase catalysis. An apparatus and procedure were developed for measuring reaction rates of water-hydrogen chemical exchange with hydrophobic catalysts. Preliminary economic evaluations of the process were made as it might apply to the AGNS fuel reprocessing plant

  12. Structural parameter identifiability analysis for dynamic reaction networks

    DEFF Research Database (Denmark)

    Davidescu, Florin Paul; Jørgensen, Sten Bay

    2008-01-01

    method based on Lie derivatives. The proposed systematic two phase methodology is illustrated on a mass action based model for an enzymatically catalyzed reaction pathway network where only a limited set of variables is measured. The methodology clearly pinpoints the structurally identifiable parameters...... where for a given set of measured variables it is desirable to investigate which parameters may be estimated prior to spending computational effort on the actual estimation. This contribution addresses the structural parameter identifiability problem for the typical case of reaction network models....... The proposed analysis is performed in two phases. The first phase determines the structurally identifiable reaction rates based on reaction network stoichiometry. The second phase assesses the structural parameter identifiability of the specific kinetic rate expressions using a generating series expansion...

  13. Studies of Heterogeneously Catalyzed Liquid-Phase Alcohol Oxidation on Platinum bySum-frequency Generation Vibrational Spectroscopy and Reaction Rate Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Christopher [Univ. of California, Berkeley, CA (United States)

    2014-05-15

    Compared to many branches of chemistry, the molecular level study of catalytically active surfaces is young. Only with the invention of ultrahigh vacuum technology in the past half century has it been possible to carry out experiments that yield useful molecular information about the reactive occurrences at a surface. The reason is two-fold: low pressure is necessary to keep a surface clean for an amount of time long enough to perform an experiment, and most atomic scale techniques that are surface speci c (x-ray photoelectron spectroscopy, electron energy loss spectroscopy, Auger electron spectroscopy, etc.) cannot be used at ambient pressures, because electrons, which act as chemical probes in these techniques, are easily scattered by molecules. Sum-frequency generation (SFG) vibrational spectroscopy is one technique that can provide molecular level information from the surface without the necessity for high vacuum. Since the advent of SFG as a surface spectroscopic tool it has proved its worth in the studies of surface catalyzed reactions in the gas phase, with numerous reactions in the gas phase having been investigated on a multitude of surfaces. However, in situ SFG characterization of catalysis at the solid-liquid interface has yet to be thoroughly pursued despite the broad interest in the use of heterogeneous catalysts in the liquid phase as replacements for homogeneous counterparts. This work describes an attempt to move in that direction, applying SFG to study the solid-liquid interface under conditions of catalytic alcohol oxidation on platinum.

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

    Science.gov (United States)

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

    2018-04-25

    Rate coefficients, k, for the gas-phase reaction of the OH radical with (E) CF3CH=CHCF3 ((E)-1,1,14,4,4-hexafluoro-2-butene, HFO-1336mzz(E)) were measured over a range of temperature (211-374 K) and bath gas pressure (20-300 Torr; He, N2) using a pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique. k1(T) was independent of pressure over this range of conditions with k1(296 K) = (1.31 ± 0.15) × 10 13 cm3 molecule 1 s 1 and k1(T) = (6.94 ± 0.80) × 10 13 exp[ (496 ± 10)/T] cm3 molecule 1 s 1, where the uncertainties are 2 and the pre-exponential term includes estimated systematic error. Rate coefficients for the OD reaction were also determined over a range of temperature (262-374 K) at 100 Torr (He). The OD rate coefficients were ~15% greater than the OH values and showed similar temperature dependent behavior with k2(T) = (7.52 ± 0.44) × 10 13 exp[ (476 ± 20)/T] and k2(296 K) = (1.53 ± 0.15) × 10 13 cm3 molecule 1 s 1. The rate coefficients for reaction 1 were also measured using a relative rate technique between 296 and 375 K with k1(296 K) measured to be (1.22 ± 0.1) × 10 13 cm3 molecule 1 s 1 in agreement with the PLP-LIF results. In addition, the 296 K rate coefficient for the O3 + (E) CF3CH=CHCF3 reaction was determined to be reaction and the significant decrease in OH reactivity compared to the (Z) CF3CH=CHCF3 stereoisomer reaction. The estimated atmospheric lifetime of (E) CF3CH=CHCF3, due to loss by reaction with OH, is estimated to be ~90 days, while the actual lifetime will depend on the location and season of its emission. Infrared absorption spectra of (E) CF3CH=CHCF3 were measured and used to estimate the 100-year time horizon global warming potentials (GWP) of 32 (atmospherically well-mixed) and 14 (lifetime-adjusted).

  15. BIG-10 fission product generation and reaction rates

    International Nuclear Information System (INIS)

    Rogers, J.W.

    1976-01-01

    Fission product generation rates for high quality fission foils and reaction rates of nonfission foils have been measured by gamma ray activation analyses. These foils were irradiated in the BIG-10 facility and the activities were measured by NaI counting techniques

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

    Science.gov (United States)

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

    2015-04-01

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

  17. The Investors- Reaction to Investment Rating Change Announcements

    OpenAIRE

    Chih-Hsiang Chang; Liang-Chien Lee; Shu-Ling Wu

    2012-01-01

    This study investigates the investors- behavioral reaction to the investment rating change announcements from the views of behavioral finance. The empirical results indicate that self-interest does affect the intention of securities firms to release investment ratings for individual stocks. In addition, behavioral pitfalls are also found in the response of retail investors to investment rating change announcements.

  18. Effects of ion and electron screening on thermonuclear reaction rates

    International Nuclear Information System (INIS)

    Brady, L.R. Jr.

    1977-01-01

    The effects of screening by ions and electrons on thermonuclear reaction rates in stellar plasmas are considered. The enhancement of the reaction rate ranges from negligible to extremely large (on the order of 10 26 or greater). In order to calculate these effects, the potential about a given reacting nucleus is determined. First, Boltzmann-Vlasov and Poisson-Boltzmann equations are solved to yield a Yukawa potential. A suitable approximation to this potential is integrated in the action integral to give the barrier penetration. The screened reaction rate is then found by the saddle-point method. In developing a general formalism to calculate the screened reaction rate and the screening factor, effects due to the finite size of the nucleus are considered and found to be negligible. An expression for the screening factor for resonant reaction rates is also derived. A different and relatively simple approach, based on work of Stewart and Pyatt (1966), is used to find the barrier penetration from the action integral in two approximations: a modified Coulomb potential and a constant-shift potential. Screening factors are calculated for carbon burning at T 6 = 100 and T 6 = 400 for a wide range of densities and also for several examples in late stellar evolution. These screening factors are, for the most part, greater than those given by most others by a few percent at low density to 4 or more orders of magnitude at T 6 = 100 and rho = 10 10 g/cm 3 . Near the edge of the crystalline lattice region, however, they are significantly lower than those of some others. The increase in reaction rates for carbon burning indicates that carbon ignition may occur at lower densities than previously thought and may affect the density at which a supernova shock may occur

  19. X particle effect for 6Li reaction rates calculations

    International Nuclear Information System (INIS)

    Kocak, G.; Balantekin, A. B.

    2009-01-01

    The inferred primordial 6 L i-7 L i abundances are different from standard big bang nucleosynthesis results, 6 L i is 1000 times larger and 7 L i is 3 times smaller than the big bang prediction. In big bang nucleosynthesis, negatively charged massive X particles a possible solution to explain this primordial Li abundances problem [1]. In this study, we consider only X particle effect for nuclear reactions to obtain S-factor and reaction rates for Li. All S-factors calculated within the Optical Model framework for d(α,γ)6 L i system. We showed that the enhancement effect of massive negatively charged X particle for 6 L i system reaction rate.(author)

  20. Direct gas-phase epoxidation of propylene to propylene oxide through radical reactions: A theoretical study

    Science.gov (United States)

    Kizilkaya, Ali Can; Fellah, Mehmet Ferdi; Onal, Isik

    2010-03-01

    The gas-phase radical chain reactions which utilize O 2 as the oxidant to produce propylene oxide (PO) are investigated through theoretical calculations. The transition states and energy profiles were obtained for each path. The rate constants were also calculated. The energetics for the competing pathways indicate that PO can be formed selectively due to its relatively low activation barrier (9.3 kcal/mol) which is in a good agreement with the experimental value (11 kcal/mol) of gas-phase propylene epoxidation. The formation of the acrolein and combustion products have relatively high activation barriers and are not favored. These results also support the recent experimental findings.

  1. Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

    2016-12-05

    Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

  2. The analysis of magnesium oxide hydration in three-phase reaction system

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin, E-mail: ntp@dlmu.edu.cn

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

  3. Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Scott [Univ of KY, dept of chemical and materials engineering; lynch, Andrew [Univ of KY, dept of chemical and materials engineering; Bachas, Leonidas [Univ of KY, Dept of Chemistry; hampson, Steve [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Ormsbee, Lindelle [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Bhattacharyya, Dibakar [Univ of KY, dept of chemical and materials engineering

    2008-06-01

    The Standard Fenton reaction has been used for In-Situ Chemical Oxidation (ISCO) of toxic organics in groundwater. However, it requires low pH operating conditions, and thus has limitations for in situ applications. In addition, hydroxyl radicals are rapidly consumed by hydroxyl scavengers found in the subsurface. These problems are alleviated through the chelate-modified Fenton (hydroxyl radical) reaction, which includes the addition of nontoxic chelate (L) such as citrate or gluconic acid. This chelate allows the reaction to take place at bear neutral pH and control hydrogen peroxide consumption by binding to Fe(II), forming an FeL complex. The chelate also binds to Fe(III), preventing its precipitation as ferric hydroxide and thus prevents problems associated with injection well plugging. The rate of TCE dechlorination in chelate-modified Fenton systems is a function of pH, H2O2 concentration, and FE:L ratio. The primary objective of this research is to model and apply this process to the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinates TCE in both the aqueous and organic phases at near-neutral pH. Other focuses of this work include determining the effect of [L]:[Fe] ratios on H2O2 and TCE degradation as well as reusability of the FE citrate solution under repeated H2O2 injections. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using established hydroxyl radial kinetics and mass transfer relationships.

  4. The time dependence of rate constants of esub(aq)sup(-) reactions

    International Nuclear Information System (INIS)

    Burcl, R.; Byakov, V.M.; Grafutin, V.I.

    1982-01-01

    Published data about the time dependence of rate constants k(esub(aq)sup(-)+Ac) of esub(aq)sup(-) reactions with the acceptor Ac are analyzed, using the results of rate constant k(Ps+Ac) measurements for positronium reactions. It is shown that neither esub(aq)sup(-) nor Ps reaction rate constants depend on time in the observable range. Experimentally found concentration dependence of k(esub(aq)sup(-)+Ac) is due to other factors, connected with the existence of electric charge of esub(aq)sup(-), e.g. ionic strength, tunnelling effect etc. (author)

  5. Constrained least squares methods for estimating reaction rate constants from spectroscopic data

    NARCIS (Netherlands)

    Bijlsma, S.; Boelens, H.F.M.; Hoefsloot, H.C.J.; Smilde, A.K.

    2002-01-01

    Model errors, experimental errors and instrumental noise influence the accuracy of reaction rate constant estimates obtained from spectral data recorded in time during a chemical reaction. In order to improve the accuracy, which can be divided into the precision and bias of reaction rate constant

  6. Estimating reaction rate constants: comparison between traditional curve fitting and curve resolution

    NARCIS (Netherlands)

    Bijlsma, S.; Boelens, H. F. M.; Hoefsloot, H. C. J.; Smilde, A. K.

    2000-01-01

    A traditional curve fitting (TCF) algorithm is compared with a classical curve resolution (CCR) approach for estimating reaction rate constants from spectral data obtained in time of a chemical reaction. In the TCF algorithm, reaction rate constants an estimated from the absorbance versus time data

  7. Effects of large rate coefficients for ion-polar neutral reactions on chemical models of dense interstellar clouds

    International Nuclear Information System (INIS)

    Herbst, E.; Leung, C.M.; Rensselaer Polytechnic Institute, Troy, NY)

    1986-01-01

    Pseudo-time-dependent models of the gas phase chemistry of dense interstellar clouds have been run with large rate coefficients for reactions between ions and polar neutral species, as advocated by Adams, Smith, and Clary. The higher rate coefficients normally lead to a reduction in both the peak and steady state abundances of polar neutrals, which can be as large as an order of magnitude but is more often smaller. Other differences between the results of these models and previous results are also discussed. 38 references

  8. Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries.

    Science.gov (United States)

    Prentice, Boone M; McLuckey, Scott A

    2013-02-01

    Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field.

  9. Nuclear reaction rates and the nova outburst

    International Nuclear Information System (INIS)

    Starrfield, S.G.; Iliadis, C.

    2000-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Zhifeng [Institute of Surface-Earth System Science, Tianjin University, Tianjin China; Pacific Northwest National Laboratory, Richland WA USA; Liu, Chongxuan [Pacific Northwest National Laboratory, Richland WA USA; School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen China; Liu, Yuanyuan [Pacific Northwest National Laboratory, Richland WA USA; School of Earth Science and Engineering, Nanjing University, Nanjing China; Bailey, Vanessa L. [Pacific Northwest National Laboratory, Richland WA USA

    2017-11-01

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

  11. Reactions of newly formed fission products in the gas phase

    International Nuclear Information System (INIS)

    Strickert, R.G.

    1976-01-01

    A dynamic gas-flow system was constructed which stopped fission products in the gas phase and rapidly separated (in less than 2 sec) volatile compounds from non-volatile ones. The filter assembly designed and used was shown to stop essentially all non-volatile fission products. Between 5 percent and 20 percent of tellurium fission-product isotopes reacted with several hydrocarbon gases to form volatile compounds, which passed through the filter. With carbon monoxide gas, volatile tellurium compound(s) (probably TeCO) were also formed with similar efficiencies. The upper limits for the yields of volatile compounds formed between CO and tin and antimony fission products were shown to be less than 0.3 percent, so tellurium nuclides, not their precursors, reacted with CO. It was found that CO reacted preferentially with independently produced tellurium atoms; the reaction efficiency of beta-produced atoms was only 27 +- 3 percent of that of the independently formed atoms. The selectivity, which was independent of the over-all reaction efficiency, was shown to be due to reaction of independently formed atoms in the gas phase. The gas phase reactions are believed to occur mainly at thermal energies because of the independence of the yield upon argon moderator mole-fraction (up to 80 percent). It was shown in some experiments that about one-half of the TeCO decomposed in passing through a filter and that an appreciable fraction (approximately 20 percent) of the tellurium atoms deposited on the filter reacted agin with CO. Other tellurium atoms on the filter surface (those formed by beta decay and those formed independently but not reacting in the gas phase) also reacted with CO, but probably somewhat less efficiently than atoms formed by TeCO decomposition. No evidence was found for formation of TeCO as a direct result of beta-decay

  12. In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research.

    Science.gov (United States)

    Wu, Jianbo; Shan, Hao; Chen, Wenlong; Gu, Xin; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao

    2016-11-01

    Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. The reaction rates of electrons with native and irradiated ribonuclease

    International Nuclear Information System (INIS)

    Schuessler, H.; Ebert, M.; Davies, J.V.

    1977-01-01

    The rate of reaction of hydrated electrons with proteins depends, amongst other things, on the conformational structure of the protein, and irradiation itself causes conformational changes in proteins. A study has been made of variations in the reaction rates of hydrated electrons with RNase pre-irradiated by the Linac or by a 60 Co γ-source. The reaction rate constants varied with the pre-irradiation dose, the concentration of phosphate buffer, the enzyme concentration and also the presence of 10 -2 M ethanol. These variations serve to emphasize the importance of the tertiary structure of biological molecules in irradiation processes and have significant implications in the mathematical analysis of the inactivation of enzymes in steady-state irradiation processes. (U.K.)

  14. On the mechanism of effective chemical reactions with turbulent mixing of reactants and finite rate of molecular reactions

    Energy Technology Data Exchange (ETDEWEB)

    Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru [Russian Academy of Sciences, Institute of Applied Mechanics (Russian Federation)

    2017-01-15

    A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into “active” and “passive” classes; the reactants of the first class are not mixed and react by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.

  15. Non extensive corrections to stellar nuclear reactions rate

    Energy Technology Data Exchange (ETDEWEB)

    Assuncao, M. [Universidade Federal de Sao Paulo (DCET/UNIFESP), Diadema, SP (Brazil). Dept. de Ciencias Exatas e da Terra; Silveira, F.E.M. [Universidade Federal do ABC, Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas; Lima, J.A.S. [Universidade de Sao Paulo (IAG/USP), SP (Brazil). Inst. de Astronomia, Geofisica e Ciencias Atmosfericas

    2010-07-01

    Full text: Stellar nucleosynthesis is widely accepted as the basic mechanism for creation of chemical elements in the Universe. In particular, nuclear reactions occurring in the Sun are recognized as responsible for its energy generation. The problem of to determine the energy generation mechanism in stars was firstly attacked by Gamow in the framework of his quantum mechanical theory of potential barrier penetration. According to that approach, the reactions rate is calculated by averaging the penetration factor over the velocity distribution of the plasma particles. A randomization of that distribution is expected as a consequence of the reactions. However, diffusion processes in the macroscopic environment should balance the resulting particles number depletion. Therefore, matter, energy, and momentum might steadily flow. In other words, a quasi-stationary equilibrium state must be attained. In this work, the potential barrier penetration approach to stellar nuclear reactions rate has been rediscussed with basis on Tsallis nonextensive statistics. The investigation has been restricted to non-resonant reactions, for which the S-factor can be regarded as a constant. It has been found that, within the extended formulation, the nonextensive q-parameter is constrained to a maximum value. Accordingly, the q-energy has been shown to exhibit a minimum. The q-Gamow peak has been derived and, in connection with the usual Gaussian approximation, the corresponding half q-width has been also estimated. Plots of the q-energy, q-Gamow peak and half q-width for some reactions with stellar physics interest have been produced. (author)

  16. Engineered Alloy Structures by Friction Stir Reaction Processing, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase I effort examines the feasibility of an innovative surface modification technology incorporating friction stir reaction processing for producing...

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

    International Nuclear Information System (INIS)

    Newton, J. R.; Longland, R.; Iliadis, C.

    2008-01-01

    We address the problem of extrapolating experimental thermonuclear reaction rates toward high stellar temperatures (T>1 GK) by using statistical model (Hauser-Feshbach) results. Reliable reaction rates at such temperatures are required for studies of advanced stellar burning stages, supernovae, and x-ray bursts. Generally accepted methods are based on the concept of a Gamow peak. We follow recent ideas that emphasized the fundamental shortcomings of the Gamow peak concept for narrow resonances at high stellar temperatures. Our new method defines the effective thermonuclear energy range (ETER) by using the 8th, 50th, and 92nd percentiles of the cumulative distribution of fractional resonant reaction rate contributions. This definition is unambiguous and has a straightforward probability interpretation. The ETER is used to define a temperature at which Hauser-Feshbach rates can be matched to experimental rates. This matching temperature is usually much higher compared to previous estimates that employed the Gamow peak concept. We suggest that an increased matching temperature provides more reliable extrapolated reaction rates since Hauser-Feshbach results are more trustwhorthy the higher the temperature. Our ideas are applied to 21 (p,γ), (p,α), and (α,γ) reactions on A=20-40 target nuclei. For many of the cases studied here, our extrapolated reaction rates at high temperatures differ significantly from those obtained using the Gamow peak concept

  18. Compilation and R-matrix analysis of Big Bang nuclear reaction rates

    International Nuclear Information System (INIS)

    Descouvemont, Pierre; Adahchour, Abderrahim; Angulo, Carmen; Coc, Alain; Vangioni-Flam, Elisabeth

    2004-01-01

    We use the R-matrix theory to fit low-energy data on nuclear reactions involved in Big Bang nucleosynthesis. Special attention is paid to the rate uncertainties which are evaluated on statistical grounds. We provide S factors and reaction rates in tabular and graphical formats

  19. Students' Ideas about Reaction Rate and Its Relationship with Concentration or Pressure

    Science.gov (United States)

    Cakmakci, Gultekin; Leach, John; Donnelly, James

    2006-01-01

    This cross-sectional study identifies key conceptual difficulties experienced by upper secondary school and pre-service chemistry teachers (N = 191) in the area of reaction rates. Students' ideas about reaction rates were elicited through a series of written tasks and individual interviews. In this paper, students' ideas related to reaction rate…

  20. Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold

    International Nuclear Information System (INIS)

    Leitner, David M.; Wolynes, Peter G.

    2006-01-01

    A variety of unimolecular reactions exhibit measured rates that exceed Rice-Ramsperger-Kassel-Marcus (RRKM) predictions. We show using the local random matrix theory (LRMT) of vibrational energy flow how the quantum localization of the vibrational states of a molecule, by violating the ergodicity assumption, can give rise to such an enhancement of the apparent reaction rate. We present an illustrative calculation using LRMT for a model 12-vibrational mode organic molecule to show that below the ergodicity threshold the reaction rate may exceed many times the RRKM prediction due to quantum localization of vibrational states

  1. Neutron detector for fusion reaction-rate measurements

    International Nuclear Information System (INIS)

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

    1993-01-01

    We have developed a fast, sensitive neutron detector for recording the fusion reaction-rate history of inertial-confinement fusion (ICF) experiments. The detector is based on the fast rise-time of a commercial plastic scintillator (BC-422) and has a response 7 neutrons

  2. Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K.

    Science.gov (United States)

    Akhgarnusch, Amou; Tang, Wai Kit; Zhang, Han; Siu, Chi-Kit; Beyer, Martin K

    2016-09-14

    The recombination reactions of gas-phase hydrated electrons (H2O)n˙(-) with CO2 and O2, as well as the charge exchange reaction of CO2˙(-)(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions. Converted to room temperature condensed phase, this yields hydration enthalpies of CO2˙(-) and O2˙(-), ΔHhyd(CO2˙(-)) = -334 ± 44 kJ mol(-1) and ΔHhyd(O2˙(-)) = -404 ± 28 kJ mol(-1). Quantum chemical calculations show that the charge exchange reaction proceeds via a CO4˙(-) intermediate, which is consistent with a fully ergodic reaction and also with the small efficiency. Ab initio molecular dynamics simulations corroborate this picture and indicate that the CO4˙(-) intermediate has a lifetime significantly above the ps regime.

  3. Reaction rates for neutrino processes

    International Nuclear Information System (INIS)

    Shalitin, D.

    1978-01-01

    Some integrals involved in neutrino processes are evaluated by transformation to a special system of reference - usually to the center of mass system (CM). Rather simple analytic expressions are obtained for reaction rates and, though less simple, for moments. An interesting result thus obtained is for an isotropic interaction (in CM) of a neutrino with a monoenergetic isotropic gas of extreme relativistic electrons: it is found that the probability of the scattered neutrino to have energy in a certain range is independent of this energy. (Auth.)

  4. Chemical kinetics: on the heterogeneous catalysis processes leading to an exchange between two phases. Example: isotopic exchange reactions; Cinetique chimique: sur les processus de catalyse 'heterogene' conduisant a un echange entre deux phases. Exemple: reactions d'echange isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Dirian, G; Grandcollot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    For an exchange reaction between a gaseous and a liquid phase proceeding by 'heterogeneous' catalysis in the liquid phase, diffusion in the liquid and the chemical reaction are two simultaneous and indivisible processes. We have nevertheless been able to establish criteria making it possible to distinguish between a really homogeneous kinetic process and a pseudo-homogeneous one. (author) [French] Pour une reaction d'echange entre une phase gazeuse et une phase liquide procedant par catalyse 'heterogene' en phase liquide, la diffusion dans le liquide et la reaction chimique sont deux etapes simultanees et indissociables. Nous avons pu neanmoins etablir des criteres permettant de distinguer entre une cinetique homogene vraie et une cinetique pseudo-homogene. (auteur)

  5. Liquid Film Diffusion on Reaction Rate in Submerged Biofilters

    DEFF Research Database (Denmark)

    Christiansen, Pia; Hollesen, Line; Harremoës, Poul

    1995-01-01

    Experiments were carried out in order to investigate the influence of liquid film diffusion on reaction rate in a submerged biofilter with denitrification and in order to compare with a theoretical study of the mass transfer coefficient. The experiments were carried out with varied flow, identified...... by the empty bed velocity of inflow and recirculation, respectively 1.3, 2.8, 5.6 and 10.9 m/h. The filter material consisted of 3 mm biostyren spheres. The results indicate that the influence of liquid film diffusion on reaction rate can be ignored....

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

    International Nuclear Information System (INIS)

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

    2002-01-01

    We study the astrophysical reaction rate for the formation of 9 Be through the three body reaction α(αn,γ). This reaction is one of the key reactions which could bridge the mass gap at A=8 nuclear systems to produce intermediate-to-heavy mass elements in alpha- and neutron-rich environments such as r-process nucleosynthesis in supernova explosions, s-process nucleosynthesis in asymptotic giant branch (AGB) stars, and primordial nucleosynthesis in baryon inhomogeneous cosmological models. To calculate the thermonuclear reaction rate in a wide range of temperatures, we numerically integrate the thermal average of cross sections assuming a two-steps formation through a metastable 8 Be, α+α[rlhar2] 8 Be(n,γ) 9 Be. Off-resonant and on-resonant contributions from the ground state in 8 Be are taken into account. As input cross section, we adopt the latest experimental data by photodisintegration of 9 Be with laser-electron photon beams, which covers all relevant resonances in 9 Be. Experimental data near the neutron threshold are added with γ-ray flux corrections and a new least-squares analysis is made to deduce resonance parameters in the Breit-Wigner formulation. Based on the photodisintegration cross section, we provide the reaction rate for α(αn,γ) 9 Be in the temperature range from T 9 =10 -3 to T 9 =10 1 (T 9 is the temperature in units of 10 9 K) both in the tabular form and in the analytical form for potential usage in nuclear reaction network calculations. The calculated reaction rate is compared with the reaction rates of the CF88 and the NACRE compilations. The CF88 rate, which is based on the photoneutron cross section for the 1/2 + state in 9 Be by Berman et al., is valid at T 9 >0.028 due to lack of the off-resonant contribution. The CF88 rate differs from the present rate by a factor of two in a temperature range T 9 ≥0.1. The NACRE rate, which adopted different sources of experimental information on resonance states in 9 Be, is 4-12 times

  7. Phase transformations in the reaction cell of TiNi-based sintered systems

    Science.gov (United States)

    Artyukhova, Nadezhda; Anikeev, Sergey; Yasenchuk, Yuriy; Chekalkin, Timofey; Gunther, Victor; Kaftaranova, Maria; Kang, Ji-Hoon; Kim, Ji-Soon

    2018-05-01

    The present work addresses the structural-phase state changes of porous TiNi-based compounds fabricated by reaction sintering (RS) of Ti and Ni powders with Co, Mo, and no additives introduced. The study also emphasizes the features of a reaction cell (RC) during the transition from the solid- to liquid-phase sintering. Mechanisms of phase transformations occurring in the solid phase, involving the low-melting Ti2Ni phase within the RC, have been highlighted. Also, the intermediate Ti2Ni phase had a crucial role to provide both the required RS behavior and modified phase composition of RS samples, and besides, it is found to be responsible for the near-equiatomic TiNi saturation of the melt. Both cobalt and molybdenum additives are shown to cause additional structuring of the transition zone (TZ) at the Ti2Ni‑TiNi interface and broadening of this zone. The impact of Co and Mo on the Ti2Ni phase is evident through fissuring of this phase layer, which is referred to solidified stresses increased in the layer due to post-alloying defects in the structure.

  8. Effects of network dissolution changes on pore-to-core upscaled reaction rates for kaolinite and anorthite reactions under acidic conditions

    KAUST Repository

    Kim, Daesang

    2013-11-01

    We have extended reactive flow simulation in pore-network models to include geometric changes in the medium from dissolution effects. These effects include changes in pore volume and reactive surface area, as well as topological changes that open new connections. The computed changes were based upon a mineral map from an X-ray computed tomography image of a sandstone core. We studied the effect of these changes on upscaled (pore-scale to core-scale) reaction rates and compared against the predictions of a continuum model. Specifically, we modeled anorthite and kaolinite reactions under acidic flow conditions during which the anorthite reactions remain far from equilibrium (dissolution only), while the kaolinite reactions can be near-equilibrium. Under dissolution changes, core-scale reaction rates continuously and nonlinearly evolved in time. At higher injection rates, agreement with predictions of the continuum model degraded significantly. For the far-from-equilibrium reaction, our results indicate that the ability to correctly capture the heterogeneity in dissolution changes in the reactive mineral surface area is critical to accurately predict upscaled reaction rates. For the near-equilibrium reaction, the ability to correctly capture the heterogeneity in the saturation state remains critical. Inclusion of a Nernst-Planck term to ensure neutral ionic currents under differential diffusion resulted in at most a 9% correction in upscaled rates.

  9. On the existence of and mechanism for microwave-specific reaction rate enhancement.

    Science.gov (United States)

    Dudley, Gregory B; Richert, Ranko; Stiegman, A E

    2015-04-01

    The use of microwave radiation to drive chemical reactions has become ubiquitous in almost all fields of chemistry. In all of these areas it is principally due to rapid and convenient heating resulting in significantly higher rates of reaction, with other advantages including enhanced product selectivity and control of materials properties. Although microwave heating continues to grow as an enabling technology, fundamental research into the nature of microwave heating has not grown at the same rate. In the case of chemical reactions run in homogeneous solution, particularly synthetic organic reactions, there is considerable controversy over the origins of rate enhancement, with a fundamental question being whether there exist microwave-specific effects, distinct from what can be attained under conventional convective heating, that can accelerate a reaction rate. In this Perspective, we discuss unique aspects of microwave heating of molecules in solution and discuss the origin and nature of microwave-specific effects arising from the process of "selective heating" of reactants in solution. Integral to this discussion is work from the field of dielectric relaxation spectroscopy, which provides a model for selective heating by Debye relaxation processes. The Perspective also includes a critical discussion of hypotheses of non-thermal effects (alternatively classified here as resonant processes) and an outline of specific reaction parameters for chemical systems in which microwave-specific Debye relaxation processes can result in observable reaction rate enhancement.

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

    Science.gov (United States)

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

    2018-01-01

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

  11. Temperature Dependent Rate Coefficients for the Gas-Phase Reaction of the OH Radical with Linear (L2, L3) and Cyclic (D3, D4) Permethylsiloxanes.

    Science.gov (United States)

    Bernard, François; Papanastasiou, Dimitrios K; Papadimitriou, Vassileios C; Burkholder, James B

    2018-04-19

    Permethylsiloxanes are emitted into the atmosphere during production and use as personal care products, lubricants, and cleaning agents. The predominate atmospheric loss process for permethylsiloxanes is expected to be via gas-phase reaction with the OH radical. In this study, rate coefficients, k(T), for the OH radical gas-phase reaction with the two simplest linear and cyclic permethylsiloxanes were measured using a pulsed laser photolysis-laser induced fluorescence technique over the temperature range of 240-370 K and a relative rate method at 294 K: hexamethyldisiloxane ((CH 3 ) 3 SiOSi(CH 3 ) 3 , L 2 ), k 1 ; octamethyltrisiloxane ([(CH 3 ) 3 SiO] 2 Si(CH 3 ) 2 , L 3 ), k 2 ; hexamethylcyclotrisiloxane ([-Si(CH 3 ) 2 O-] 3 , D 3 ), k 3 ; and octamethylcyclotetrasiloxane ([-Si(CH 3 ) 2 O-] 4 , D 4 ), k 4 . The obtained k(294 K) values and temperature-dependence expressions for the 240-370 K temperature range are (cm 3 molecule -1 s -1 , 2σ absolute uncertainties): k 1 (294 K) = (1.28 ± 0.08) × 10 -12 , k 1 ( T) = (1.87 ± 0.18) × 10 -11 exp(-(791 ± 27)/ T); k 2 (294 K) = (1.72 ± 0.10) × 10 -12 , k 2 ( T) = 1.96 × 10 -13 (T/298) 4.34 exp(657/ T); k 3 (294 K) = (0.82 ± 0.05) × 10 -12 , k 3 ( T) = (1.29 ± 0.19) × 10 -11 exp(-(805 ± 43)/ T); and k 4 (294 K) = (1.12 ± 0.10) × 10 -12 , k 4 ( T) = (1.80 ± 0.26) × 10 -11 exp(-(816 ± 43)/ T). The cyclic molecules were found to be less reactive than the analogous linear molecule with the same number of -CH 3 groups, while the linear and cyclic permethylsiloxane reactivity both increase with the increasing number of CH 3 - groups. The present results are compared with previous rate coefficient determinations where available. The permethylsiloxanes included in this study are atmospherically short-lived compounds with estimated atmospheric lifetimes of 11, 8, 17, and 13 days, respectively.

  12. Gas-phase ion-molecule reactions and high-pressure mass spectrometer, 1

    International Nuclear Information System (INIS)

    Hiraoka, Kenzo

    1977-01-01

    The reasons for the fact that the research in gas-phase ion-molecule reactions, to which wide interest is shown, have greatly contributed to the physical and chemical fields are that, first it is essential in understanding general phenomena concerning ions, second, it can furnish many unique informations in the dynamics of chemical reactions, and third, usefulness of '' chemical ionization'' methods has been established as its application to chemical analysis. In this review, the history and trend of studies and equipments in gas-phase ion-molecule reactions are surveyed. The survey includes the chemical ionization mass spectrometer for simultaneously measuring the positive and negative ions utilizing a quadrupole mass spectrometer presented by Hunt and others, flowing afterglow method derived from the flowing method which traces neutral chemical species mainly optically, ion cyclotron resonance mass spectrometer, trapped ion mass spectrometer and others. Number of reports referred to ion-molecule reactions issued during the last one year well exceeds the total number of reports concerning mass spectrometers presented before 1955. This truly shows how active the research and development are in this field. (Wakatsuki, Y.)

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

    Science.gov (United States)

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

    2014-08-21

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

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

    Science.gov (United States)

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

    2003-04-01

    The present invention is a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber substantially matching a local heat transfer rate of a catalytic thermal chemical reaction. The key to the invention is a thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from the reaction chamber to the heat transfer chamber substantially matches the local heat transfer rate.

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

    Science.gov (United States)

    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.

  16. Computational and experimental studies on stabilities, reactions and reaction rates of cations and ion-dipole complexes

    NARCIS (Netherlands)

    Ervasti, H.K.

    2008-01-01

    In this thesis, ion stability, ion-molecule reactions and reaction rates are studied using mass spectrometry and molecular modelling. In Chapter 2 the effect of functional group substitution on neutral and ionised ketene are studied. Electron-donating substituents show a stabilising positive

  17. Chemical dynamics simulations of X- + CH3Y → XCH3 + Y- gas-phase S(N)2 nucleophilic substitution reactions. Nonstatistical dynamics and nontraditional reaction mechanisms.

    Science.gov (United States)

    Manikandan, Paranjothy; Zhang, Jiaxu; Hase, William L

    2012-03-29

    Extensive classical chemical dynamics simulations of gas-phase X(-) + CH(3)Y → XCH(3) + Y(-) S(N)2 nucleophilic substitution reactions are reviewed and discussed and compared with experimental measurements and predictions of theoretical models. The primary emphasis is on reactions for which X and Y are halogen atoms. Both reactions with the traditional potential energy surface (PES), which include pre- and postreaction potential energy minima and a central barrier, and reactions with nontraditional PESs are considered. These S(N)2 reactions exhibit important nonstatistical atomic-level dynamics. The X(-) + CH(3)Y → X(-)---CH(3)Y association rate constant is less than the capture model as a result of inefficient energy transfer from X(-)+ CH(3)Y relative translation to CH(3)Y rotation and vibration. There is weak coupling between the low-frequency intermolecular modes of the X(-)---CH(3)Y complex and higher frequency CH(3)Y intramolecular modes, resulting in non-RRKM kinetics for X(-)---CH(3)Y unimolecular decomposition. Recrossings of the [X--CH(3)--Y](-) central barrier is important. As a result of the above dynamics, the relative translational energy and temperature dependencies of the S(N)2 rate constants are not accurately given by statistical theory. The nonstatistical dynamics results in nonstatistical partitioning of the available energy to XCH(3) +Y(-) reaction products. Besides the indirect, complex forming atomic-level mechanism for the S(N)2 reaction, direct mechanisms promoted by X(-) + CH(3)Y relative translational or CH(3)Y vibrational excitation are possible, e.g., the roundabout mechanism.

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

    Science.gov (United States)

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

    2016-11-05

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

  19. Ion-neutral gas reactions in a collision/reaction cell in inductively coupled plasma mass spectrometry: Correlation of ion signal decrease to kinetic rate constants

    Energy Technology Data Exchange (ETDEWEB)

    Gray, Patrick J. [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States); Department of Chemistry, The Ohio State University, 120 18th Avenue, Columbus, OH 43210 (United States); Olesik, John W., E-mail: olesik.2@osu.edu [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States)

    2015-03-01

    Reaction gas flow rate dependent Ar{sub 2}{sup +} and Ar{sup +} signals are correlated to fundamental kinetic rate coefficients. A simple calculation, assuming that gas exits the reaction cell due only to effusion, is described to estimate the gas pressure in the reaction cell. The value of the product of the kinetic rate constant and the ion residence time in the reaction cell can be determined from experimental measurement of the decrease in an ion signal as a function of reaction gas flow rate. New kinetic rate constants are determined for the reaction of CH{sub 3}F with Ar{sup +} and Ar{sub 2}{sup +}. - Highlights: • How to determine pressure and the product of the kinetic rate constant times the ion residence time in reaction cell • Relate measured ICP-DRC-MS signals versus gas flow rate to kinetic rate constants measured previously using SIFT-MS • Describe how to determine previously unmeasured kinetic rate constants using ICP-DRC-MS.

  20. Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Niobium

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This test method describes procedures for measuring reaction rates by the activation reaction 93Nb(n,n′)93mNb. 1.2 This activation reaction is useful for monitoring neutrons with energies above approximately 0.5 MeV and for irradiation times up to about 30 years. 1.3 With suitable techniques, fast-neutron reaction rates for neutrons with energy distribution similar to fission neutrons can be determined in fast-neutron fluences above about 1016cm−2. In the presence of high thermal-neutron fluence rates (>1012cm−2·s−1), the transmutation of 93mNb due to neutron capture should be investigated. In the presence of high-energy neutron spectra such as are associated with fusion and spallation sources, the transmutation of 93mNb by reactions such as (n,2n) may occur and should be investigated. 1.4 Procedures for other fast-neutron monitors are referenced in Practice E 261. 1.5 Fast-neutron fluence rates can be determined from the reaction rates provided that the appropriate cross section information ...

  1. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs.

    Science.gov (United States)

    Ruokolainen, Miina; Gul, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio

    2016-02-15

    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and 7-ethoxycoumarin with phase I metabolites of the same compounds produced in vitro by human liver microsomes (HLM). Reaction products were analysed by UHPLC-MS. TiO2 photocatalysis simulated the in vitro phase I metabolism in HLM more comprehensively than did EC-Fenton or EC. Even though TiO2 photocatalysis, EC-Fenton and EC do not allow comprehensive prediction of phase I metabolism, all three methods produce several important metabolites without the need for demanding purification steps to remove the biological matrix. Importantly, TiO2 photocatalysis produces aliphatic and aromatic hydroxylation products where direct EC fails. Furthermore, TiO2 photocatalysis is an extremely rapid, simple and inexpensive way to generate oxidation products in a clean matrix and the reaction can be simply initiated and quenched by switching the UV lamp on/off. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Reaction of hydrogen atoms produced by radiolysis and photolysis in solid phase at 4 and 77 K

    International Nuclear Information System (INIS)

    Miyazaki, Tetsuo

    1991-01-01

    The behavior of H atoms in the solid phase has been reviewed with special attention to comparison of H atoms produced by radiolysis with those produced by photolysis. The paper consists of three parts. I -Production of H atoms: (1) the experimental results which indicate H-atom formation in the radiolysis of solid alkane are summarized; (2) ESR saturation behavior of trapped H atoms depends upon the method of H-atom-production, i.e. photolysis or radiolysis, and upon the initial energy of H atoms in the photolysis. II - Diffusion of H atoms: (1) activation energies for thermally-activated diffusion of H atoms are shown; (2) quantum diffusion of H atoms in solid H 2 is explained in terms of repetition of tunneling reaction H 2 + H → H + H 2 . III -Reaction of H atoms: (1) reactions and trapping processes of hot H atoms have been shown in solid methane and argon by use of hot H atoms with specified initial energy; (2) when H atoms are produced by the radiolysis of solvent alkane or by the photolysis of HI in the alkane mixtures at 77 K, the H atoms react very selectively with solute alkane at low concentration. The selective reaction of the H atom has been found in eight matrices; (3) activation energy for a hydrogen-atom-abstraction reaction by thermal H atoms at low temperatures is less than than several kJ mol -1 because of quantum tunneling. The absolute rate constants for H 2 (D 2 , HD) + H(D) tunneling reactions have been determined experimentally in solid hydrogen at 4.2K; (4) theoretical studies for tunneling reactions H 2 (D 2 ,HD) + H(D) at ultralow temperatures were reviewed. The calculated rate constants were compared with the rate constants obtained experimentally. (author)

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

    Science.gov (United States)

    Tsujiuchi, Yutaka; Masumoto, Hiroshi; Goto, Takashi

    2016-04-01

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

  4. Studies of gas phase ion/molecule reactions by Fourier transform ion cyclotron resonance mass spectrometry

    International Nuclear Information System (INIS)

    Kleingeld, J.C.

    1984-01-01

    An important field in which Fourier-transform ion cyclotron resonance has useful applications is that of gas phase ion chemistry, the subject of this thesis. First, the general picture of ion-molecule reactions in the gas phase is discussed. Next, some positive ion-molecule reactions are described, whereas the remaining chapters deal with negative ion-molecule reactions. Most of these studies have been performed using the FT-ICR method. Reactions involving H 3 O - and NH 4 - ions are described whereas the other chapters deal with larger organic complexes. (Auth.)

  5. Pycnonuclear reaction rates for binary ionic mixtures

    Science.gov (United States)

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

    1992-01-01

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

  6. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

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

    Science.gov (United States)

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

    2015-12-01

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

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

    International Nuclear Information System (INIS)

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

    1980-09-01

    The Interlaboratory Reaction Rate UILRR) program is establishing the capability to accurately measure neutron-induced reactions and reaction rates for reactor fuels and materials development programs. The goal for the principal fission reactions, 235 U, 238 U and 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

  9. On the solid–liquid phase diagrams of binary mixtures of even saturated fatty alcohols: Systems exhibiting peritectic reaction

    Energy Technology Data Exchange (ETDEWEB)

    Carareto, Natália D.D. [EXTRAE, Department of Food Engineering, Food Engineering Faculty, University of Campinas, UNICAMP, CEP 13083-862 Campinas, SP (Brazil); Santos, Adenílson O. dos [Social Sciences, Health and Technology Center, University of Maranhão, UFMA, CEP 65900-410 Imperatriz, MA (Brazil); Rolemberg, Marlus P. [Institute of Science and Technology, University of Alfenas, UNIFAL, Rodovia José AurélioVilela, CEP 37715400 Poços de Caldas, MG (Brazil); Cardoso, Lisandro P. [Institute of Physics GlebWataghin, University of Campinas, UNICAMP, C.P. 6165, CEP 13083-970 Campinas, SP (Brazil); Costa, Mariana C. [School of Applied Science, University of Campinas, UNICAMP, CEP 13484-350 Limeira, SP (Brazil); Meirelles, Antonio J.A., E-mail: tomze@fea.unicamp.br [EXTRAE, Department of Food Engineering, Food Engineering Faculty, University of Campinas, UNICAMP, CEP 13083-862 Campinas, SP (Brazil)

    2014-08-10

    Highlights: • SLE of binary mixtures of saturated fatty alcohols was studied. • Experimental data were obtained using DSC and stepscan DSC. • Microscopy and X-ray diffraction used as complementary techniques. • Systems presented eutectic, peritectic and metatectic points. - Abstract: The solid–liquid phase diagrams of the following binary mixtures of even saturated fatty alcohols are reported in the literature for the first time: 1-octanol (C8OH) + 1-decanol (C10OH), 1-decanol + 1-dodecanol (C12OH), 1-dodecanol + 1-hexadecanol (C16OH) and 1-tetradecanol (C14OH) + 1-octadecanol (C18OH). The phase diagrams were obtained by differential scanning calorimetry (DSC) using a linear heating rate of 1 K min{sup −1} and further investigated by using a stepscan DSC method. X-ray diffraction (XRD) and polarized light microscopy were also used to complement the characterization of the phase diagrams which have shown a complex global behavior, presenting not only peritectic and eutectic reactions, but also the metatectic reaction and partial immiscibility on solid state.

  10. On the solid–liquid phase diagrams of binary mixtures of even saturated fatty alcohols: Systems exhibiting peritectic reaction

    International Nuclear Information System (INIS)

    Carareto, Natália D.D.; Santos, Adenílson O. dos; Rolemberg, Marlus P.; Cardoso, Lisandro P.; Costa, Mariana C.; Meirelles, Antonio J.A.

    2014-01-01

    Highlights: • SLE of binary mixtures of saturated fatty alcohols was studied. • Experimental data were obtained using DSC and stepscan DSC. • Microscopy and X-ray diffraction used as complementary techniques. • Systems presented eutectic, peritectic and metatectic points. - Abstract: The solid–liquid phase diagrams of the following binary mixtures of even saturated fatty alcohols are reported in the literature for the first time: 1-octanol (C8OH) + 1-decanol (C10OH), 1-decanol + 1-dodecanol (C12OH), 1-dodecanol + 1-hexadecanol (C16OH) and 1-tetradecanol (C14OH) + 1-octadecanol (C18OH). The phase diagrams were obtained by differential scanning calorimetry (DSC) using a linear heating rate of 1 K min −1 and further investigated by using a stepscan DSC method. X-ray diffraction (XRD) and polarized light microscopy were also used to complement the characterization of the phase diagrams which have shown a complex global behavior, presenting not only peritectic and eutectic reactions, but also the metatectic reaction and partial immiscibility on solid state

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

    Energy Technology Data Exchange (ETDEWEB)

    Thanh, Vo Hong, E-mail: vo@cosbi.eu [The Microsoft Research - University of Trento Centre for Computational and Systems Biology, Piazza Manifattura 1, Rovereto 38068 (Italy); Priami, Corrado, E-mail: priami@cosbi.eu [The Microsoft Research - University of Trento Centre for Computational and Systems Biology, Piazza Manifattura 1, Rovereto 38068 (Italy); Department of Mathematics, University of Trento, Trento (Italy)

    2015-08-07

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

  12. Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model

    NARCIS (Netherlands)

    Bickelhaupt, F. Matthias; Houk, Kendall N.

    2017-01-01

    The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction

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

    Science.gov (United States)

    Gehret, Austin U.

    2017-01-01

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

  14. [Preparation of Coated CMC-Fe0 Using Rheological Phase Reaction Method and Research on Degradation of TCE in Water].

    Science.gov (United States)

    Fan, Wen-jing; Cheng, Yue; Yu, Shu-zhen; Fan, Xiao-feng

    2015-06-01

    The coated nanoscale zero-valent iron (coated CMC-Fe0) was synthesized with cheap and environment friendly CMC as the coating agent using rheological phase reaction. The sample was characterized by means of XRD, SEM, TEM and N2 adsorption-stripping and used to study reductive dechlorination of TCE. The experimental results indicated that the removal rate of TCE was about 100% when the CMC-Fe0 dosage was 6 g x L(-1), the initial TCE concentration was 5 mg x L(-1) and the reaction time was 40 h. The TCE degradation reaction of coated CMC-Fe0 followed a pseudo-first-order kinetic model. Finally, the product could be simply recovered.

  15. Non-stationary filtration mode during chemical reactions with the gas phase

    Science.gov (United States)

    Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey

    2015-04-01

    An experimental and numerical study of filtration accompanied by chemical reactions between displacing fluid and solid skeleton is considered. Glass balls (400-500 μm in diameter) were placed in 1 cm gap between two glass sheets and were used as model porous medium. The baking soda was added to the glass balls. The 70% solution of acetic acid was used as the displacer. The modeling porous medium was saturated with a mineral oil, and then 70% solution of colored acetic acid was pumped through the medium. The glass balls and a mineral oil have a similar refractive index, so the model porous medium was optically transparent. During the filtration, the gas phase was generated by the chemical reactions between the baking soda and acetic acid, and time-dependent displacement of the chemical reaction front was observed. The front of the chemical reaction was associated with the most intensive gas separation. The front moved, stopped, and then moved again to the area where it had been already. We called this process a secondary oxidation wave. To describe this effect, we added to the balance equations a term associated with the formation and disappearance of phases due to chemical reactions. The equations were supplemented by Darcy's law for multiphase filtration. Nonstationarity front propagation of the chemical reaction in the numerical experiment was observed at Damköhler numbers greater than 100. The mathematical modelling was agreed well with the experimental results.

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

    DEFF Research Database (Denmark)

    Nielsen, Jens Bredal

    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...... of the thermokinetic description of reaction rates to include the influence of effecters. 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...

  17. New determination of the 2H(d,p)3H and 2H(d,n)3He reaction rates at astrophysical energies

    International Nuclear Information System (INIS)

    Tumino, A.; Spartà, R.; Spitaleri, C.; Pizzone, R. G.; La Cognata, M.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Mukhamedzhanov, A. M.; Typel, S.; Tognelli, E.; Degl'Innocenti, S.; Prada Moroni, P. G.; Burjan, V.; Kroha, V.; Hons, Z.; Mrazek, J.; Piskor, S.; Lamia, L.

    2014-01-01

    The cross sections of the 2 H(d,p) 3 H and 2 H(d,n) 3 He reactions have been measured via the Trojan Horse method applied to the quasi-free 2 H( 3 He,p 3 H) 1 H and 2 H( 3 He,n 3 He) 1 H processes at 18 MeV off the proton in 3 He. For the first time, the bare nucleus S(E) factors have been determined from 1.5 MeV, across the relevant region for standard Big Bang nucleosynthesis, down to the thermal energies of deuterium burning in the pre-main-sequence (PMS) phase of stellar evolution, as well as of future fusion reactors. Both the energy dependence and the absolute value of the S(E) factors deviate by more than 15% from the available direct data and existing fitting curves, with substantial variations in the electron screening by more than 50%. As a consequence, the reaction rates for astrophysics experience relevant changes, with a maximum increase of up to 20% at the temperatures of the PMS phase. From a recent primordial abundance sensitivity study, it turns out that the 2 H(d,n) 3 He reaction is quite influential on 7 Li, and the present change in the reaction rate leads to a decrease in its abundance by up to 10%. The present reaction rates have also been included in an updated version of the FRANEC evolutionary code to analyze their influence on the central deuterium abundance in PMS stars with different masses. The largest variation of about 10%-15% pertains to young stars (≤1 Myr) with masses ≥1 M ☉ .

  18. MOLECULAR SPECTROSCPY AND REACTIONS OF ACTINIDES IN THE GAS PHASE AND CRYOGENIC MATRICES

    Energy Technology Data Exchange (ETDEWEB)

    Heaven, Michael C.; Gibson, John K.; Marcalo, Joaquim

    2009-02-01

    In this chapter we review the spectroscopic data for actinide molecules and the reaction dynamics for atomic and molecular actinides that have been examined in the gas phase or in inert cryogenic matrices. The motivation for this type of investigation is that physical properties and reactions can be studied in the absence of external perturbations (gas phase) or under minimally perturbing conditions (cryogenic matrices). This information can be compared directly with the results from high-level theoretical models. The interplay between experiment and theory is critically important for advancing our understanding of actinide chemistry. For example, elucidation of the role of the 5f electrons in bonding and reactivity can only be achieved through the application of experimentally verified theoretical models. Theoretical calculations for the actinides are challenging due the large numbers of electrons that must be treated explicitly and the presence of strong relativistic effects. This topic has been reviewed in depth in Chapter 17 of this series. One of the goals of the experimental work described in this chapter has been to provide benchmark data that can be used to evaluate both empirical and ab initio theoretical models. While gas-phase data are the most suitable for comparison with theoretical calculations, there are technical difficulties entailed in generating workable densities of gas-phase actinide molecules that have limited the range of species that have been characterized. Many of the compounds of interest are refractory, and problems associated with the use of high temperature vapors have complicated measurements of spectra, ionization energies, and reactions. One approach that has proved to be especially valuable in overcoming this difficulty has been the use of pulsed laser ablation to generate plumes of vapor from refractory actinide-containing materials. The vapor is entrained in an inert gas, which can be used to cool the actinide species to room

  19. Solid gas reaction phase diagram under high gas pressure

    International Nuclear Information System (INIS)

    Ishizaki, K.

    1992-01-01

    This paper reports that to evaluate which are the stable phases under high gas pressure conditions, a solid-gas reaction phase diagram under high gas pressure (HIP phase diagram) has been proposed by the author. The variables of the diagram are temperature, reactant gas partial pressure and total gas pressure. Up to the present time the diagrams have been constructed using isobaric conditions. In this work, the stable phases for a real HIP process were evaluated assuming an isochoric condition. To understand the effect of the total gas pressure on stability is of primary importance. Two possibilities were considered and evaluated, those are: the total gas pressure acts as an independent variable, or it only affects the fugacity values. The results of this work indicate that the total gas pressure acts as an independent variable, and in turn also affects the fugacity values

  20. Rate constants for some electrophilic reactions of benzyl, benzhydryl, and trityl cations in solution

    International Nuclear Information System (INIS)

    Ujdak, R.J.; Jones, R.L.; Dorfman, L.M.

    1976-01-01

    Absolute rate constants have been determined by the pulse radiolysis technique for several electrophilic reactions of the benzyl, the benzhydryl, and the trityl cation in 1,2-dichloroethane solution. The rate constants for the reactions of these carbonium ions with chloride ion, with bromide ion, and with iodide ion are all very nearly the same, namely 6 x 10 10 M -1 s -1 at 24 0 C. The values very likely represent the diffusion controlled limit for the ion combination reactions. The rate constants for the reactions with triethylamine, tri-n-propylamine, and tri-n-butylamine range from 2.0 x 10 9 to 7 x 10 6 M -1 s -1 at 24 0 C. With increasing phenyl substitution, the decreasing trend in the magnitude of the rate constant is consistent with the combined electronic and steric effects. With increasing size of the amine, the decrease in the value of the rate constant seems to indicate that the steric effect predominates. The values of the rate constants for reactions of benzyl and benzhydryl cation with methanol, ethanol, and 2-propanol indicate the following. The rate constant is higher for reaction with the alcohol dimer in solution than with alcohol monomer. The rate constants for reaction with alcohol monomer have values of 1 x 10 8 M -1 s -1 or lower

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

    Science.gov (United States)

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

    2017-11-01

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

  2. Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

    Science.gov (United States)

    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.

  3. Coloring Rate of Phenolphthalein by Reaction with Alkaline Solution Observed by Liquid-Droplet Collision.

    Science.gov (United States)

    Takano, Yuuka; Kikkawa, Shigenori; Suzuki, Tomoko; Kohno, Jun-ya

    2015-06-11

    Many important chemical reactions are induced by mixing two solutions. This paper presents a new way to measure rates of rapid chemical reactions induced by mixing two reactant solutions using a liquid-droplet collision. The coloring reaction of phenolphthalein (H2PP) by a reaction with NaOH is investigated kinetically. Liquid droplets of H2PP/ethanol and NaOH/H2O solutions are made to collide, which induces a reaction that transforms H2PP into a deprotonated form (PP(2-)). The concentration of PP(2-) is evaluated from the RGB values of pixels in the colored droplet images, and is measured as a function of the elapsed time from the collision. The obtained rate constant is (2.2 ± 0.7) × 10(3) M(-1) s(-1), which is the rate constant for the rate-determining step of the coloring reaction of H2PP. This method was shown to be applicable to determine rate constants of rapid chemical reactions between two solutions.

  4. Explore the reaction mechanism of the Maillard reaction: a density functional theory study.

    Science.gov (United States)

    Ren, Ge-Rui; Zhao, Li-Jiang; Sun, Qiang; Xie, Hu-Jun; Lei, Qun-Fang; Fang, Wen-Jun

    2015-05-01

    The mechanism of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution. The Maillard reaction is a cascade of consecutive and parallel reaction. In the present model system study, glucose and glycine were taken as the initial reactants. On the basis of previous experimental results, the mechanisms of Maillard reaction have been proposed, and the possibility for the formation of different compounds have been evaluated through calculating the relative energy changes for different steps of reaction under different pH conditions. Our calculations reveal that the TS3 in Amadori rearrangement reaction is the rate-determining step of Maillard reaction with the activation barriers of about 66.7 and 68.8 kcal mol(-1) in the gaseous phase and aqueous solution, respectively. The calculation results are in good agreement with previous studies and could provide insights into the reaction mechanism of Maillard reaction, since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.

  5. Surface reaction rate and probability of ozone and alpha-terpineol on glass, polyvinyl chloride, and latex paint surfaces.

    Science.gov (United States)

    Shu, Shi; Morrison, Glenn C

    2011-05-15

    Ozone can react homogeneously with unsaturated organic compounds in buildings to generate undesirable products. However, these reactions can also occur on indoor surfaces, especially for low-volatility organics. Conversion rates of ozone with α-terpineol, a representative low-volatility compound, were quantified on surfaces that mimic indoor substrates. Rates were measured for α-terpineol adsorbed to beads of glass, polyvinylchloride (PVC), and dry latex paint, in a plug flow reactor. A newly defined second-order surface reaction rate coefficient, k(2), was derived from the flow reactor model. The value of k(2) ranged from 0.68 × 10(-14) cm(4)s(-1)molecule(-1) for α-terpineol adsorbed to PVC to 3.17 × 10(-14) cm(4)s(-1)molecule(-1) for glass, but was insensitive to relative humidity. Further, k(2) is only weakly influenced by the adsorbed mass but instead appears to be more strongly related to the interfacial activity α-terpineol. The minimum reaction probability ranged from 3.79 × 10(-6) for glass at 20% RH to 6.75 × 10(-5) for PVC at 50% RH. The combination of high equilibrium surface coverage and high reactivity for α-terpineol suggests that surface conversion rates are fast enough to compete with or even overwhelm other removal mechanisms in buildings such as gas-phase conversion and air exchange.

  6. Neutron Scattering in Hydrogenous Moderators, Studied by Time Dependent Reaction Rate Method

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, L G; Moeller, E; Purohit, S N

    1966-03-15

    The moderation and absorption of a neutron burst in water, poisoned with the non-1/v absorbers cadmium and gadolinium, has been followed on the time scale by multigroup calculations, using scattering kernels for the proton gas and the Nelkin model. The time dependent reaction rate curves for each absorber display clear differences for the two models, and the separation between the curves does not depend much on the absorber concentration. An experimental method for the measurement of infinite medium reaction rate curves in a limited geometry has been investigated. This method makes the measurement of the time dependent reaction rate generally useful for thermalization studies in a small geometry of a liquid hydrogenous moderator, provided that the experiment is coupled to programs for the calculation of scattering kernels and time dependent neutron spectra. Good agreement has been found between the reaction rate curve, measured with cadmium in water, and a calculated curve, where the Haywood kernel has been used.

  7. Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

    Science.gov (United States)

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

    1986-01-01

    The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

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

    Science.gov (United States)

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

    2017-09-01

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

  9. Experimental and theoretical studies on gas-phase reactions of NO3 radicals with three methoxyphenols: Guaiacol, creosol, and syringol

    Science.gov (United States)

    Yang, Bo; Zhang, Haixu; Wang, Youfeng; Zhang, Peng; Shu, Jinian; Sun, Wanqi; Ma, Pengkun

    2016-01-01

    Methoxyphenols, lignin pyrolysis products, are major biomass combustion components and are considered potential tracers for wood smoke emissions. Their atmospheric reactivity, however, has not been well characterized. Guaiacol, creosol, and syringol are three typical methoxyphenols generated in relatively high concentrations in fresh wood smoke. In this study, the gas-phase reactions of NO3 radicals with these methoxyphenols were investigated using a laboratory-built vacuum ultraviolet photoionization gas time-of-flight mass spectrometer (VUV-GTOFMS) and off-line GC-MS. By combining experimental and theoretical methods, 4-nitroguaiacol, 6-nitroguaiacol, and 4,6-dinitroguaiacol were determined as the primary degradation products for guaiacol; similarly, 6-nitrocreosol and 3-nitrosyringol were identified for creosol and syringol, respectively. Using the relative rate method, rate constants at 298 K and 1 atm for the gas-phase reactions of guaiacol, creosol, and syringol with NO3 radicals were measured to be 3.2 × 10-12, 2.4 × 10-13, and 4.0 × 10-13 cm3 molecule-1 s-1, respectively. At a typical tropospheric concentration of NO3 radicals (5 × 108 molecule cm-3), atmospheric lifetimes for guaiacol, creosol, and syringol toward NO3 radicals were 0.2, 2.3, and 1.4 h, respectively. These results indicate that the reaction with NO3 radicals can be a major sink for methoxyphenols at night.

  10. The Influence of Mixing in High Temperature Gas Phase Reactions

    DEFF Research Database (Denmark)

    Østberg, Martin

    1996-01-01

    by injection of NH3 with carrier gas into the flue gas. NH3 can react with NO and form N2, but a competing reaction path is the oxidation of NH3 to NO.The SNR process is briefly described and it is shown by chemical kinetic modelling that OH radicals under the present conditions will initiate the reaction......The objective of this thesis is to describe the mixing in high temperature gas phase reactions.The Selective Non-Catalytic Reduction of NOx (referred as the SNR process) using NH3 as reductant was chosen as reaction system. This in-furnace denitrification process is made at around 1200 - 1300 K...... diffusion. The SNR process is simulated using the mixing model and an empirical kinetic model based on laboratory experiments.A bench scale reactor set-up has been built using a natural gas burner to provide the main reaction gas. The set-up has been used to perform an experimental investigation...

  11. Effects of Undercooling and Cooling Rate on Peritectic Phase Crystallization Within Ni-Zr Alloy Melt

    Science.gov (United States)

    Lü, P.; Wang, H. P.

    2018-04-01

    The liquid Ni-16.75 at. pct Zr peritectic alloy was substantially undercooled and containerlessly solidified by an electromagnetic levitator and a drop tube. The dependence of the peritectic solidification mode on undercooling was established based on the results of the solidified microstructures, crystal growth velocity, as well as X-ray diffraction patterns. Below a critical undercooling of 124 K, the primary Ni7Zr2 phase preferentially nucleates and grows from the undercooled liquid, which is followed by a peritectic reaction of Ni7Zr2+L → Ni5Zr. The corresponding microstructure is composed of the Ni7Zr2 dendrites, peritectic Ni5Zr phase, and inter-dendritic eutectic. Nevertheless, once the liquid undercooling exceeds the critical undercooling, the peritectic Ni5Zr phase directly precipitates from this undercooled liquid. However, a negligible amount of residual Ni7Zr2 phase still appears in the microstructure, indicating that nucleation and growth of the Ni7Zr2 phase are not completely suppressed. The micromechanical property of the peritectic Ni5Zr phase in terms of the Vickers microhardness is enhanced, which is ascribed to the transition of the peritectic solidification mode. To suppress the formation of the primary phase completely, this alloy was also containerlessly solidified in free fall experiments. Typical peritectic solidified microstructure forms in large droplets, while only the peritectic Ni5Zr phase appears in smaller droplets, which gives an indication that the peritectic Ni5Zr phase directly precipitates from the undercooled liquid by completely suppressing the growth of the primary Ni7Zr2 phase and the peritectic reaction due to the combined effects of the large undercooling and high cooling rate.

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

    Science.gov (United States)

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

    2015-01-01

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

  13. Ozonation of norfloxacin and levofloxacin in water: Specific reaction rate constants and defluorination reaction.

    Science.gov (United States)

    Ling, Wencui; Ben, Weiwei; Xu, Ke; Zhang, Yu; Yang, Min; Qiang, Zhimin

    2018-03-01

    The degradation kinetics and mechanism of two typical fluoroquinolones (FQs), norfloxacin (NF) and levofloxacin (LOF), by ozone in water were investigated. Semi-continuous mode and competition kinetics mode experiments were conducted to determine the reaction rate constants of target FQs with ozone and OH, separately. Results indicate that both NF and LOF were highly reactive toward ozone, and the reactivity was strongly impacted by the solution pH. The specific reaction rate constants of the diprotonated, monoprotonated and deprotonated species were determined to be 7.20 × 10 2 , 8.59 × 10 3 , 4.54 × 10 5  M -1  s -1 respectively for NF and 1.30 × 10 3 , 1.40 × 10 4 , 1.33 × 10 6  M -1  s -1 respectively for LOF. The reaction rate constants of target FQs toward OH were measured to be (4.81-7.41) × 10 9  M -1  s -1 in the pH range of 6.3-8.3. Furthermore, NF was selected as a model compound to clarify the degradation pathways, with a particular focus on the defluorination reaction. The significant release of F - ions and the formation of three F-free organic byproducts indicated that defluorination was a prevalent pathway in ozonation of FQs, while six F-containing organic byproducts indicated that ozone also attacked the piperazinyl and quinolone moieties. Escherichia coli growth inhibition tests revealed that ozonation could effectively eliminate the antibacterial activity of target FQ solutions, and the residual antibacterial activity had a negative linear correlation with the released F - concentration. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2017-02-09

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

  15. Putting Reaction Rates and Collision Theory in the Hands of Your Students.

    Science.gov (United States)

    Evenson, Andy

    2002-01-01

    Describes a simulation that can be used to give concrete analogies of collision theory and the factors that affect reaction rates including temperature, concentration, catalyst, and molecular orientation. The simulation works best if done as an introduction to the concepts to help prevent misconceptions about reaction rates and collision theory.…

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

    NARCIS (Netherlands)

    Harrevelt, R. van; Nyman, G.; Manthe, U.

    2007-01-01

    In previous work [T. Wu, H. J. Werner, and U. Manthe, Science 306, 2227 (2004)], accurate quantum reaction rate calculations of the rate constant for the H+CH4 -> CH3+H-2 reaction have been presented. Both the electronic structure calculations and the nuclear dynamics calculations are converged with

  17. Phase development and kinetics of high temperature Bi-2223 phase

    International Nuclear Information System (INIS)

    Yavuz, M.; Maeda, H.; Hua, K.L.; Shi, X.D.

    1998-01-01

    The two-dimensional nucleation (random)-growth mechanism were observed as a support for the related previous works, which is attributable to the growth of the Bi-2223 grain in the a-b plane direction of the Bi-2212 matrix is being much faster than in the c-direction, or that the early-formed plate-like 2212 phase confines the 2223 product. At the beginning of the reaction, the additional phases are partially melted. Because of the structure, composition and thermal fluctuation, the 2223 nucleates and grows in the phase boundary between the liquid phase and Bi-2212. It was shown here that the nucleation and the growth rate were relatively fast between 0 and 36 h. At the final stage, between 36 and 60 h, because of the impingement of the growth fronts of different nuclei, the high formation rate of 2223 is suppressed. The major reactant 2212 remains as a solid and its plate-like configuration determines the two dimensional nature of the reaction. The amount of liquid forms during reaction is small. (orig.)

  18. Sulphide phases in Y zeolite for hydro-treatment reactions; Phase sulfures dans une zeolithe Y pour l'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Leyrit, P

    1999-06-28

    Several types of single (Mo, Co, Pd, Pt) or binary (MoCo, PdCo, PtCo) sulphides phases supported on a HY zeolite were studied. The catalysts were first prepared and characterised in the oxide form. Their reactivity was then evaluated in toluene hydrogenation and 4.6-dimethyl-dibenzo-thiophene hydro-desulfurization reactions. Characterisation of sulphide phases supported on HY zeolite was carried out by elemental analysis, X-Ray Diffraction (XRD), Transmission Electron Microscopy and Scanning Transmission Electron Microscopy (STEM), Extended X-Ray Absorption Fine Structure (EXAFS) and Temperature Programmed Reduction coupled with HS analysis. The results show that. compared with alumina supported catalysts, zeolite used as a support enables extremely active catalysts to be obtained. It appears in particular that molybdenum sulphide phases inside the zeolite have a very high intrinsic activity at low molybdenum content. This activity is attributed to highly dispersed molybdenum sulphide phases differing from MoS{sub 2} slabs and probably present as clusters. The influence of cobalt depends of its concentration. Thus at low loadings cobalt has a strong negative effect. It has been shown, in the molybdenum case, that cobalt interaction leads to an increase in the sulphur content of the molybdenum phases. At higher cobalt loading, the formation of a mixed phase is possible but the degree of promotion remains limited. This work emphasises the advantages of using zeolite supported sulphide phases, and especially Mo and Pd phases, in the hydro-treatment reactions. It seems however that single phases present a greater interest than binary phases. (author)

  19. Gas phase reactions of nitrogen oxides with olefins

    Energy Technology Data Exchange (ETDEWEB)

    Altshuller, A P; Cohen, I

    1961-01-01

    The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

  20. Connecting localized DNA strand displacement reactions

    Science.gov (United States)

    Mullor Ruiz, Ismael; Arbona, Jean-Michel; Lad, Amitkumar; Mendoza, Oscar; Aimé, Jean-Pierre; Elezgaray, Juan

    2015-07-01

    Logic circuits based on DNA strand displacement reactions have been shown to be versatile enough to compute the square root of four-bit numbers. The implementation of these circuits as a set of bulk reactions faces difficulties which include leaky reactions and intrinsically slow, diffusion-limited reaction rates. In this paper, we consider simple examples of these circuits when they are attached to platforms (DNA origamis). As expected, constraining distances between DNA strands leads to faster reaction rates. However, it also induces side-effects that are not detectable in the solution-phase version of this circuitry. Appropriate design of the system, including protection and asymmetry between input and fuel strands, leads to a reproducible behaviour, at least one order of magnitude faster than the one observed under bulk conditions.Logic circuits based on DNA strand displacement reactions have been shown to be versatile enough to compute the square root of four-bit numbers. The implementation of these circuits as a set of bulk reactions faces difficulties which include leaky reactions and intrinsically slow, diffusion-limited reaction rates. In this paper, we consider simple examples of these circuits when they are attached to platforms (DNA origamis). As expected, constraining distances between DNA strands leads to faster reaction rates. However, it also induces side-effects that are not detectable in the solution-phase version of this circuitry. Appropriate design of the system, including protection and asymmetry between input and fuel strands, leads to a reproducible behaviour, at least one order of magnitude faster than the one observed under bulk conditions. Electronic supplementary information (ESI) available. See DOI: 10.1039/C5NR02434J

  1. Effects of Surfactants on the Rate of Chemical Reactions

    Directory of Open Access Journals (Sweden)

    B. Samiey

    2014-01-01

    Full Text Available Surfactants are self-assembled compounds that depend on their structure and electric charge can interact as monomer or micelle with other compounds (substrates. These interactions which may catalyze or inhibit the reaction rates are studied with pseudophase, cooperativity, and stoichiometric (classical models. In this review, we discuss applying these models to study surfactant-substrate interactions and their effects on Diels-Alder, redox, photochemical, decomposition, enzymatic, isomerization, ligand exchange, radical, and nucleophilic reactions.

  2. Direct determination of enthalpies of solid phase reactions by immersion method; Determination directe des enthalpies de reaction en phase solide par une methode de plongee

    Energy Technology Data Exchange (ETDEWEB)

    Roux, A; Richard, M; Eyraud, L; Stevanovic, M; Elston, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-07-01

    It is not generally possible to measure the enthalpy change corresponding to solid phase reactions using the dynamic differential thermal analysis method because these reactions are usually too slow at the temperature of operation of present equipment. A ballistic differential thermal analysis apparatus has been developed which is based on an immersion-compensation method; it overcomes the difficulties previously encountered. This apparatus has been used after calibration for determining the enthalpies of formation of calcium and cadmium titanates. and also the Wigner energies of BeO, MgO and Al{sub 2}O{sub 3} samples irradiated at variable dose at a temperature of under 100 deg. C. (authors) [French] Il n'est generalement pas possible de mesurer la variation d'enthalpie correspondant aux reactions en phase solide par la methode d'analyse thermique differentielle dynamique. En effet, ces reactions sont le plus souvent trop lentes aux temperatures d'utilisation des dispositifs actuels. Un appareil d'analyse thermique differentielle balistique, base sur une methode de plongee avec compensation, a ete mis au point et permet de surmonter les difficultes precedentes. Apres etalonnages, cet appareil a ete utilise pour la determination des enthalpies de formation du titanate de calcium et du titanate de cadmium ainsi que pour celle des energies Wigner emmagasinees dans des echantillons de BeO, MgO et Al{sub 2}O{sub 3} irradies a une temperature inferieure a 100 deg. C et a differentes doses. (auteurs)

  3. Kinetics and Mechanism of the Gas-Phase Reaction of Selected Carbonyls with Cl Atoms between 250 and 340 K

    Science.gov (United States)

    Hasson, A. S.; Algrim, L.; Abdelhamid, A.; Tyndall, G. S.; Orlando, J. J.

    2013-12-01

    Carbonyls are important products from the gas phase degradation of most volatile organic compounds. Their atmospheric reactions therefore have a significant impact on atmospheric composition, particularly in aged air masses. While the reactions of short-chain linear carbonyls are well understood, the chemistry of larger (> C6) and branched carbonyl is more uncertain. To provide insight into these reactions, the reactions of three carbonyls (methyl isopropyl ketone, MIK; di-isopropyl ketone, DIK; and diethyl ketone, DEK) with chlorine atoms were investigated between 250 and 340 K and 1 atm in the presence and absence of NOx and an HO2 source (methanol). Experiments were performed in a photochemical reactor using a combination of long-path Fourier transform infra-red spectroscopy, proton transfer reaction mass spectrometry and gas chromatography with flame ionization detection. The kinetics were studied using the relative rate technique with butanone and isopropanol as the reference compounds. The Arrhenius expression for the three rate coefficients was determined to be k(DEK+Cl) = 3.87 x 10-11e(2 × 7 kJ/mol)/RT cm3 molecules-1 s-1 , k(MIPK+Cl) = 7.20 x 10-11e(0.2× 8 kJ/mol)/RT cm3 molecules-1 s-1 , and k(DIPK+Cl) = 3.33 x 10-10e(-3× 8 kJ/mol)/RT cm3 molecules-1 s-1 . Measured reaction products accounted for 38-72 % of the reacted carbon and were consistent with strong deactivation of the carbon atom adjacent to the carbonyl group with respect to H-atom abstraction by Cl atoms. The product distributions also provide insight into radical recycling from the organic peroxy + HO2 reaction, and the relative rates of isomerization, fragmentation and reaction with O2 for carbonyl-containing alkoxy radicals. Implications of these results will be discussed.

  4. Reaction rate calculations via transmission coefficients

    International Nuclear Information System (INIS)

    Feit, M.D.; Alder, B.J.

    1985-01-01

    The transmission coefficient of a wavepacket traversing a potential barrier can be determined by steady state calculations carried out in imaginary time instead of by real time dynamical calculations. The general argument is verified for the Eckart barrier potential by a comparison of transmission coefficients calculated from real and imaginary time solutions of the Schroedinger equation. The correspondence demonstrated here allows a formulation for the reaction rate that avoids difficulties due to both rare events and explicitly time dependent calculations. 5 refs., 2 figs

  5. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

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

    Science.gov (United States)

    Olbris, Donald J.; Herzfeld, Judith

    2002-01-01

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

  7. Nanoparticle growth by particle-phase chemistry

    Science.gov (United States)

    Apsokardu, Michael J.; Johnston, Murray V.

    2018-02-01

    The ability of particle-phase chemistry to alter the molecular composition and enhance the growth rate of nanoparticles in the 2-100 nm diameter range is investigated through the use of a kinetic growth model. The molecular components included are sulfuric acid, ammonia, water, a non-volatile organic compound, and a semi-volatile organic compound. Molecular composition and growth rate are compared for particles that grow by partitioning alone vs. those that grow by a combination of partitioning and an accretion reaction in the particle phase between two organic molecules. Particle-phase chemistry causes a change in molecular composition that is particle diameter dependent, and when the reaction involves semi-volatile molecules, the particles grow faster than by partitioning alone. These effects are most pronounced for particles larger than about 20 nm in diameter. The modeling results provide a fundamental basis for understanding recent experimental measurements of the molecular composition of secondary organic aerosol showing that accretion reaction product formation increases linearly with increasing aerosol volume-to-surface-area. They also allow initial estimates of the reaction rate constants for these systems. For secondary aerosol produced by either OH oxidation of the cyclic dimethylsiloxane (D5) or ozonolysis of β-pinene, oligomerization rate constants on the order of 10-3 to 10-1 M-1 s-1 are needed to explain the experimental results. These values are consistent with previously measured rate constants for reactions of hydroperoxides and/or peroxyacids in the condensed phase.

  8. Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

    International Nuclear Information System (INIS)

    Fagerstroem, K.

    1993-01-01

    The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

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

    Science.gov (United States)

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

    2014-01-01

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

  10. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  11. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs

    NARCIS (Netherlands)

    Ruokolainen, Miina; Gül, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio

    2016-01-01

    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and

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

    Science.gov (United States)

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

    1985-02-01

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

  13. RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

    Science.gov (United States)

    Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

  14. Reaction rate constant for uranium in water and water vapor

    Energy Technology Data Exchange (ETDEWEB)

    TRIMBLE, D.J.

    1998-11-09

    The literature on uranium oxidation in water and oxygen free water vapor was reviewed. Arrhenius rate equations were developed from the review data. These data and equations will be used as a baseline from which to compare reaction rates measured for K Basin fuel.

  15. Non-equilibrium effects in high temperature chemical reactions

    Science.gov (United States)

    Johnson, Richard E.

    1987-01-01

    Reaction rate data were collected for chemical reactions occurring at high temperatures during reentry of space vehicles. The principle of detailed balancing is used in modeling kinetics of chemical reactions at high temperatures. Although this principle does not hold for certain transient or incubation times in the initial phase of the reaction, it does seem to be valid for the rates of internal energy transitions that occur within molecules and atoms. That is, for every rate of transition within the internal energy states of atoms or molecules, there is an inverse rate that is related through an equilibrium expression involving the energy difference of the transition.

  16. Communication: Control of chemical reactions using electric field gradients

    Energy Technology Data Exchange (ETDEWEB)

    Deshmukh, Shivaraj D.; Tsori, Yoav, E-mail: tsori@bgu.ac.il [Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel)

    2016-05-21

    We examine theoretically a new idea for spatial and temporal control of chemical reactions. When chemical reactions take place in a mixture of solvents, an external electric field can alter the local mixture composition, thereby accelerating or decelerating the rate of reaction. The spatial distribution of electric field strength can be non-trivial and depends on the arrangement of the electrodes producing it. In the absence of electric field, the mixture is homogeneous and the reaction takes place uniformly in the reactor volume. When an electric field is applied, the solvents separate and the reactants are concentrated in the same phase or separate to different phases, depending on their relative miscibility in the solvents, and this can have a large effect on the kinetics of the reaction. This method could provide an alternative way to control runaway reactions and to increase the reaction rate without using catalysts.

  17. Communication: Control of chemical reactions using electric field gradients.

    Science.gov (United States)

    Deshmukh, Shivaraj D; Tsori, Yoav

    2016-05-21

    We examine theoretically a new idea for spatial and temporal control of chemical reactions. When chemical reactions take place in a mixture of solvents, an external electric field can alter the local mixture composition, thereby accelerating or decelerating the rate of reaction. The spatial distribution of electric field strength can be non-trivial and depends on the arrangement of the electrodes producing it. In the absence of electric field, the mixture is homogeneous and the reaction takes place uniformly in the reactor volume. When an electric field is applied, the solvents separate and the reactants are concentrated in the same phase or separate to different phases, depending on their relative miscibility in the solvents, and this can have a large effect on the kinetics of the reaction. This method could provide an alternative way to control runaway reactions and to increase the reaction rate without using catalysts.

  18. Helium generation reaction rates for 6Li and 10B in benchmark facilities

    International Nuclear Information System (INIS)

    Farrar, Harry IV; Oliver, B.M.; Lippincott, E.P.

    1980-01-01

    The helium generation rates for 10 B and 6 Li have been measured in two benchmark reactor facilities having neutron spectra similar to those found in a breeder reactor. The irradiations took place in the Coupled Fast Reactivity Measurements Facility (CFRMF) and in the 10% enriched 235 U critical assembly, BIG-10. The helium reaction rates were obtained by precise high-sensitivity gas mass spectrometric analyses of the helium content of numerous small samples. Comparison of these reaction rates with other reaction rates measured in the same facilities, and with rates calculated from published cross sections and from best estimates of the neutron spectral shapes, indicate significant discrepancies in the calculated values. Additional irradiations in other benchmark facilities have been undertaken to better determine the energy ranges where the discrepancies lie

  19. Determination of the rate of crystal growth from the gas phase under conditions of turbulent free convection

    Science.gov (United States)

    Alad'Ev, S. I.

    1987-04-01

    Crystal growth in vertical and horizontal cylindrical vials, with the substrate and the source serving as the vial ends, is investigated analytically, assuming that the medium consists of a binary mixture of an active and an inert gas. The active gas is made up of the gaseous products of reactions taking place at the substrate and at the source. It is shown that turbulent free convection leads to an increase in crystal growth rate. All other conditions being equal, crystal growth in vertical vials is greater than that in horizontal ones; in both cases crystal growth rate increases with the vial radius, temperature gradient in the gas phase, and gas phase density. The results are compared with experimental data on the growth of Ge crystals in the Ge-GeI4 system.

  20. GAS-PHASE REACTIONS OF POLYCYCLIC AROMATIC HYDROCARBON ANIONS WITH MOLECULES OF INTERSTELLAR RELEVANCE

    International Nuclear Information System (INIS)

    Demarais, Nicholas J.; Yang Zhibo; Martinez, Oscar; Wehres, Nadine; Bierbaum, Veronica M.; Snow, Theodore P.

    2012-01-01

    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C 6 H – 5 ), naphthalenide (C 10 H – 7 ), and anthracenide (C 14 H – 9 ) with atomic H, H 2 , and D 2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O 2 , CO 2 , N 2 O, C 2 H 2 , CH 3 OH, CH 3 CN, (CH 3 ) 2 CO, CH 3 CHO, CH 3 Cl, and (CH 3 CH 2 ) 2 O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  1. Gas-phase Reactions of Polycyclic Aromatic Hydrocarbon Anions with Molecules of Interstellar Relevance

    Science.gov (United States)

    Demarais, Nicholas J.; Yang, Zhibo; Martinez, Oscar; Wehres, Nadine; Snow, Theodore P.; Bierbaum, Veronica M.

    2012-02-01

    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C6H- 5), naphthalenide (C10H- 7), and anthracenide (C14H- 9) with atomic H, H2, and D2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O2, CO2, N2O, C2H2, CH3OH, CH3CN, (CH3)2CO, CH3CHO, CH3Cl, and (CH3CH2)2O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  2. Timing differences in the generation of ground reaction forces between the initial and secondary landing phases of the drop vertical jump.

    Science.gov (United States)

    Bates, Nathaniel A; Ford, Kevin R; Myer, Gregory D; Hewett, Timothy E

    2013-08-01

    Rapid impulse loads imparted on the lower extremity from ground contact when landing from a jump may contribute to ACL injury prevalence in female athletes. The drop jump and drop landing tasks enacted in the first and second landings of drop vertical jumps, respectively, have been shown to elicit separate neuromechanical responses. We examined the first and second landings of a drop vertical jump for differences in landing phase duration, time to peak force, and rate of force development. 239 adolescent female basketball players completed drop vertical jumps from an initial height of 31cm. In-ground force platforms and a three dimensional motion capture system recorded force and positional data for each trial. Between the first and second landing, rate of force development experienced no change (P>0.62), landing phase duration decreased (P=0.01), and time to peak ground reaction force increased (P0.12). The current results have important implications for the future assessment of ACL injury risk behaviors. Rate of force development remained unchanged between first and second landings from equivalent fall height, while time to peak reaction force increased during the second landing. Neither factor was dependent on the total time duration of landing phase, which decreased during the second landing. Shorter time to peak force may increase ligament strain and better represent the abrupt joint loading that is associated with ACL injury risk. © 2013.

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

    Science.gov (United States)

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

    2000-01-01

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

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

    Science.gov (United States)

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

    2012-07-01

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

  5. Measurement and analysis of reaction rate distributions of cores with spectrum shifter region

    International Nuclear Information System (INIS)

    Matsuura, Shigekazu; Shiroya, Seiji; Unesaki, Hironobu; Takeda, Toshikazu; Aizawa, Otohiko; Kanda, Keiji.

    1995-01-01

    A study for the neutronic characteristics of the spectrum-controlled neutron irradiation fields using various reflector materials was performed. Spectrum shifter regions were constructed in the upper reflector region of the solid moderated core (B-Core) of the Kyoto University Critical Assembly (KUCA). Beryllium, graphite and aluminum were selected as the loading materials for the spectrum shifter. Two tight-pitch lattice cores with different moderator-to-fuel volume ratio (V m /V f ) of 0.97 and 0.65 have been used. Axial reaction rate distributions of gold, nickel and indium wires were measured, and the spectrum index was defined as the Cd ratio of the gold wire and the ratio of gold reaction rate to nickel reaction rate. Using the conventional design calculation procedure, the experimental and calculated reaction rate and spectrum index show several disagreements. Detailed treatment of the neutron streaming effect, heterogeneous cell structure and depression factor are shown to be necessary for improving the agreement between experimental and calculated values. (author)

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  7. Sulphide phases in Y zeolite for hydro-treatment reactions; Phase sulfures dans une zeolithe Y pour l'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Leyrit, P.

    1999-06-28

    Several types of single (Mo, Co, Pd, Pt) or binary (MoCo, PdCo, PtCo) sulphides phases supported on a HY zeolite were studied. The catalysts were first prepared and characterised in the oxide form. Their reactivity was then evaluated in toluene hydrogenation and 4.6-dimethyl-dibenzo-thiophene hydro-desulfurization reactions. Characterisation of sulphide phases supported on HY zeolite was carried out by elemental analysis, X-Ray Diffraction (XRD), Transmission Electron Microscopy and Scanning Transmission Electron Microscopy (STEM), Extended X-Ray Absorption Fine Structure (EXAFS) and Temperature Programmed Reduction coupled with HS analysis. The results show that. compared with alumina supported catalysts, zeolite used as a support enables extremely active catalysts to be obtained. It appears in particular that molybdenum sulphide phases inside the zeolite have a very high intrinsic activity at low molybdenum content. This activity is attributed to highly dispersed molybdenum sulphide phases differing from MoS{sub 2} slabs and probably present as clusters. The influence of cobalt depends of its concentration. Thus at low loadings cobalt has a strong negative effect. It has been shown, in the molybdenum case, that cobalt interaction leads to an increase in the sulphur content of the molybdenum phases. At higher cobalt loading, the formation of a mixed phase is possible but the degree of promotion remains limited. This work emphasises the advantages of using zeolite supported sulphide phases, and especially Mo and Pd phases, in the hydro-treatment reactions. It seems however that single phases present a greater interest than binary phases. (author)

  8. The rate coefficients of unimolecular reactions in the systems with power-law distributions

    Science.gov (United States)

    Yin, Cangtao; Guo, Ran; Du, Jiulin

    2014-08-01

    The rate coefficient formulae of unimolecular reactions are generalized to the systems with the power-law distributions based on nonextensive statistics, and the power-law rate coefficients are derived in the high and low pressure limits, respectively. The numerical analyses are made of the rate coefficients as functions of the ν-parameter, the threshold energy, the temperature and the number of degrees of freedom. We show that the new rate coefficients depend strongly on the ν-parameter different from one (thus from a Boltzmann-Gibbs distribution). Two unimolecular reactions, CH3CO→CH3+CO and CH3NC→CH3CN, are taken as application examples to calculate their power-law rate coefficients, which obtained with the ν-parameters slightly different from one can be exactly in agreement with all the experimental studies on these two reactions in the given temperature ranges.

  9. I. Activation energies for the gas phase reactions of hydrogen atom with carbon monoxide and with ethylene. II. Rate constants for the reactions of benzyl cation with triethylphosphine and with triethylarsine in 1,2-dichloroethane

    International Nuclear Information System (INIS)

    Wang, H.Y.

    1976-01-01

    Two H-atom reactions H + CO + H 2 → HCO + H 2 and H + C 2 H 4 → C 2 H 5 * were separately studied from room temperature to about 100 0 C, and the activation energies for these two reactions were determined in this temperature range. For H + C 2 H 4 system, a small activation energy of 0.2 kcal/mole was obtained in the present narrow temperature range. The low activation energy indicates that the pre-exponential factor has a predominant contribution to the rate constant of this reaction and has about the same magnitude as that of the rate constant. For H + CO system, a fairly large activation energy of more than 7 kcal/mole was speculated in the potential energy surfaces of the system. The activation energy obtained in the present work, however, has a low value of about 2 kcal/mole. This low value reveals the low level of crossing of this reaction in the potential energy surface and thus indicates considerable complexity involved in the surface. Carbonium ions can be formed from chosen solutes in pulse-irradiated 1,2-dichloroethane (RCl) solutions. Upon irradiation, the electrons generated from the ionization of the solvent become localized on chloride ions as a result of their reaction with the neutral solvent molecules. The solvent counterion, RCl + , on the other hand, is free to exchange charge with the solute molecule. By choosing appropriate solutes, carbonium ion can be formed through a dissociative ionization process in the exchange. The benzyl cation was formed from its precursor compound dibenzylmercury and its reactions with two nucleophiles, triethylphosphine and triethylarsine, were separately studied. The formation and decay of benzyl cation were observed at 363 nm, the position of the maximum of its absorption band, and the second-order rate constants for the two reactions were determined at room temperature

  10. Nanoparticle growth by particle-phase chemistry

    Directory of Open Access Journals (Sweden)

    M. J. Apsokardu

    2018-02-01

    Full Text Available The ability of particle-phase chemistry to alter the molecular composition and enhance the growth rate of nanoparticles in the 2–100 nm diameter range is investigated through the use of a kinetic growth model. The molecular components included are sulfuric acid, ammonia, water, a non-volatile organic compound, and a semi-volatile organic compound. Molecular composition and growth rate are compared for particles that grow by partitioning alone vs. those that grow by a combination of partitioning and an accretion reaction in the particle phase between two organic molecules. Particle-phase chemistry causes a change in molecular composition that is particle diameter dependent, and when the reaction involves semi-volatile molecules, the particles grow faster than by partitioning alone. These effects are most pronounced for particles larger than about 20 nm in diameter. The modeling results provide a fundamental basis for understanding recent experimental measurements of the molecular composition of secondary organic aerosol showing that accretion reaction product formation increases linearly with increasing aerosol volume-to-surface-area. They also allow initial estimates of the reaction rate constants for these systems. For secondary aerosol produced by either OH oxidation of the cyclic dimethylsiloxane (D5 or ozonolysis of β-pinene, oligomerization rate constants on the order of 10−3 to 10−1 M−1 s−1 are needed to explain the experimental results. These values are consistent with previously measured rate constants for reactions of hydroperoxides and/or peroxyacids in the condensed phase.

  11. Reaction rate constant for radiative association of CF{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Öström, Jonatan, E-mail: jonatan.ostrom@gmail.com; Gustafsson, Magnus, E-mail: magnus.gustafsson@ltu.se [Applied Physics, Division of Materials Science, Department of Engineering Science and Mathematics, Luleå University of Technology, 97187 Luleå (Sweden); Bezrukov, Dmitry S. [Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow, 119991 (Russian Federation); Nyman, Gunnar [Department of Chemistry and Molecular Biology, University of Gothenburg, 41296 Gothenburg (Sweden)

    2016-01-28

    Reaction rate constants and cross sections are computed for the radiative association of carbon cations (C{sup +}) and fluorine atoms (F) in their ground states. We consider reactions through the electronic transition 1{sup 1}Π → X{sup 1}Σ{sup +} and rovibrational transitions on the X{sup 1}Σ{sup +} and a{sup 3}Π potentials. Semiclassical and classical methods are used for the direct contribution and Breit–Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius–Kooij formula in five temperature intervals with a relative difference of <3%. The fit parameters will be added to the online database KIDA. For a temperature of 10–250 K, the rate constant is about 10{sup −21} cm{sup 3} s{sup −1}, rising toward 10{sup −16} cm{sup 3} s{sup −1} for a temperature of 30 000 K.

  12. Evaluation of Chemical Kinetic for Mathematics Model Reduction of Cadmium Reaction Rate, Constant and Reaction Orde in to Electrochemical Process

    International Nuclear Information System (INIS)

    Prayitno

    2007-01-01

    The experiment was reduction of cadmium rate with electrochemical influenced by time process, concentration, current strength and type of electrode plate. The aim of the experiment was to know the influence, mathematic model reduction of cadmium the reaction rate, reaction rate constant and reaction orde influenced by time process, concentration, current strength and type of electrode plate. Result of research indicate the time processing if using plate of copper electrode is during 30 minutes and using plate of aluminium electrode is during 20 minutes. Condition of strong current that used in process of electrochemical is only 0.8 ampere and concentration effective is 5.23 mg/l. The most effective type Al of electrode plate for reduction from waste and the efficiency of reduction is 98 %. (author)

  13. Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Titanium

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This test method covers procedures for measuring reaction rates by the activation reactions 46Ti(n,p) 46Sc + 47Ti(n, np)46Sc. Note 1—Since the cross section for the (n,np) reaction is relatively small for energies less than 12 MeV and is not easily distinguished from that of the (n,p) reaction, this test method will refer to the (n,p) reaction only. 1.2 The reaction is useful for measuring neutrons with energies above approximately 4.4 MeV and for irradiation times up to about 250 days (for longer irradiations, see Practice E 261). 1.3 With suitable techniques, fission-neutron fluence rates above 109 cm–2·s–1 can be determined. However, in the presence of a high thermal-neutron fluence rate, 46Sc depletion should be investigated. 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 units of measurement are included in this standard. 1.6 This standard does not purport to address all...

  14. Thermodynamic and molecular origin of interfacial rate enhancements and endo-selectivities of a Diels-Alder reaction.

    Science.gov (United States)

    Beniwal, Vijay; Kumar, Anil

    2017-02-08

    Organic reactions in general display large rate accelerations when performed under interfacial conditions, such as on water or at ionic liquid interfaces. However, a clear picture of the physicochemical factors responsible for this large rate enhancements is not available. To gain an understanding of the thermodynamic and molecular origin of these large rate enhancements, we performed a Diels-Alder reaction between cyclopentadiene and methyl acrylate at ionic liquid/n-hexane interfaces. This study describes, for the first time, a methodology for the calculation of the activation parameters of an interfacial reaction. It has been seen that the energy of activation for an interfacial reaction is much smaller than that of the corresponding homogeneous reaction, resulting into the large rate acceleration for the interfacial reaction. Furthermore, the study describes the effects of the alkyl chain length of ionic liquid cations, the extent of heterogeneity, and the polarity of ionic liquids on the rate constants and stereoselectivity of the reaction.

  15. Supported liquid phase catalyst coating in micro flow Mizoroki-Heck reaction

    NARCIS (Netherlands)

    Stouten, S.C.; Noël, T.; Wang, Q.; Hessel, V.

    2015-01-01

    A Supported Liquid Phase Catalyst (SLPC) coating was successfully applied for the Mizoroki–Heck reaction in micro flow. Foremost, extended on stream operation was enabled and the on stream performance stability was verified. Stable catalytic activity was achieved during two consecutive runs totaling

  16. Toward the first study of chemical reaction dynamics of Mu with vibrational-state-selected reactants in the gas phase: The Mu+H2*(v=1) reaction by stimulated Raman pumping

    International Nuclear Information System (INIS)

    Bakule, Pavel; Sukhorukov, Oleksandr; Matsuda, Yasuyuki; Pratt, Francis; Gumplinger, Peter; Momose, Takamasa; Torikai, Eiko; Fleming, Donald

    2009-01-01

    Stimulated Raman pumping (SRP) is used to produce H 2 in its first vibrational state, in order to measure, for the first time, the Mu+H 2 *(v=1)→MuH+H reaction rate at room temperature, as a prototypical example of new directions in gas-phase muonium chemistry, utilizing the pulsed muon beam and a new dedicated laser system at the RIKEN/RAL Laboratory. Reported here is a preliminary result but the final results are expected to provide definitive new tests of reaction rate theory on the highly accurate H 3 potential energy surface. The major difficulty in this experiment, compared to the standard SRP process, is to ensure a homogeneous excitation over a volume of several cm 3 and of sufficient intensity to ensure a measurable Mu relaxation rate. The techniques used to accomplish this are described. The experiment utilizes the 2nd harmonic output of a Nd:YAG laser (532 nm) with pulse energies up to 500 mJ at a repetition rate of 25 Hz. Different optical setups have been constructed and tested in order to optimize the number of laser-pumped H 2 molecules and their overlap with the stopping profile of the muon beam in the reaction cell (total volume ∼100x40x4mm 3 ). The first result of this experiment gives a measured relaxation rate due to laser excitation of λ*=0.085±0.051μs -1 , consistent with theory but limited by both low statistics and particularly a high background relaxation rate.

  17. Determination of rate constants for the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Racz, A.; Walter, T.; Stimming, U. [Munich Technical Univ., Garching (Germany). Dept. of Physics

    2008-07-01

    The oxygen reduction reaction (ORR) in fuel cells is a complex and fundamental electrochemical reaction. However, greater insight is needed into this multi-electron reaction in order to develop efficient and innovative catalysts. The rotating ring disc electrode (RRDE) is a useful tool for studying reaction intermediates of the ORR and to better understand the reaction pathway. Carbon materials such as carbon nanofilaments-platelets (CNF-PL) have high electrical conductivity and may be considered for fuel cells. In particular Pt and RuSe{sub x}, deposited on CNF-PL materials could act as efficient catalysts in fuel cells. This study used the RRDE to evaluate the oxygen reduction kinetics of these catalysts in oxygen-saturated, diluted sulphuric acid at room temperature. Kinetic data and hydrogen peroxide formation were determined by depositing a thin-film of the catalyst on the Au disc. The values for the constants k1, k2 and k3 were obtained using diagnostic criteria and expressions to calculate the rate constants of the cathodic oxygen reduction reaction for RuSe on new carbon supports. A potential dependency of the constants k1 and k2 for RuSe{sub x}/CNF-PL was observed. The transition of the Tafel slopes for this catalyst was obtained. 4 refs., 1 fig.

  18. A randomised controlled trial of two infusion rates to decrease reactions to antivenom.

    Directory of Open Access Journals (Sweden)

    Geoffrey K Isbister

    Full Text Available BACKGROUND: Snake envenoming is a major clinical problem in Sri Lanka, with an estimated 40,000 bites annually. Antivenom is only available from India and there is a high rate of systemic hypersensitivity reactions. This study aimed to investigate whether the rate of infusion of antivenom reduced the frequency of severe systemic hypersensitivity reactions. METHODS AND FINDINGS: This was a randomized comparison trial of two infusion rates of antivenom for treatment of non-pregnant adult patients (>14 y with snake envenoming in Sri Lanka. Snake identification was by patient or hospital examination of dead snakes when available and confirmed by enzyme-immunoassay for Russell's viper envenoming. Patients were blindly allocated in a 11 randomisation schedule to receive antivenom either as a 20 minute infusion (rapid or a two hour infusion (slow. The primary outcome was the proportion with severe systemic hypersensitivity reactions (grade 3 by Brown grading system within 4 hours of commencement of antivenom. Secondary outcomes included the proportion with mild/moderate hypersensitivity reactions and repeat antivenom doses. Of 1004 patients with suspected snakebites, 247 patients received antivenom. 49 patients were excluded or not recruited leaving 104 patients allocated to the rapid antivenom infusion and 94 to the slow antivenom infusion. The median actual duration of antivenom infusion in the rapid group was 20 min (Interquartile range[IQR]:20-25 min versus 120 min (IQR:75-120 min in the slow group. There was no difference in severe systemic hypersensitivity reactions between those given rapid and slow infusions (32% vs. 35%; difference 3%; 95%CI:-10% to +17%;p = 0.65. The frequency of mild/moderate reactions was also similar. Similar numbers of patients in each arm received further doses of antivenom (30/104 vs. 23/94. CONCLUSIONS: A slower infusion rate would not reduce the rate of severe systemic hypersensitivity reactions from current high

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Timing differences in the generation of ground reaction forces between the initial and secondary landing phases of the drop vertical jump ☆

    Science.gov (United States)

    Bates, Nathaniel A.; Ford, Kevin R.; Myer, Gregory D.; Hewett, Timothy E.

    2014-01-01

    Background Rapid impulse loads imparted on the lower extremity from ground contact when landing from a jump may contribute to ACL injury prevalence in female athletes. The drop jump and drop landing tasks enacted in the first and second landings of drop vertical jumps, respectively, have been shown to elicit separate neuromechanical responses. We examined the first and second landings of a drop vertical jump for differences in landing phase duration, time to peak force, and rate of force development. Methods 239 adolescent female basketball players completed drop vertical jumps from an initial height of 31 cm. In-ground force platforms and a three dimensional motion capture system recorded force and positional data for each trial. Findings Between the first and second landing, rate of force development experienced no change (P > 0.62), landing phase duration decreased (P = 0.01), and time to peak ground reaction force increased (P 0.12). Interpretation The current results have important implications for the future assessment of ACL injury risk behaviors. Rate of force development remained unchanged between first and second landings from equivalent fall height, while time to peak reaction force increased during the second landing. Neither factor was dependent on the total time duration of landing phase, which decreased during the second landing. Shorter time to peak force may increase ligament strain and better represent the abrupt joint loading that is associated with ACL injury risk. PMID:23899938

  1. Gas phase ion/molecule reactions as studied by Fourier Transform Ion Cyclotron Resonance mass spectrometry

    International Nuclear Information System (INIS)

    Joergensen, S.I.

    1985-01-01

    The subject of this thesis is gas phase ion/molecule reactions as studied by Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry (chapter 2 contains a short description of this method). Three chapters are mainly concerned with mechanistic aspects of gas phase ion/molecule reactions. An equally important aspect of the thesis is the stability and reactivity of α-thio carbanions, dipole stabilized carbanions and homoenolate anions, dealt with in the other four chapters. (Auth.)

  2. A model for reaction rates in turbulent reacting flows

    Science.gov (United States)

    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.

  3. Stability of Transition-metal Carbides in Liquid Phase Reactions Relevant for Biomass-Based Conversion

    NARCIS (Netherlands)

    Souza Macêdo, L.; Stellwagen, D.R.; Teixeira da Silva, V.; Bitter, J.H.

    2015-01-01

    Transition-metal carbides have been employed for biobased conversions aiming to replace the rare noble metals. However, when reactions are in liquid phase, many authors have observed catalyst deactivation. The main routes of deactivation in liquid phase biobased conversions are coke deposition,

  4. The reaction process of the Bi-Sr-Ca-Cu-O system and the forming mechanism of the 2212 superconducting phase

    International Nuclear Information System (INIS)

    Xiong Guohong; Wang Minquan; Fan Xianping; Tang Xiaoming

    1993-01-01

    The reaction process and the reaction behavior of each component in the Bi-Sr-Ca-Cu-O system are presented in this paper. It reveals that the reaction is carried out in three different stages: forming of an insulating interphase at 680 C-790 C, forming of the 2212 superconducting phase at 790 C-860 C and forming of semiconducting phases in the presence of the liquid phase at 860 C-970 C. It is also confirmed that the 2212 superconducting phase (T c =85 K) is formed by the reaction of a trinary interphase together with CuO, SrO and CaO. A new two-step method is presented to prepare the 2212 superconducting phase by a presynthesized interphase. (orig.)

  5. The reaction process of the Bi-Sr-Ca-Cu-O system and the forming mechanism of the 2212 superconducting phase

    Science.gov (United States)

    Xiong, Guohong; Wang, Minquan; Fan, Xianping; Tang, Xiaoming

    1993-02-01

    The reaction process and the reaction behavior of each component in the Bi-Sr-Ca-Cu-O system are presented in this paper. It reveals that the reaction is carried out in three different stages: forming of an insulating interphase at 680°C 790°C, forming of the 2212 superconducting phase at 790°C 860°C and forming often semiconducting phases in the presence of the liquid phase at 860°C 970°C. It is also confirmed that the 2212 superconducting phase ( T c=85 K) is formed by the reaction of a trinary interphase together with CuO, SrO and CaO. A new two-step method is presented to prepare the 2212 superconducting phase by a presynthesized interphase.

  6. The reaction process of the Bi-Sr-Ca-Cu-O system and the forming mechanism of the 2212 superconducting phase

    Energy Technology Data Exchange (ETDEWEB)

    Xiong Guohong (Zhejiang Univ., Hangzhou (China). Dept. of Materials Science and Engineering); Wang Minquan (Zhejiang Univ., Hangzhou (China). Dept. of Materials Science and Engineering); Fan Xianping (Zhejiang Univ., Hangzhou (China). Dept. of Materials Science and Engineering); Tang Xiaoming (Zhejiang Univ., Hangzhou (China). Center for Analysis and Measurement)

    1993-02-01

    The reaction process and the reaction behavior of each component in the Bi-Sr-Ca-Cu-O system are presented in this paper. It reveals that the reaction is carried out in three different stages: forming of an insulating interphase at 680 C-790 C, forming of the 2212 superconducting phase at 790 C-860 C and forming of semiconducting phases in the presence of the liquid phase at 860 C-970 C. It is also confirmed that the 2212 superconducting phase (T[sub c]=85 K) is formed by the reaction of a trinary interphase together with CuO, SrO and CaO. A new two-step method is presented to prepare the 2212 superconducting phase by a presynthesized interphase. (orig.)

  7. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

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

    Science.gov (United States)

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

    1991-01-01

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

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

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    The stability of thermonuclear burning of hydrogen and helium accreted onto neutron stars is strongly dependent on the mass accretion rate. The burning behavior is observed to change from Type I X-ray bursts to stable burning, with oscillatory burning occurring at the transition. Simulations predict the transition at a 10 times higher mass accretion rate than observed. Using numerical models we investigate how the transition depends on the hydrogen, helium, and CNO mass fractions of the accreted material, as well as on the nuclear reaction rates of 3α and the hot-CNO breakout reactions 15 O(α, γ) 19 Ne and 18 Ne(α, p) 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 15 O(α, γ) 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 15 O(α, γ) 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.

  11. Solid-Phase Reactions of Iminium Ions: Cyclized Peptide Derivatives

    DEFF Research Database (Denmark)

    Wang, Yuanyuan

    formation of N,N’-aminals by nucleophilic attack of the peptide backbone is reversible under strongly acidic conditions and the N,N’-aminal is likely to be the kinetic product of many INCIC reactions. In addition, the N,N’-aminals are stable in the absence of acid but could be converted to the THIQ...... derivatives in solution phase under acid conditions in the presence of an active C-nucleophile in the side chain. The high yielding nature of the aminal formation is confirmed by solution phase synthesis. The introduced azide and alkyne residues in the side chain of N,N’-aminal products were further......BB may undergo auto-oxidation to quinazoline-2,4-diones in the absence of a suitable nucleophile on the side chain or backbone of the peptide (Chapter 4). The structure is confirmed by comparison with products obtained from solution-phase synthesis under the same conditions, one of which was confirmed...

  12. Measurements of rates of some reactions related to radiolytic effect on aqueous iodide solution

    International Nuclear Information System (INIS)

    Shiraishi, H.; Okuda, H.; Ishigure, K.

    1986-01-01

    A number of reactions takes place concurrently when aqueous iodide solution is subjected to radiation field. In order to help analyze this complicated radiation effect measurements of rate constants were undertaken for several important reactions. One of these concerns reduction of hypoiodous acid by hydrogen peroxide. For this reaction catalytic effect was found to be significant, and old rate data was revised. Measurements on reactions involving radicals were carried out by use of pulse radiolysis technique, which also include reexamination of results by previous workers. The reactions studied are (1) oxidation of iodide ion by hydroxyl radical (2) recombination reactions of atomic iodine and diiodide ion and (3) reduction of atomic and molecular iodine either by superoxide ion or by hydroperoxyl radical

  13. Corrosion potential detection method, potential characteristic simulation method for reaction rate and plant monitoring system using the same

    International Nuclear Information System (INIS)

    Sakai, Masanori; Onaka, Noriyuki; Takahashi, Tatsuya; Yamanaka, Hiroshi.

    1995-01-01

    In a calculation controlling device for a plant monitoring system, concentrations of materials concerning reaction materials in a certain state of a reaction process, and an actually measured value for the potential of a material in this state are substituted into a reaction rate equation obtained in accordance with a reaction process model. With such procedures, a relation between the reaction rate (current value) and the potential of the material can be obtained. A potential at which the reaction rates of an anode reaction and a cathode reaction contained in a corrosion reaction are made equal is determined by a numerical value calculation, based on an electrochemical hybrid potential logic by using the reaction rate equation, the reaction rate information relative to the corrosion reaction of the material and the concentration of the material concerning the corrosion reaction is obtained by a numerical value calculation. Then, simulation for the corrosion potential is enabled based on the handling corresponding to the actual reaction. Further, even for a portion which can not be measured actually, the corrosion potential can be recognized by simulation. (N.H.)

  14. Reevaluation of the O+(2P) reaction rate coefficients derived from atmosphere explorer C observations

    International Nuclear Information System (INIS)

    Chang, T.; Torr, D.G.; Richards, P.G.; Solomon, S.C.

    1993-01-01

    O + ( 2 P) is an important species for studies of the ionosphere and thermosphere: its emission at 7320 angstrom can be used as a diagnostic of the thermospheric atomic oxygen density. Unfortunately, there are no laboratory measurements of the O and N 2 reaction rates which are needed to determine the major sinks of O + ( 2 P). The reaction rates that are generally used were determined from aeronomic data by Rusch et al. but there is evidence that several important inputs that they used should be changed. The authors have recalculated the O and N 2 reaction rates for O + ( 2 P) using recent improvements in the solar EUV flux, cross sections, and photoelectron fluxes. For the standard solar EUV flux, the new N 2 reaction rate of 3.4 ± 1.5 x 10 -10 cm 3 s -1 is close to the value obtained by Rusch et al., but the new O reaction rate of 4.0 ± 1.9 x 10 -10 cm 3 s -1 is about 8 times larger. These new reaction rates are derived using neutral densities, electron density, and solar EUV fluxes measured by Atmosphere Explorer C in 1974 during solar minimum. The new theoretical emission rates are in good agreement with the data for the two orbits studied by Rusch et al. and they are in reasonable agreement with data from five additional orbits that are used in this study. The authors have also examined the effect of uncertainties in the solar EUV flux on the derived reaction rates and found that 15% uncertainties in the solar flux could cause additional uncertainties of up to a factor of 1.5 in the O quenching rate. 19 refs., 4 figs., 8 tabs

  15. 2-16 Thermonuclear Reaction Rates in rp Process of sd

    Institute of Scientific and Technical Information of China (English)

    Lam; Yihua[1; Nadezda; A.; Smirnova[2; W.A.; Richter[3

    2014-01-01

    Recently, we have constructed a new set of isospin non-conserving (INC) shell-model Hamiltonians as a combinationof isospin conserving (IC) Hamiltonian, Coulomb interaction and effective isospin-symmetry breaking forcesof nuclear origin[1]. The advantage is that Coulomb effects are taken into account with great care, thus the new ap-Fig. 1 (color online) The comparison of resonant rates of23Al(p;)24Si calculated by IC and INC Hamiltonians. TheINC Hamiltonians of OB+USD, OB+USDA, OB+USDBwere constructed in Ref. [5]; whereas (cd-USD), (cd-USDA),(cd-USDB) are INC Hamiltonians in Ref. [1]. USD, USDA,USDB are IC Hamiltonians in Ref. [6].proach allows one to describe more accurately and topredict unknown nuclear level schemes and decay modes.Since the approximate isospin-symmetry becomes broken,a realistic amount of isospin-mixing in nuclearstates is thus introduced. Among numerous applicationsto the structure of proton-rich nuclei, we usedthe new Hamiltonian to calculate resonant reaction andnon-resonant reaction (direct capture) rates of radiativeproton-capture reactions important for astrophysical rpprocess.

  16. Estimation of the Polymerization Rate of Liquid Propylene Using Adiabatic Reaction Calorimetry and Reaction Dilatometry

    NARCIS (Netherlands)

    Al-haj Ali, Mohammad; Betlem, Ben; Roffel, Brian; Weickert, Günter

    2007-01-01

    The use of pressure-drop and constant-pressure dilatometry for obtaining rate data for liquid propylene polymerization in filled batch reactors was examined. The first method uses reaction temperature and pressure as well as the compressibility of the reactor contents to calculate the polymerization

  17. Stellar evolution and the triple-α reactions

    International Nuclear Information System (INIS)

    Suda, Takuma

    2014-01-01

    Nuclear reaction rates play a crucial role in the evolution of stars. For low-mass stars, the triple-α reaction controls the helium burning stars in the red giant and asymptotic giant branch (AGB) phase. More importantly, the cross section of the triple-α reaction has a great impact on the helium ignition at the center of the electron degenerate helium core of red giants and on the helium shell flashes of AGB stars. It is to be noted that stellar evolution models are influenced not only by the value of the cross section, but also by the temperature dependence of the reaction rate. In this paper, I present the impact of the triple-α reaction rates on the evolution of low-mass metal-free stars and intermediate-mass AGB stars. According to the previous study, the constraint on the triple-α reaction rate is derived based on stellar evolution theory. It is found that the recent revisions of the rate proposed by nuclear physics calculations satisfy the condition for the ignition of the helium core flash in low-mass stars

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

    Science.gov (United States)

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

    2011-09-29

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

  19. Absolute calibration of the Rh-103(n,n')Rh-103m reaction rate

    International Nuclear Information System (INIS)

    Taylor, W.H.; Murphy, M.F.; March, M.R.

    1979-05-01

    The uncertainties in determining the absolute values of the Rh-103(n, n') Rh-103m reaction rate (which is widely used as a neutron damage flux monitor) have been reduced to approximately +-5%. This has been achieved with the use of a calibrated source of Pd-103-Rh-103m activity supplied by the IAEA. Agreement to within 3% between measured and calculated values of the reaction rate (normalised to the U-238 fission rate) has been achieved. (author)

  20. Reevaluation of the O(+)(2P) reaction rate coefficients derived from Atmosphere Explorer C observations

    Science.gov (United States)

    Chang, T.; Torr, D. G.; Richards, P. G.; Solomon, S. C.

    1993-01-01

    O(+)(2P) is an important species for studies of the ionosphere and thermosphere: its emission at 7320 A can be used as a diagnostic of the thermospheric atomic oxygen density. Unfortunately, there are no laboratory measurements of the O and N2 reaction rates which are needed to determine the major sinks of (O+)(2p). We have recalculated the O and N2 reaction rates for O(+) (2P) using recent improvements in the solar EUV flux, cross sections, and photoelectron fluxes. For the standard solar EUV flux, the new N2 reaction rate of 3.4 +/- 1.5 x 10 exp -10 cu cm/s is close to the value obtained by Rusch et al. (1977), but the new O reaction rate of 4.0 +/- 1.9 x 10 exp -10 cu cm/sec is about 8 times larger. These new reaction rates are derived using neutral densities, electron density, and solar EUV fluxes measured by Atmosphere Explorer C in 1974 during solar minimum. The new theoretical emission rates are in good agreement with the data for the two orbits studied by Rusch et al.

  1. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    International Nuclear Information System (INIS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH 3 + , NH 4 + , NH 3 OH + , and NH 2 OH + ) and neutral molecules having one carbonyl group (H 2 CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  2. Some Insights into Formamide Formation through Gas-phase Reactions in the Interstellar Medium

    Science.gov (United States)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH_{3}^{+}, NH_{4}^{+}, NH3OH+, and NH2OH+) and neutral molecules having one carbonyl group (H2CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  3. Analysis of the flow with phase change and chemical reaction with the particle interaction method. Report under the contract between JNC and Toshiba Corporation

    International Nuclear Information System (INIS)

    Shirakawa, Noriyuki; Horie, Hideki; Yamamoto, Yuichi

    2001-02-01

    The numerical thermohydraulic analysis of a LMFR component should involve its whole boundary in order to evaluate the effect of chemical reaction within it. Therefore, it becomes difficult mainly due to computing time to adopt microscopic approach for the chemical reaction directly. Thus, the thermohydraulic code is required to model the chemically reactive fluid dynamics with constitutive correlations. The reaction rate depends on the binary contact areas between components such as continuous liquids, droplets, solid particles, and bubbles. The contact areas change sharply according to the interface state between components. Since no experiments to study the jet flow with sodium-water chemical reaction have been done, the goal of this study is to obtain the knowledge of flow regimes and contact areas by analyzing the fluid dynamics of multi-phase and reactive components mechanistically with the particle interaction method. In this fiscal year, following works were performed: 1) Development and coding of the interfacial area model, 2) Development and coding of the phase change model, 3) Verification of the fundamental functions of the models, and 4) Literature investigation of the related experiments. (author)

  4. SENSMG: First-Order Sensitivities of Neutron Reaction Rates, Reaction-Rate Ratios, Leakage, keff, and α Using PARTISN

    Energy Technology Data Exchange (ETDEWEB)

    Favorite, Jeffrey A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-11-21

    SENSMG is a tool for computing first-order sensitivities of neutron reaction rates, reaction-rate ratios, leakage, keff, and α using the PARTISN multigroup discrete-ordinates code. SENSMG computes sensitivities to all of the transport cross sections and data (total, fission, nu, chi, and all scattering moments), two edit cross sections (absorption and capture), and the density for every isotope and energy group. It also computes sensitivities to the mass density for every material and derivatives with respect to all interface locations. The tool can be used for one-dimensional spherical (r) and two-dimensional cylindrical (r-z) geometries. The tool can be used for fixed-source and eigenvalue problems. The tool implements Generalized Perturbation Theory (GPT) as discussed by Williams and Stacey. Section II of this report describes the theory behind adjoint-based sensitivities, gives the equations that SENSMG solves, and defines the sensitivities that are output. Section III describes the user interface, including the input file and command line options. Section IV describes the output. Section V gives some notes about the coding that may be of interest. Section VI discusses verification, which is ongoing. Section VII lists needs and ideas for future work. Appendix A lists all of the input files whose results are presented in Sec. VI.

  5. Measurement of reaction rates of interest in stellar structure and evolution

    International Nuclear Information System (INIS)

    Terrasi, F.; D''Onofrio, A.; Campajola, L.; Imbriani, G.; Gialanella, L.; Greife, U.; Rolfs, C.; Strieder, F.; Trautvetter, H.P.; Roca, V.; Romano, M.; Straniero, O.

    1998-01-01

    Accurate determinations of reaction rates at astrophysical energies are very important in stellar structure and evolution studies. The cases of two key reactions, namely 7 Be(p,γ) 8 B and 12 C(α,γ) 16 O are discussed, both from the point of view of their astrophysical interest and of the experimental difficulties in the measurement of their cross section. (orig.)

  6. Rate constant computation on some elementary reactions of Hg during combustion

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qing; Yang, Bo-wen; Bai, Jing-ru [Northeast Dianli Univ., Jilin (China). Inst. of Energy and Power Engineering

    2013-07-01

    The geometry optimizations of reactants, products and transition states were made by the quantum chemistry MP2 method at the SDD basis function level for Hg, and 6-311++G(3df, 3pd) for others. The properties of stable minimums were validated by vibration frequencies analysis. Furthermore, the microcosmic chemical reaction mechanisms of reactions were investigated by ab initio calculations of quantum chemistry. On the basis of the geometry optimization, reaction rate constants within 298-2,000 K are calculated neither from experimental data nor by estimated, but directly from Quantum Chemistry software-Khimera.

  7. Absolute calibration of the Rh-103 (n, n') Rh-103m reaction rate

    International Nuclear Information System (INIS)

    Taylor, W.H.; Murphy, M.F.; March, M.R.

    1979-05-01

    The uncertainties in determining the absolute values of the Rh-103 (n, n') Rh-103m reaction rate (which is widely used as a neutron damage flux monitor) have been reduced to ∼±5%. This has been achieved with the use of a calibrated source of Pd-103-Rh-103m activity supplied by the I.A.E.A. Agreement to within 3% between measured and calculated values of the reaction rate (normalised to the U-238 fission rate) has been achieved. (author)

  8. Kinetics of silica-phase transitions

    International Nuclear Information System (INIS)

    Duffy, C.J.

    1993-07-01

    In addition to the stable silica polymorph quartz, several metastable silica phases are present in Yucca Mountain. The conversion of these phases to quartz is accompanied by volume reduction and a decrease in the aqueous silica activity, which may destabilize clinoptilolite and mordenite. The primary reaction sequence for the silica phases is from opal or glass to disordered opal-CT, followed by ordering of the opal-CT and finally by the crystallization of quartz. The ordering of opal-CT takes place in the solid state, whereas the conversion of opal-CT takes place through dissolution-reprecipitation involving the aqueous phase. It is proposed that the rate of conversion of opal-CT to quartz is controlled by diffusion of defects out of a disordered surface layer formed on the crystallizing quartz. The reaction rates are observed to be dependent on temperature, pressure, degree of supersaturation, and pH. Rate equations selected from the literature appear to be consistent with observations at Yucca Mountain

  9. Computer investigations on the asymptotic behavior of the rate coefficient for the annihilation reaction A + A → product and the trapping reaction in three dimensions.

    Science.gov (United States)

    Litniewski, Marek; Gorecki, Jerzy

    2011-06-28

    We have performed intensive computer simulations of the irreversible annihilation reaction: A + A → C + C and of the trapping reaction: A + B → C + B for a variety of three-dimensional fluids composed of identical spherical particles. We have found a significant difference in the asymptotic behavior of the rate coefficients for these reactions. Both the rate coefficients converge to the same value with time t going to infinity but the convergence rate is different: the O(t(-1/2)) term for the annihilation reaction is higher than the corresponding term for the trapping reaction. The simulation results suggest that ratio of the terms is a universal quantity with the value equal to 2 or slightly above. A model for the annihilation reaction based on the superposition approximation predicts the difference in the O(t(-1/2)) terms, but overestimates the value for the annihilation reaction by about 30%. We have also performed simulations for the dimerization process: A + A → E, where E stands for a dimer. The dimerization decreases the reaction rate due to the decrease in the diffusion constant for A. The effect is successfully predicted by a simple model.

  10. Simulation of the catalyst layer in PEMFC based on a novel two-phase lattice model

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Jiejing; Yang Wei; Xu Li [School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072 (China); Wang Yuxin, E-mail: yxwang@tju.edu.cn [School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072 (China)

    2011-08-01

    Highlights: > We propose a novel two phase lattice model of catalyst layer in PEMFC. > The model features a catalyst phase and a mixed ionomer and pores phase. > Transport and electrochemical reaction in the lattice are simulated. > The model enables more accurate results than pore-solid two phase model. > Profiles of oxygen level and reaction rate across catalyst layer vary with cell current. - Abstract: A lattice model of catalyst layer in proton exchange membrane fuel cells (PEMFCs), consisting of randomly distributed catalyst phase (C phase) and mixed ionomer-pore phase (IP phase), was established by means of Monte Carlo method. Transport and electrochemical reactions in the model catalyst layer were calculated. The newly proposed C-IP model was compared with previously established pore-solid two phase model. The variation of oxygen level and reaction rate along the thickness of catalyst layer with cell current was discussed. The effect of ionomer distribution across catalyst layer was studied by comparing profiles of oxygen level, reaction rate and overpotential, as well as corresponding polarization curves.

  11. ICR studies of some anionic gas phase reactions and FTICR software design

    International Nuclear Information System (INIS)

    Noest, A.J.

    1983-01-01

    This thesis consists of two parts. Part one (Chs. 1-5) reports experimental results from mostly drift-cell ICR studies of negative ion-molecule reactions; part two (Chs. 6-11) concerns the design of software for an FTICR instrument. The author discusses successively: 1. ion cyclotron resonance spectrometry; 2. the gas phase allyl anion; 3. the (M-H) and (M-H2) anions from acetone; 4. negative ion-molecule reactions of aliphatic nitrites studied by cyclotron resonance; 5. homoconjugation versus charge-dipole interaction effects in the stabilization of carbanions in the gas phase; 6. the Fourier Transform ICR method; 7. the FTICR-software; 8. an efficient adaptive matcher filter for fast transient signals; 9. reduction of spectral peak height errors by time-domain weighing; 10. Chirp excitation; 11. Compact data storage. The book concludes with a Dutch and English summary (G.J.P.)

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

    Science.gov (United States)

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

    2017-12-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-02-25

    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.

  14. Cross sections and reaction rates of d+{sup 8}Li reactions involved in Big Bang nucleosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Balbes, M.J. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Farrell, M.M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Boyd, R.N. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics]|[Department of Astronomy, Ohio State University, Columbus, OH 43210 (United States); Gu, X. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Hencheck, M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kalen, J.D. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Mitchell, C.A. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kolata, J.J. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Lamkin, K. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Smith, R. [Division of Nuclear Medicine, Department of Radiology, Hospital of the University of Pennsylvania, Philadelphia, PA 19104 (United States); Tighe, R. [Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States); Ashktorab, K. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Becchetti, F.D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Brown, J. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Roberts, D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Wang, T.F. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Humphrey, D. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Vourvopoulos, G. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Islam, M.S. [Department of Physics, Ball State University, Muncie, IN 47306 (United States)

    1995-02-20

    We have measured angular distributions of the {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H and {sup 2}H({sup 8}Li, {sup 9}Be)n reactions at E{sub c.m.}=1.5 to 2.8 MeV using an {sup 8}Li-radioactive-beam technique. Astrophysical S-factors and reaction rates were calculated from the measured cross sections. Although the {sup 2}H({sup 8}Li, {sup 9}Be)n cross section is small, it can contribute to {sup 9}Be synthesis. The {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H reaction has a sufficiently large cross section to destroy {sup 8}Li, which may decrease the synthesis of heavier elements. No products from the {sup 2}H({sup 8}Li, {sup 9}Li)p reaction were detected. We also present the results of calculations using the inhomogeneous model of primordial nucleosynthesis in several regions of parameter space. ((orig.))

  15. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Computational Chemistry Group, Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2014-01-10

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH{sub 3}{sup +}, NH{sub 4}{sup +}, NH{sub 3}OH{sup +}, and NH{sub 2}OH{sup +}) and neutral molecules having one carbonyl group (H{sub 2}CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  16. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Insight into organic reactions from the direct random phase approximation and its corrections

    Energy Technology Data Exchange (ETDEWEB)

    Ruzsinszky, Adrienn [Department of Physics, Temple University, Philadelphia, Pennsylvania 19122 (United States); Zhang, Igor Ying; Scheffler, Matthias [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany)

    2015-10-14

    The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges.

  18. Insight into organic reactions from the direct random phase approximation and its corrections

    International Nuclear Information System (INIS)

    Ruzsinszky, Adrienn; Zhang, Igor Ying; Scheffler, Matthias

    2015-01-01

    The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges

  19. Calculation of multigroup reaction rates for the Ghana Research ...

    African Journals Online (AJOL)

    The discrete ordinate spatial model, which pro-vides solution to the differential form of the transport equation by the Carlson-SN (N=4) approach was adopted to solve the Ludwig-Boltzmann multigroup neutron transport equation for this analysis. The results show that for any fissile resonance absorber, the reaction rates ...

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

    Science.gov (United States)

    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.

  1. Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-107 K).

    Science.gov (United States)

    Ocaña, A J; Blázquez, S; Ballesteros, B; Canosa, A; Antiñolo, M; Albaladejo, J; Jiménez, E

    2018-02-21

    Ethanol, CH 3 CH 2 OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH 3 CH 2 OH (k(T)) between 21 and 107 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(107 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10 -11 (T/300 K) -(0.71±0.10) cm 3 molecule -1 s -1 . In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (∼10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10 -11 cm 3 molecule -1 s -1 at 100 K and around 1 × 10 -10 cm 3 molecule -1 s -1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

  2. Measurement of reaction rates of interest in stellar structure and evolution

    Energy Technology Data Exchange (ETDEWEB)

    Terrasi, F; D` Onofrio, A [Dipt. di Scienze Ambientali, Seconda Univ. di Napoli, Caserta (Italy); [INFN, Napoli (Italy); Campajola, L; Imbriani, G [INFN, Napoli (Italy); [Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); Gialanella, L [INFN, Napoli (Italy); [Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); [Inst. fuer Experimentalphysik III, Ruhr-Univ. Bochum, Bochum (Germany); Greife, U; Rolfs, C; Strieder, F; Trautvetter, H P [Inst. fuer Experimentalphysik III, Ruhr-Univ. Bochum, Bochum (Germany); Roca, V; Romano, M [INFN, Napoli (Italy); [Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); Straniero, O [Osservatorio Astronomico di Collurania, Teramo (Italy)

    1998-06-01

    Accurate determinations of reaction rates at astrophysical energies are very important in stellar structure and evolution studies. The cases of two key reactions, namely {sup 7}Be(p,{gamma}){sup 8}B and {sup 12}C({alpha},{gamma}){sup 16}O are discussed, both from the point of view of their astrophysical interest and of the experimental difficulties in the measurement of their cross section. (orig.)

  3. Optimized reaction mechanism rate rules for ignition of normal alkanes

    KAUST Repository

    Cai, Liming; Pitsch, Heinz; Mohamed, Samah; Raman, Venkat; Bugler, John; Curran, Henry; Sarathy, Mani

    2016-01-01

    fidelity reacting flow simulations capable of improving combustor design and operation. The development of such models for many new fuel components and/or surrogate molecules is greatly facilitated by the application of reaction classes and rate rules

  4. The gas phase reaction of ozone with 1,3-butadiene: formation yields of some toxic products

    Science.gov (United States)

    Kramp, Franz; Paulson, Suzanne E.

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separate experiments, small quantities of 1,3,5-trimethyl benzene were added as a tracer for OH. Formation yields of acrolein of (52±7)%, 1,2-epoxy-3-butene of (3.1±0.5)% and OH radicals of (13±3)% were observed. In addition, the rate coefficient of the gas-phase reaction of ozone with 1,2-epoxy-3-butene was measured both directly and relative to propene, finding an average of (1.6±0.4)×10 -18 cm 3 molecule -1 s -1, respectively, at 296±2 K. The results are briefly discussed in terms of the effect of atmospheric processing on the toxicity of 1,3-butadiene.

  5. Reaction rate constants of HO2 + O3 in the temperature range 233-400 K

    Science.gov (United States)

    Wang, Xiuyan; Suto, Masako; Lee, L. C.

    1988-01-01

    The reaction rate constants of HO2 + O3 were measured in the temperature range 233-400 K using a discharge flow system with photofragment emission detection. In the range 233-253 K, the constants are approximately a constant value, and then increase with increasing temperature. This result suggests that the reaction may have two different channels. An expression representing the reaction rate constants is presented.

  6. Effect of crystallochemistry of starting materials on the rate of smectite to illite reaction

    International Nuclear Information System (INIS)

    Sato, Tsutomu; Isobe, Hiroshi; Ohnuki, Toshihiko; Murakami, Takashi

    1995-01-01

    A series of hydrothermal experiments was performed to determine the effect of layer charge of starting materials on the smectite to illite reaction rate that might be applied to nuclear-waste repository design. The experiments were conducted on K-saturated fractions of Wyoming smectite (SWy-1) and Tsukinuno smectite (SKu-F) in a closed system at temperatures of 95, 150, 200, 250, 300 C for run durations of up to 477 days with a 1:20 mass ratio of solid to deionized water. The mean layer charge and tetrahedral charge of SKu-F are larger than those of SWy-1. The proportion of smectite layers in illite/smectite interstratified minerals rapidly decreases, and then slowly decreases with increase in reaction time; a plot of ln (100/% smectite) vs. time produces two distinct straight lines in all experiments. These lines are suggestive of two first-order kinetic processes with different rates for this reaction; the first process has a greater rate than the second one. An Arrhenius plot of the reaction rates for each process produces a folding and straight lines for the first and second processes, respectively, suggesting that there are at least two parallel processes in the first process, and a dominant process is different between high- and low-temperature reactions. The activation energies of the first and second processes determined from the plots are the same for the two starting materials, meaning that the reaction mechanisms for the two starting materials are the same. However, the rate of the first process is different between the two starting materials, although that of the second process is similar. The difference in the rate of the first process results possibly from the difference in the amount of layer charge between the two starting smectites

  7. Rate constant for reaction of hydroxyl radicals with bicarbonate ions

    International Nuclear Information System (INIS)

    Buxton, G.V.; Elliot, A.J.

    1986-01-01

    The rate constant for reaction of hydroxyl radicals with the bicarbonate ion has been determined to be 8.5 x 10 6 dm 3 mol -1 s -1 . This value was calculated from: the measured rate of formation of the CO 3 - radical in pulsed electron irradiation of bicarbonate solutions over the pH range 7.0 to 9.4; the pK for the equilibrium HCO 3 - = CO 3 2- + H + ; and the rate constant for hydroxyl radicals reacting with the carbonate ion. (author)

  8. Thermoneutral isotope exchange reactions of cations in the gas phase

    International Nuclear Information System (INIS)

    Ausloos, P.; Lias, S.G.

    1981-01-01

    Rate constants have been measured for reactions of the type AD 2 + + MH → MD + ADH + , where AD 2 + is CD 3 CND + , CD 3 CDOD + , (CD 3 COCD 3 )D + , or (C 2 D 5 ) 2 OD + and the MH molecules are alcohols, acids, mercaptans, H 2 S, AsH 3 , PH 3 , or aromatic molecules. Rate constants are also presented for the reactions Ar/sub H/D + + D 2 O → Ar/sub d/D + + HDO, where Ar/sub H/D + is a deuteronated aromatic molecule and Ar/sub D/D + is the same species with a D atom incorporated on the ring. In all but two cases, the competing deuteron transfer is sufficiently endothermic that it cannot be observed under the conditions of the ICR experiments at 320 to 420 K. The efficiencies of the isotope exchange reactions are interpreted in terms of estimated potential surface cross sections for the reactions AD 2 + + MH → [AD 2 + MH] → [ADMHD + ] → [ADH + MD] → ADH + + MD. When the formation of the [ADMHD + ] complex is estimated to be thermoneutral or slightly endothermic, the isotope exchange process is inefficient (probability of a reactive collision 2 + MH] → [ADMHD + ] is exothermic. For most of the systems, trends in reaction efficiency appear to be related to factors such as dipole moments of reactant species (or for aromatic compounds, the electron-donating or -withdrawing properties of ring substituents) which influence the relative orientation of the two reactant species in the complex

  9. Calculation of rate coefficients of some proton-transfer ion-molecule reactions in weakly ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.

    1985-01-01

    A classical collision theory is used to describe thermal bimolecular rate coefficeints for reaction between positive and negative ions and polar molecules in a carrier gas. Special attention is paid to ion-molecule reaction in which proton transfer occurs. These reactions play an important role in terrestrial plasma devices, in ionosphere, in planetary atmospheres and in interstellar matter. The equilibrium rate coefficients of the reactions are calculated based on a microscopic reactive cross section derived from a long distance polar molecule-ion potential. The results are compared with experimental values of afterglow measurements. (D.Gy.)

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

    Science.gov (United States)

    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 (Dpsolid, 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.

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

    Science.gov (United States)

    Miles, A. M.

    1982-01-01

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

  12. Recent developments in semiclassical mechanics: eigenvalues and reaction rate constants

    International Nuclear Information System (INIS)

    Miller, W.H.

    1976-04-01

    A semiclassical treatment of eigenvalues for a multidimensional non-separable potential function and of the rate constant for a chemical reaction with an activation barrier is presented. Both phenomena are seen to be described by essentially the same semiclassical formalism, which is based on a construction of the total Hamiltonian in terms of the complete set of ''good'' action variables (or adiabatic invariants) associated with the minimum in the potential energy surface for the eigenvalue case, or the saddle point in the potential energy surface for the case of chemical reaction

  13. Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

    Science.gov (United States)

    Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

    1999-01-01

    Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

  14. Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

    Science.gov (United States)

    Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

    1999-01-01

    Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

  15. Evaporation rates and surface profiles on heterogeneous surfaces with mass transfer and surface reaction

    Energy Technology Data Exchange (ETDEWEB)

    Flytzani-Stephanopoulos, M; Schmidt, L D

    1979-01-01

    Simple models incorporating surface reaction and diffusion of volatile products through a boundary layer are developed to calculate effective rates of evaporation and local surface profiles on surfaces having active and inactive regions. The coupling between surface heterogeneities with respect to a particular reaction and external mass transfer may provide a mechanism for the surface rearrangement and metal loss encountered in several catalytic systems of practical interest. Calculated transport rates for the volatilization of platinum in oxidizing environments and the rearrangement of this metal during the ammonia oxidation reaction agree well with published experimental data.

  16. Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

    Science.gov (United States)

    Lewis, Scott Romak

    Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

  17. Determination of the enzyme reaction rate in a differential fixed-bed reactor: a case study

    Directory of Open Access Journals (Sweden)

    Baruque Filho E.A.

    2001-01-01

    Full Text Available The reaction rate of starch hydrolysis catalyzed by a glucoamylase covalently bound to chitin particles was measured in a Differential Fixed-Bed Reactor (DFBR. Under selected test conditions the initial reaction rate may represent biocatalyst activity. Some aspects which influence measurement of the initial reaction rate of an immobilized enzyme were studied: the amount of desorbed enzyme and its hydrolytic activity, the extent of pore blockage of the biocatalyst caused by substrate solution impurities and the internal and external diffusional mass transfer effects. The results showed that the enzyme glucoamylase was firmly bound to the support, as indicated by the very low amount of desorbed protein found in the recirculating liquid. Although this protein was very active, its contribution to the overall reaction rate was negligible. It was observed that the biocatalyst pores were susceptible to being blocked by the impurities of the starch solution. This latter effect was accumulative, increasing with the number of sequential experiments carried out. When the substrate solution was filtered before use, very reliable determinations of immobilized enzyme reaction rates could be performed in the DFBR. External and internal diffusional resistences usually play a significant role in fixed-bed reactors. However, for the experimental system studied, internal mass transfer effects were not significant, and it was possible to select an operational condition (recirculation flow rate value that minimized the external diffusional limitations.

  18. New determination of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reaction rates at astrophysical energies

    Energy Technology Data Exchange (ETDEWEB)

    Tumino, A.; Spartà, R.; Spitaleri, C.; Pizzone, R. G.; La Cognata, M.; Rapisarda, G. G.; Romano, S.; Sergi, M. L. [Laboratori Nazionali del Sud-INFN, Catania (Italy); Mukhamedzhanov, A. M. [Cyclotron Institute Texas A and M University-College Station, Texas (United States); Typel, S. [GSI Helmholtzzentrum für Schwerionenforschung GmbH-Theorie Darmstadt (Germany); Tognelli, E.; Degl' Innocenti, S.; Prada Moroni, P. G. [Dipartimento di Fisica, Università di Pisa, and INFN-Sezione di Pisa, Pisa (Italy); Burjan, V.; Kroha, V.; Hons, Z.; Mrazek, J.; Piskor, S. [Nuclear Physics Institute of ASCR-Rez near Prague (Czech Republic); Lamia, L., E-mail: tumino@lns.infn.it [Dipartimento di Fisica e Astronomia, Università degli Studi di Catania, Catania (Italy)

    2014-04-20

    The cross sections of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions have been measured via the Trojan Horse method applied to the quasi-free {sup 2}H({sup 3}He,p {sup 3}H){sup 1}H and {sup 2}H({sup 3}He,n {sup 3}He){sup 1}H processes at 18 MeV off the proton in {sup 3}He. For the first time, the bare nucleus S(E) factors have been determined from 1.5 MeV, across the relevant region for standard Big Bang nucleosynthesis, down to the thermal energies of deuterium burning in the pre-main-sequence (PMS) phase of stellar evolution, as well as of future fusion reactors. Both the energy dependence and the absolute value of the S(E) factors deviate by more than 15% from the available direct data and existing fitting curves, with substantial variations in the electron screening by more than 50%. As a consequence, the reaction rates for astrophysics experience relevant changes, with a maximum increase of up to 20% at the temperatures of the PMS phase. From a recent primordial abundance sensitivity study, it turns out that the {sup 2}H(d,n){sup 3}He reaction is quite influential on {sup 7}Li, and the present change in the reaction rate leads to a decrease in its abundance by up to 10%. The present reaction rates have also been included in an updated version of the FRANEC evolutionary code to analyze their influence on the central deuterium abundance in PMS stars with different masses. The largest variation of about 10%-15% pertains to young stars (≤1 Myr) with masses ≥1 M {sub ☉}.

  19. Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

    Science.gov (United States)

    Gupta, S; Basant, N; Mohan, D; Singh, K P

    2016-07-01

    Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

  20. Relationship between reaction layer thickness and leach rate for nuclear waste glasses

    International Nuclear Information System (INIS)

    Chick, L.A.; Pederson, L.R.

    1984-02-01

    Three leaching tests, devised to distinguish among several proposed nuclear waste glass leaching mechanisms, were carried out for four different waste glasses. In the first test, the influence of a pre-formed reaction layer on elemental release was evaluated. In the second test, glass specimens were replaced with fresh samples halfway through the leaching experiment, to evaluate the influence of the concentration of glass components in leaching. Finally, regular replacement of the leachant at fixed time intervals essentially removed the variable changing solution concentration, and allowed an assessment of the influence of reaction layer thickness on the leaching rate. Results for all glasses tested indicated that the reaction layer presented little or no barrier to leaching, and that most of the retardation on leaching rates generally observed are attributable to saturation effects. 20 references, 6 figures, 1 table

  1. Understanding and Improvement of an Experiment Measuring Chemical Reaction Rates by Monitoring Volume Change of a Gas: On the Reaction between HCl(aq) and Mg(s)

    International Nuclear Information System (INIS)

    Bang, Jeong Ah; Yoon, Hee Sook; Jeong, Dae Hong; Choi, Won Ho

    2006-01-01

    In this study we analyzed and improved an experiment measuring chemical reaction rates introduced in the high school science textbooks through an understanding of the phenomena observed in carrying out the experiment. For this purpose, the contents of textbooks related to the experiment were analyzed, and the problems observed in carrying out the experiment were addressed through experimental analysis. When the experiment was carried out by the method of aquatic transposition presented in textbooks, the observed volume change of H 2 gas was delayed and chemical reaction rate was increased in the early stage of reaction period. To resolve these problems, an improved method for measuring the reaction rates was suggested. In the improved experiment the reaction rate was measured to be constant on time, which was interpreted in terms of the concentration of H + and the surface area of magnesium

  2. The reaction between iodine and silver under severe PWR accident conditions. An experimental parameter study

    Energy Technology Data Exchange (ETDEWEB)

    Funke, F; Greger, G U; Bleier, A; Hellmann, S; Morell, W [Siemens AG, Power Generation Group, Erlangen (Germany)

    1996-12-01

    An extensive experimental parameter study was performed on the kinetics in the reaction system I{sub 2}/Ag and I{sup -}/Ag in a laboratory-scale apparatus.Starting with I{sub 2} or I{sup -} solutions and silver powder suspensions, the decrease of soluted I{sub 2} or I{sup -}, respectively, due to fixation on the silver particles, was monitored as function of time using the radioactive tracer I-131. The measured data were analyzed using a model of first order kinetics with respect to the iodine concentration. However, the analysis using first order kinetics had to be performed separately in an early, fast reaction phase and in a late, slow reaction phase. The reason for this unexpected behaviour was not identified. Thus, rate constant, two for each test, were deduced from 14 I{sub 2}/Ag main tests and from 36 I{sup -}/Ag tests. No dependencies of the rate constants were found on the parameters temperature, initial iodine concentration, presence of boric acid, type of silver educt, and pretreatment of the silver educt prior to the tests. However, the stirring of the reaction solution generally enhanced the kinetics highlighting the importance of mass transfer. The I{sup -}/Ag reaction proceeded only if there was no inertization of the reaction solution by sparging with nitrogen. The temperature-independent rate constant for the early, fast I{sub 2}/Ag reaction phase is 2E-5 m/s. However, a smaller rate constant of 6E-6 m/s is recommended for use in source term calculations with IMPAIR, which already contains a first order model. Analogously, the temperature-independent I{sup -}/Ag reaction rate constant is 8E-6 m/s in an early, fast reaction phase. For use in source term calculations, a smaller rate constant of 2E-6 m/s is recommended. The lower bound of the I{sup -}/Ag rate constant was 3E-8 m/s which could be used in very conservative source term calculations. (author) 20 figs., 6 tabs., 15 refs.

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

    Science.gov (United States)

    Maher, K.; Steefel, Carl; White, A.F.; Stonestrom, David A.

    2009-01-01

    the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO2(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws. ?? 2009 Elsevier Ltd.

  4. Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-10^7 K)

    Science.gov (United States)

    Ocaña, A. J.; Blázquez, S.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejoab, J.; Jiménez, E.

    2018-02-01

    Ethanol, CH3CH2OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH3CH2OH (k(T)) between 21 and 10^7 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(10^7 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10^-11 (T/300 K)-(0.71±0.10) cm^3 molecule^-1 s^-1. In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (˜10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10^-11 cm^3 molecule^-1 s^-1 at 100 K and around 1 × 10^-10 cm^3 molecule^-1 s^-1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

  5. Effects of phase lag on the information rate of a bistable Duffing oscillator

    International Nuclear Information System (INIS)

    Perkins, Edmon; Balachandran, Balakumar

    2015-01-01

    To utilize noise for systems, which are transmitting or receiving information, the information rate is a necessary metric to consider. The phase lag, which is the difference between the sender (applied forcing) and receiver (the oscillator) phases, has a significant effect on the information rate. However, this phase lag is a nonlinear function of the noise level. Here, the effects of phase lag on the information rate for a Duffing oscillator are examined and comparative discussions are made with phase lag from linear response theory. The phase lag is shown to be an important variable in calculating the information rate. - Highlights: • Simulations and Fokker–Planck analysis for Duffing oscillator response are performed. • The phase lag is found to be a nonlinear function of the noise level. • The phase lag is shown to be important for calculating the information rate metric

  6. Effects of phase lag on the information rate of a bistable Duffing oscillator

    Energy Technology Data Exchange (ETDEWEB)

    Perkins, Edmon, E-mail: edmon@umd.edu; Balachandran, Balakumar, E-mail: balab@umd.edu

    2015-02-06

    To utilize noise for systems, which are transmitting or receiving information, the information rate is a necessary metric to consider. The phase lag, which is the difference between the sender (applied forcing) and receiver (the oscillator) phases, has a significant effect on the information rate. However, this phase lag is a nonlinear function of the noise level. Here, the effects of phase lag on the information rate for a Duffing oscillator are examined and comparative discussions are made with phase lag from linear response theory. The phase lag is shown to be an important variable in calculating the information rate. - Highlights: • Simulations and Fokker–Planck analysis for Duffing oscillator response are performed. • The phase lag is found to be a nonlinear function of the noise level. • The phase lag is shown to be important for calculating the information rate metric.

  7. Effect of low and high heating rates on reaction path of Ni(V)/Al multilayer

    Energy Technology Data Exchange (ETDEWEB)

    Maj, Łukasz, E-mail: l.maj@imim.pl [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Morgiel, Jerzy; Szlezynger, Maciej [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Bała, Piotr; Cios, Grzegorz [AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, 30 Kawiory St., 30-055 Kraków (Poland)

    2017-06-01

    The effect of heating rates of Ni(V)/Al NanoFoils{sup ®} was investigated with transmission electron microscopy (TEM). The Ni(V)/Al were subjected to heating by using differential scanning calorimetry (DSC), in-situ TEM or electric pulse. Local chemical analysis was carried out using energy dispersive X-ray spectroscopy (EDS). Phase analysis was done with X-ray diffractions (XRD) and selected area electron diffractions (SAED). The experiments showed that slow heating in DSC results in development of separate exothermic effects at ∼230 °C, ∼280 °C and ∼390 °C, corresponding to precipitation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl phases, respectively, i.e. like in vanadium free Ni/Al multilayers. Further heating to 700 °C allowed to obtain a single phase NiAl foil. The average grain size (g.s.) of NiAl phase produced in the DSC heat treated foil was comparable with the Ni(V)/Al multilayer period (∼50 nm), whereas in the case of reaction initiated with electric pulse the g.s. was in the micrometer range. Upon slow heating vanadium tends to segregate to zones parallel to the original multilayer internal interfaces, while in SHS process vanadium-rich phases precipitates at grain boundaries of the NiAl phase. - Highlights: • Peaks in DSC heating of Ni(V)/Al were explained by in-situ TEM observations. • Nucleation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl at slow heating of Ni(V)/Al was documented. • Near surface NiAl obtained from NanoFoil show Ag precipitates at grain boundaries.

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

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

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

    1986-12-01

    Newly measured nuclear reaction rates for 3 H(α,γ) 7 Li (higher than previous values) and 7 Li(p,α) 4 He (lower than previous values) are shown to increase the 7 Li yield from big bang nucleosynthesis for lower baryon to photon ratio (eta ≤ 4 x 10 -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 7 Li in big bang baryon density determinations. The new 7 Li constraints imply a lower limit on eta of 2 x 10 -10 and an upper limit of 5 x 10 -10 . This lower limit to eta is concordant with that obtained from considerations of D + 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 -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,γ) 4 He reaction. 28 refs., 1 fig

  10. Quantum dynamics of fast chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Light, J.C. [Univ. of Chicago, IL (United States)

    1993-12-01

    The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.

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

    Science.gov (United States)

    Habershon, Scott

    2016-04-12

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

  12. Absolute calibration of the Rh-103 (n, n') Rh-103m reaction rate

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, W.H.; Murphy, M.F.; March, M.R. [Reactor Physics Division, Atomic Energy Establishment, Winfrith, Dorchester, Dorset (United Kingdom)

    1979-05-15

    The uncertainties in determining the absolute values of the Rh-103 (n, n') Rh-103m reaction rate (which is widely used as a neutron damage flux monitor) have been reduced to {approx}{+-}5%. This has been achieved with the use of a calibrated source of Pd-103-Rh-103m activity supplied by the I.A.E.A. Agreement to within 3% between measured and calculated values of the reaction rate (normalised to the U-238 fission rate) has been achieved. (author)

  13. Measurement from sun-synchronous orbit of a reaction rate controlling the diurnal NOx cycle in the stratosphere

    Directory of Open Access Journals (Sweden)

    A. Dudhia

    2011-05-01

    Full Text Available A reaction rate associated with the nighttime formation of an important diurnally varying species, N2O5, is determined from MIPAS-ENVISAT. During the day, photolysis of N2O5 in the stratosphere contributes to nitrogen-catalysed ozone destruction. However, at night concentrations of N2O5 increase, temporarily sequestering reactive NOx NO and NO2 in a natural cycle which regulates the majority of stratospheric ozone. In this paper, the reaction rate controlling the formation of N2O5 is determined from this instrument for the first time. The observed reaction rate is compared to the currently accepted rate determined from laboratory measurements. Good agreement is obtained between the observed and accepted experimental reaction rates within the error bars.

  14. The phase transport and reactions of γ-irradiated aqueous-ionic liquids

    International Nuclear Information System (INIS)

    Howett, S.; Joseph, J.; Noel, J.J.; Wren, J.C.

    2010-01-01

    A novel technology based on the transfer of chemical species across water/ionic liquid interfaces via specific complexation reactions is currently being considered for the separation and sequestration of metal ion contaminants from radioactive waste effluents in the nuclear fuel cycle. An ideal solvent for these applications should have a high intrinsic selectivity for a targeted metal or group of metals (e.g., trans-Pu actinides, lanthanides, or other fission products), an efficient switching mechanism (between complexation and decomplexation), and a high immiscibility with aqueous solutions. These characteristics must be maintained in the chemical, radiation, and mass transport environments present during the separation process. Ionic liquids (ILs) have an almost negligible vapour pressure and high thermal stability. Their ability to dissolve a wide range of substrate molecules and potential to be highly resilient in radiation fields make ILs particularly promising media. The separation efficiency of the biphasic system will depend on many parameters, including the aqueous oxidation state of the targeted metal ion, and the thermodynamics and kinetics of interfacial transport and metal-ligand complex formation at the water/IL interface or in the IL phase. The most uncertain and unstudied area for these applications is the effect of ionizing radiation on the stability and separation efficiency of the biphasic system. The present study investigates the effect of γ-radiation on gas/IL and water/IL interfacial stability and mass transfer with trihexyltetradecylphosphonium bis(trifluoromethyl-sulfonyl)imide, a phosphonium-based IL. The IL, in contact with either gas or water, was irradiated at a dose rate of 6.4 kGy·h -1 . Gas-phase samples were analyzed by gas chromatography-mass spectrometry (GC-MS) and the changes in the IL and aqueous phases were monitored by conductivity measurements and Raman spectroscopy. In this paper we discuss these observations and their

  15. The correlation schemes in calculations of the rate constants of some radiation chemical reactions

    International Nuclear Information System (INIS)

    Zagorets, P.A.; Shostenko, A.G.; Kim, V.

    1983-01-01

    The various correlation relationships of the evaluation of the rate constants of radiation chemical reactions of addition, abstraction and isomerization were considered. It was shown that neglection of the influence of solvent can result in errors in calculations of rate constants equalling two orders in magnitude. Several examples of isokinetic relationship are given. The methods of calculation of transmission coefficient of reaction addition have been discussed. (author)

  16. Rate constant and reaction coordinate of Trp-cage folding in explicit water

    NARCIS (Netherlands)

    Juraszek, J.; Bolhuis, P.G.

    2008-01-01

    We report rate constant calculations and a reaction coordinate analysis of the rate-limiting folding and unfolding process of the Trp-cage mini-protein in explicit solvent using transition interface sampling. Previous transition path sampling simulations revealed that in this (un)folding process the

  17. Deuterium isotope effects in condensed-phase thermochemical decomposition reactions of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

    International Nuclear Information System (INIS)

    Shackelford, S.A.; Coolidge, M.B.; Goshgarian, B.B.; Loving, B.A.; Rogers, R.N.; Janney, J.L.; Ebinger, M.H.

    1985-01-01

    The deuterium isotope effect was applied to condensed-phase thermochemical reactions of HMX and HMX-d 8 by using isothermal techniques. Dissimilar deuterium isotope effects revealed a mechanistic dependence of HMX upon different physical states which may singularly predominate in a specific type of thermal event. Solid-state HMX thermochemical decomposition produces a primary deuterium isotope effect (DIE), indicating that covalent C-H bond rupture is the rate-controlling step in this phase. An apparent inverse DIE is displayed by the mixed melt phase and can be attributed to C-H bond contraction during a weakening of molecular lattice forces as the solid HMX liquefies. The liquid-state decomposition rate appears to be controlled by ring C-N bond cleavage as evidenced by a secondary DIE and higher molecular weight products. These results reveal a dependence of the HMX decomposition process on physical state and lead to a broader mechanistic interpretation which explains the seemingly contradictory data found in current literature reviews. 33 references, 9 figures, 5 tables

  18. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    International Nuclear Information System (INIS)

    Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso

    2012-01-01

    Highlights: ► Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. ► Gas chromatography and computational potential energy surfaces were performed. ► A mechanism in steps looked like the most probable mechanism. ► A spin–orbit coupling appeared at the singlet and triple diradical open structures. ► A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463–503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10 13 s −1 , respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G ∗∗ level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin–orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

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

    Science.gov (United States)

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

    2012-04-05

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

  20. Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

    Science.gov (United States)

    Franczuk, Barbara; Danikiewicz, Witold

    2018-03-01

    Ion-molecule reactions of Me2S2 with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction ( m/z 47), SN2 ( m/z 79), and E2 elimination - addition sequence of reactions ( m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent SN2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results. [Figure not available: see fulltext.

  1. Direct characterization of phase transformations and morphologies in moving reaction zones in Al/Ni nanolaminates using dynamic transmission electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kim, J.S., E-mail: judy.kim@materials.ox.ac.uk [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Chemical Engineering and Materials Science/Molecular and Cellular Biology, University of California-Davis, 1 Shields Avenue, Davis, CA 95616 (United States); LaGrange, T.; Reed, B.W. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Knepper, R.; Weihs, T.P. [Department of Materials Science and Engineering, Johns Hopkins University, 3400 N. Charles St., Baltimore, MD 21218 (United States); Browning, N.D. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States); Chemical Engineering and Materials Science/Molecular and Cellular Biology, University of California-Davis, 1 Shields Avenue, Davis, CA 95616 (United States); Campbell, G.H. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (United States)

    2011-05-15

    Highlights: > Fast phase transformations are examined in Al/Ni reactive nanolaminates. > Results visible only by dynamic transmission electron microscopy at ns resolution. > NiAl forms under 15 ns after reaction front in all three stoichiometries studied. > DTEM imaging reveals a transient cellular morphology in nonequiatomic films. - Abstract: Phase transformations and transient morphologies are examined as exothermic formation reactions self-propagate across Al/Ni nanolaminate films. The rapid evolution of these phases and sub-micrometer morphological features requires nanoscale temporal and spatial resolution that is not available with traditional in situ electron microscopy. This work uses dynamic transmission electron microscopy to identify intermetallic products and phase morphologies, as exothermic formation reactions self-propagate in nanolaminate films grown with 3:2, 2:3 and 1:1 Al/Ni atomic ratios. Single-shot diffraction patterns with 15 ns temporal resolution reveal that the NiAl intermetallic forms within {approx}15 ns of the reaction front's arrival in all three types of films and is the only intermetallic phase to form, as the reactions self-propagate and quench very rapidly. Time-resolved imaging reveals a transient cellular morphology in the Al-rich and Ni-rich foils, but not in the equiatomic films. The cellular features in the Al-rich and Ni-rich films are attributed to a cooling trajectory through a two-phase field of liquid + NiAl.

  2. Uranium fluoride chemistry. Part 1. The gas phase reaction of uranium hexafluoride with alcohols

    International Nuclear Information System (INIS)

    Schnautz, N.G.; Venter, P.J.

    1992-01-01

    The reaction between uranium hexafluoride (UF 6 ) and simple alcohols in the gas phase was observed to proceed by way of three possible reaction pathways involving dehydration, deoxygenative fluorination, and ether formation. These reactions can best be explained by assuming that alcohols first react with UF 6 to afford the alkoxy uranium pentafluoride intermediate ROUF 5 , which reacts further to give the dehydration, deoxygenative fluorination, and ether products. In each of the above three reaction pathways, UF 6 is transformed to UOF 4 , which being as reactive toward alcohols as UF 6 , reacts further with the alcohol in question to finally afford the unreactive uranyl fluoride (UO 2 F 2 ). 6 refs., 2 tabs

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

    Science.gov (United States)

    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).

  4. Modeling the pH and temperature dependence of aqueousphase hydroxyl radical reaction rate constants of organic micropollutants using QSPR approach.

    Science.gov (United States)

    Gupta, Shikha; Basant, Nikita

    2017-11-01

    Designing of advanced oxidation process (AOP) requires knowledge of the aqueous phase hydroxyl radical ( ● OH) reactions rate constants (k OH ), which are strictly dependent upon the pH and temperature of the medium. In this study, pH- and temperature-dependent quantitative structure-property relationship (QSPR) models based on the decision tree boost (DTB) approach were developed for the prediction of k OH of diverse organic contaminants following the OECD guidelines. Experimental datasets (n = 958) pertaining to the k OH values of aqueous phase reactions at different pH (n = 470; 1.4 × 10 6 to 3.8 × 10 10  M -1  s -1 ) and temperature (n = 171; 1.0 × 10 7 to 2.6 × 10 10  M -1  s -1 ) were considered and molecular descriptors of the compounds were derived. The Sanderson scale electronegativity, topological polar surface area, number of double bonds, and halogen atoms in the molecule, in addition to the pH and temperature, were found to be the relevant predictors. The models were validated and their external predictivity was evaluated in terms of most stringent criteria parameters derived on the test data. High values of the coefficient of determination (R 2 ) and small root mean squared error (RMSE) in respective training (> 0.972, ≤ 0.12) and test (≥ 0.936, ≤ 0.16) sets indicated high generalization and predictivity of the developed QSPR model. Other statistical parameters derived from the training and test data also supported the robustness of the models and their suitability for screening new chemicals within the defined chemical space. The developed QSPR models provide a valuable tool for predicting the ● OH reaction rate constants of emerging new water contaminants for their susceptibility to AOPs.

  5. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 1 covers papers on the advances of gas phase ion chemistry. The book discusses the advances in flow tubes and the measurement of ion-molecule rate coefficients and product distributions; the ion chemistry of the earth's atmosphere; and the classical ion-molecule collision theory. The text also describes statistical methods in reaction dynamics; the state selection by photoion-photoelectron coincidence; and the effects of temperature and pressure in the kinetics of ion-molecule reactions. The energy distribution in the unimolecular decomposition of ions, as well

  6. The reaction O((3)P) + HOBr: Temperature dependence of the rate constant and importance of the reaction as an HOBr stratospheric loss process

    Science.gov (United States)

    Nesbitt, F. L.; Monks, P. S.; Payne, W. A.; Stief, L. J.; Toumi, R.

    1995-01-01

    The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.

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

    International Nuclear Information System (INIS)

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

    1996-12-01

    Rates of complex formation and dissociation in NpO 2 + - 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 3+ , Eu 3+ , Dy 3+ , and Fe 3+ with CLIII. Rate determining step in each system is an intramolecular process, the NpO 2 + -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 ΔH=46.2±0.3 kJ/m and ΔS=7± J/mK (I=1.0 M); these for the acid dependent and independent dissociation pathways are ΔH=38.8±0.6 kJ/m, ΔS=-96±18 J/mK, ΔH=70.0± kJ/m, and ΔS=17±1 J/mK, respectively. An isokinetic relationship is observed between the activation parameters for CLIII complex formation with NpO 2 + , UO 2 2+ , Th 4+ , and Zr 4+ . Rates of CLIII complex formation reactions for Fe 3+ , Zr 4+ , NpO 2 + , UO 2 2+ , Th 4+ , La 3+ , Eu 3+ , and Dy 3+ correlate with cation radius rather than charge/radius ratio

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

    Science.gov (United States)

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

    2016-07-27

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

  9. Reaction kinetics aspect of U3O8 kernel with gas H2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO2 kernel

    International Nuclear Information System (INIS)

    Damunir

    2007-01-01

    The reaction kinetics aspect of U 3 O 8 kernel with gas H 2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO 2 kernel had been studied. U 3 O 8 kernel was reacted with gas H 2 in a reduction furnace at varied reaction time and temperature. The reaction temperature was varied at 600, 700, 750 and 850 °C with a pressure of 50 mmHg for 3 hours in gas N 2 atmosphere. The reation time was varied at 1, 2, 3 and 4 hours at a temperature of 750 °C using similar conditions. The reaction product was UO 2 kernel. The reaction kinetic aspect between U 3 O 8 and gas H 2 comprised the minimum activation energy (ΔE), the reaction rate constant and the O/U ratio of UO 2 kernel. The minimum activation energy was determined from a straight line slope of equation ln [{D b . R o {(1 - (1 - X b ) ⅓ } / (b.t.Cg)] = -3.9406 x 10 3 / T + 4.044. By multiplying with the straight line slope -3.9406 x 10 3 , the ideal gas constant (R) 1.985 cal/mol and the molarity difference of reaction coefficient 2, a minimum activation energy of 15.644 kcal/mol was obtained. The reaction rate constant was determined from first-order chemical reaction control and Arrhenius equation. The O/U ratio of UO 2 kernel was obtained using gravimetric method. The analysis result of reaction rate constant with chemical reaction control equation yielded reaction rate constants of 0.745 - 1.671 s -1 and the Arrhenius equation at temperatures of 650 - 850 °C yielded reaction rate constants of 0.637 - 2.914 s -1 . The O/U ratios of UO 2 kernel at the respective reaction rate constants were 2.013 - 2.014 and the O/U ratios at reaction time 1 - 4 hours were 2.04 - 2.011. The experiment results indicated that the minimum activation energy influenced the rate constant of first-order reaction and the O/U ratio of UO 2 kernel. The optimum condition was obtained at reaction rate constant of 1.43 s -1 , O/U ratio of UO 2 kernel of 2.01 at temperature of 750 °C and reaction time of 3

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

    Energy Technology Data Exchange (ETDEWEB)

    Peters, Catherine A [Princeton University

    2013-05-15

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

  11. Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Copper

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2011-01-01

    1.1 This test method covers procedures for measuring reaction rates by the activation reaction 63Cu(n,α)60Co. The cross section for 60Co produced in this reaction increases rapidly with neutrons having energies greater than about 5 MeV. 60Co decays with a half-life of 1925.27 days (±0.29 days)(1) and emits two gamma rays having energies of 1.1732278 and 1.332492 MeV (1). The isotopic content of natural copper is 69.17 % 63Cu and 30.83 % 65Cu (2). The neutron reaction, 63Cu(n,γ)64Cu, produces a radioactive product that emits gamma rays which might interfere with the counting of the 60Co gamma rays. 1.2 With suitable techniques, fission-neutron fluence rates above 109 cm−2·s−1 can be determined. The 63Cu(n,α)60Co reaction can be used to determine fast-neutron fluences for irradiation times up to about 15 years (for longer irradiations, see Practice E261). 1.3 Detailed procedures for other fast-neutron detectors are referenced in Practice E261. 1.4 This standard does not purport to address all of the...

  12. Effect of loading rate on dynamic fracture of reaction bonded silicon nitride

    Science.gov (United States)

    Liaw, B. M.; Kobayashi, A. S.; Emery, A. F.

    1986-01-01

    Wedge-loaded, modified tapered double cantilever beam (WL-MTDCB) specimens under impact loading were used to determine the room temperature dynamic fracture response of reaction bonded silicon nitride (RBSN). The crack extension history, with the exception of the terminal phase, was similar to that obtained under static loading. Like its static counterpart, a distinct crack acceleration phase, which was not observed in dynamic fracture of steel and brittle polymers, was noted. Unlike its static counterpart, the crack continued to propagate at nearly its terminal velocity under a low dynamic stress intensity factor during the terminal phase of crack propagation. These and previously obtained results for glass and RBSN show that dynamic crack arrest under a positive dynamic stress intensity factor is unlikely in static and impact loaded structural ceramics.

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

    CERN Document Server

    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.

  14. Standard Test Method for Measuring Reaction Rates by Radioactivation of Neptunium-237

    CERN Document Server

    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 237Np(n,f)F.P. 1.2 The reaction is useful for measuring neutrons with energies from approximately 0.7 to 6 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 units 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.

  15. Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

    2011-07-01

    Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

  16. Large area isotopic silicon targets for astrophysical reaction rate studies in Si-26

    NARCIS (Netherlands)

    Greene, JP; Berg, GPA

    2005-01-01

    For measurements of stellar reaction rates of proton rich nuclei involving resonance levels just above threshold, targets of Si-28 were used in studies of the Si-21(He-4, He-6)Si-26 reaction using the Research Center for Nuclear Physics (RCNP) Ring Cyclotron at Osaka University. Resonance structure

  17. Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Aluminum

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2011-01-01

    1.1 This test method covers procedures measuring reaction rates by the activation reaction 27Al(n,α)24Na. 1.2 This activation reaction is useful for measuring neutrons with energies above approximately 6.5 MeV and for irradiation times up to about 2 days (for longer irradiations, see Practice E261). 1.3 With suitable techniques, fission-neutron fluence rates above 106 cm−2·s−1 can be determined. 1.4 Detailed procedures for other fast neutron detectors are referenced in Practice E261. 1.5 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.

  18. Applications of the absolute reaction rate theory to biological responses in electric and magnetic fields

    International Nuclear Information System (INIS)

    Brannen, J.P.; Wayland, J.R.

    1976-01-01

    This paper develops a theoretical foundation for the study of biological responses of electric and magnetic fields. The basis of the development is the absolute reaction rate theory and the effects of fields on reaction rates. A simple application to the response of Bacillus subtilis var niger in a microwave field is made. Potential areas of application are discussed

  19. Rates of ionic reactions with charged nanoparticles in aqueous media

    NARCIS (Netherlands)

    Duval, J.F.L.; Leeuwen, van H.P.

    2012-01-01

    A theory is developed to evaluate the electrostatic correction for the rate of reaction between a small ion and a charged ligand nanoparticle. The particle is assumed to generally consist of an impermeable core and a shell permeable to water and ions. A derivation is proposed for the ion diffusion

  20. A Fluorogenic Aromatic Nucleophilic Substitution Reaction for Demonstrating Normal-Phase Chromatography and Isolation of Nitrobenzoxadiazole Chromophores

    Science.gov (United States)

    Key, Jessie A.; Li, Matthew D.; Cairo, Christopher W.

    2011-01-01

    Normal-phase chromatography is an essential technique for monitoring chemical reactions, identifying the presence of specific components, as well as the purification of organic compounds. An experiment to facilitate the instruction and understanding of the concepts behind normal-phase chromatography at the introductory and intermediate…

  1. Influence of phase transition on pattern formation during catalytic reactions

    OpenAIRE

    Andrade, Roberto Fernandes Silva; Lima, D.; Cunha, F. B.

    2000-01-01

    p.434–445 We investigate the influence of the order of surface phase transitions on pattern formation during chemical reaction on mono-crystal catalysts. We use a model consisting of two partial differential equations, one of which describes the dynamics of the surface state with the help of a Ginzburg–Landau potential. Second- or first-order transitions are described by decreasing or increasing the relative value of the third-order coefficient of the potential. We concentrate on the stabi...

  2. The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2017-09-07

    A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

  3. Neutrino-induced charged-current reaction rates for r-process nuclei

    CERN Document Server

    Langanke, K

    2001-01-01

    Neutrino-induced reactions play an important role during and after the r-process if it occurs in an environment with extreme neutrino fluxes, as in the neutrino-driven wind model or neutron star mergers. The neutrino reactions can excite the daughter nucleus above the neutron threshold, which is quite low for r-process nuclei. Thus the daughter nucleus will decay by emission of one or several neutrons. We have calculated the relevant total (nu sub e , e sup -) cross sections as well as the partial neutron spallation cross sections for r-process nuclei with neutron numbers N=41-135 and proton numbers Z=21-82. The supernova neutrino spectrum is described by a Fermi-Dirac distribution with various temperature parameters between T=2.8 MeV and T=10 MeV and with the degeneracy parameters alpha=0 and alpha=3. Our calculations of the nuclear response are based on the random phase approximation and consider allowed as well as forbidden transitions.

  4. Control rod effects on reaction rate distributions in tight pitched PuO2-UO2 fuel assembly

    International Nuclear Information System (INIS)

    Gil, Choong-Sup; Okumura, Keisuke; Ishiguro, Yukio

    1991-11-01

    Investigations were made for the heterogeneity effects caused by insertion or withdrawal of a B 4 C control rod on fine structure of reaction rates distributions in a tight pitched PuO 2 -UO 2 fuel assembly. Analysis was carried out by using the VIM and SRAC codes with the libraries based on JENDL-2 for the hexagonal fuel assembly basically corresponding to the PROTEUS-LWHCR experimental core. The reaction rates are affected more remarkably by the withdrawal of the control rod rather than its insertion. The changes of the reaction rates were decomposed into three terms of spectrum shifts, the changes of effective cross sections with fine groups, and their higher order components. From the analysis, it is concluded that most changes of reaction rates are caused by spectral shifts. The SRAC code with fine group constants can predict the distribution of reaction rates and their ratios with the accuracy of about 5 % except for the values related to Pu-242 capture rate, as compared with the VIM results. To increase the accuracy, it is necessary to generate the effective cross sections of the fuel near control rods with consideration of the heterogeneities in the fuel assembly. (author)

  5. Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

    KAUST Repository

    Nurlaela, Ela

    2016-01-25

    The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.

  6. Optimization of o-phtaldialdehyde/2-mercaptoethanol postcolumn reaction for the hydrophilic interaction liquid chromatography determination of memantine utilizing a silica hydride stationary phase.

    Science.gov (United States)

    Douša, Michal; Pivoňková, Veronika; Sýkora, David

    2016-08-01

    A rapid procedure for the determination of memantine based on hydrophilic interaction chromatography with fluorescence detection was developed. Fluorescence detection after postcolumn derivatization with o-phtaldialdehyde/2-mercaptoethanol was performed at excitation and emission wavelengths of 345 and 450 nm, respectively. The postcolumn reaction conditions such as reaction temperature, derivatization reagent flow rate, and reagents concentration were studied due to steric hindrance of amino group of memantine. The derivatization reaction was applied for the hydrophilic interaction liquid chromatography method which was based on Cogent Silica-C stationary phase with a mobile phase consisting of a mixture of 10 mmol/L citric acid and 10 mmol/L o-phosphoric acid (pH 6.0) with acetonitrile using an isocratic composition of 2:8 v/v. The benefit of the reported approach consists in a simple sample pretreatment and a quick and sensitive hydrophilic interaction chromatography method. The developed method was validated in terms of linearity, accuracy, precision, and selectivity according to the International Conference on Harmonisation guidelines. The developed method was successfully applied for the analysis of commercial memantine tablets. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  8. Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

    International Nuclear Information System (INIS)

    Xuelei Chu; Ohmoto, Hiroshi

    1991-01-01

    For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

  9. Communication: Equilibrium rate coefficients from atomistic simulations: The O(3P) + NO(2Π) → O2(X3Σg−) + N(4S) reaction at temperatures relevant to the hypersonic flight regime

    International Nuclear Information System (INIS)

    Castro-Palacio, Juan Carlos; Bemish, Raymond J.; Meuwly, Markus

    2015-01-01

    The O( 3 P) + NO( 2 Π) → O 2 (X 3 Σ g − ) + N( 4 S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20 000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions

  10. Communication: Equilibrium rate coefficients from atomistic simulations: The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction at temperatures relevant to the hypersonic flight regime.

    Science.gov (United States)

    Castro-Palacio, Juan Carlos; Bemish, Raymond J; Meuwly, Markus

    2015-03-07

    The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20,000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions.

  11. Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Nickel

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This test method covers procedures for measuring reaction rates by the activation reaction 58Ni(n,p)58Co. 1.2 This activation reaction is useful for measuring neutrons with energies above approximately 2.1 MeV and for irradiation times up to about 200 days in the absence of high thermal neutron fluence rates (for longer irradiations, see Practice E 261). 1.3 With suitable techniques fission-neutron fluence rates densities above 107 cm−2·s−1 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 units 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. Note—The burnup corrections were com...

  12. Thermonuclear F-19(p,alpha(0))O-16 reaction rate

    Czech Academy of Sciences Publication Activity Database

    He, J. J.; Lombardo, I.; Dell'Aquila, D.; Xu, Yi; Zang, L. Y.; Liu, W. P.

    2018-01-01

    Roč. 42, č. 1 (2018), č. článku 015001. ISSN 1674-1137 Institutional support: RVO:61389005 Keywords : asymptotic giant branch (AGB) star * nucleosynthesis * astrophysical S factor * cross section * reaction rate Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics OBOR OECD: Astronomy (including astrophysics,space science) Impact factor: 5.084, year: 2016

  13. Phase space conduits for reaction in multidimensional systems : HCN isomerization in three dimensions

    NARCIS (Netherlands)

    Waalkens, Holger; Burbanks, Andrew; Wiggins, Stephen

    2004-01-01

    The three-dimensional hydrogen cyanide/isocyanide isomerization problem is taken as an example to present a general theory for computing the phase space structures which govern classical reaction dynamics in systems with an arbitrary (finite) number of degrees of freedom. The theory, which is

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

    Science.gov (United States)

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

    2014-06-28

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

  15. Irradiation of fish fillets: Relation of vapor phase reactions to storage quality

    Science.gov (United States)

    Spinelli, J.; Dollar, A.M.; Wedemeyer, G.A.; Gallagher, E.C.

    1969-01-01

    Fish fillets irradiated under air, nitrogen, oxygen, or carbon dioxide atmospheres developed rancidlike flavors when they were stored at refrigerated temperatures. Packing and irradiating under vacuum or helium prevented development of off-flavors during storage.Significant quantities of nitrate and oxidizing substances were formed when oxygen, nitrogen, or air were present in the vapor or liquid phases contained in a Pyrex glass model system exposed to ionizing radiation supplied by a 60Co source. It was demonstrated that the delayed flavor changes that occur in stored fish fillets result from the reaction of vapor phase radiolysis products and the fish tissue substrates.

  16. Mechanism of the CO2-Ca(OH)2 reaction

    International Nuclear Information System (INIS)

    Chew, V.S.; Cheh, C.H.; Glass, R.W.

    1983-01-01

    Recent studies clearly showed the importance of moisture in achieving high Ca(OH) 2 absorbent utilization for removing CO 2 from gas streams at ambient temperatures. However, the role of moisture and the mechanism of the reaction was not well understood. This paper summarizes the results of a study of the mechanism of the CO 2 -Ca(OH) 2 reaction with emphasis on the role of moisture. The reaction between Ca(OH) 2 and CO 2 in moist N 2 was found to be first order with respect to the reactants with a rate constant of about 100 min -1 . At high humidities, the rate of reaction was chemically controlled, but at low humidities, the reaction rate was limited by the diffusion through the carbonate layer formed by the reaction. Calculations showed that capillary condensation could have occurred only in about 2% of the pore volume and was unlikely to have affected the reaction rate significantly by allowing the reaction to occur in the liquid phase. It was, therefore, concluded that the main role of moisture was to improve the Ca(OH) 2 utilization by lowering the resistance to diffusion through the carbonate layer

  17. Nonequilibrium Contribution to the Rate of Reaction. III. Isothermal Multicomponent Systems

    Science.gov (United States)

    Shizgal, B.; Karplus, M.

    1970-10-01

    The nonequilibrium contribution to the reaction rate of an isothermal multicomponent system is obtained by solution of the appropriate Chapman-Enskog equation; the system is composed of reactive species in contact with a heat bath of inert atoms M.

  18. Luteal phase of the menstrual cycle increases sweating rate during exercise

    Directory of Open Access Journals (Sweden)

    Garcia A.M.C.

    2006-01-01

    Full Text Available The present study evaluated whether the luteal phase elevation of body temperature would be offset during exercise by increased sweating, when women are normally hydrated. Eleven women performed 60 min of cycling exercise at 60% of their maximal work load at 32ºC and 80% relative air humidity. Each subject participated in two identical experimental sessions: one during the follicular phase (between days 5 and 8 and the other during the luteal phase (between days 22 and 25. Women with serum progesterone >3 ng/mL, in the luteal phase were classified as group 1 (N = 4, whereas the others were classified as group 2 (N = 7. Post-exercise urine volume (213 ± 80 vs 309 ± 113 mL and specific urine gravity (1.008 ± 0.003 vs 1.006 ± 0.002 changed (P < 0.05 during the luteal phase compared to the follicular phase in group 1. No menstrual cycle dependence was observed for these parameters in group 2. Sweat rate was higher (P < 0.05 in the luteal (3.10 ± 0.81 g m-2 min-1 than in the follicular phase (2.80 ± 0.64 g m-2 min-1 only in group 1. During exercise, no differences related to menstrual cycle phases were seen in rectal temperature, heart rate, rate of perceived exertion, mean skin temperature, and pre- and post-exercise body weight. Women exercising in a warm and humid environment with water intake seem to be able to adapt to the luteal phase increase of basal body temperature through reduced urinary volume and increased sweating rate.

  19. Reaction rates and electrical resistivities of the hydrogen isotopes with, and their solubilities in, liquid lithium

    International Nuclear Information System (INIS)

    Pulham, R.J.; Adams, P.F.; Hubberstey, P.; Parry, G.; Thunder, A.E.

    1976-01-01

    The rate of reaction, k, of hydrogen and of deuterium with liquid lithium have been determined up to pressures of 20kNm -2 and at temperatures between 230 and 270 0 C. The reaction is first order with an apparent activation energy of 52.8 and 55.2 kJmol -1 for hydrogen and deuterium, respectively. The deuterium isotope effect, k/sub H/k/sub D/, decreases from 2.95 at 230 to 2.83 at 270 0 C. Tritium is predicted to react even more slowly than deuterium. The freezing point of lithium is depressed by 0.082 and 0.075 0 C, respectively, by dissolved hydride and deuteride giving eutectics at 0.016 mol percent H and 0.012 mol percent D in the metal-salt phase diagrams. The depression and eutectic concentration are expected to be less for tritium. The increase in the resistivity of liquid lithium caused by dissolved hydrogen isotopes is linear and relatively large, 5 x 10 -8 Ωm (mol percent H or D) -1 . The solubility of lithium hydride and deuteride was determined from the marked change in resistivity on saturation. The liquidus of the metal-salt phase diagram rises steeply from the eutectic point to meet the two-immiscible liquid region. Tritium is expected to be less soluble than deuterium. The partial molar enthalpies of solution are 44.2 and 55.0 kJmol -1 for hydrogen and deuterium, respectively. These values are used to calculate the solvation enthalpies of the isotope anions in the metal

  20. Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

  1. Possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime

    Energy Technology Data Exchange (ETDEWEB)

    Chumakov, G A; Slinko, M G

    1979-05-01

    The possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime was demonstrated by analyzing a kinetic model of hydrogen interaction with oxygen over a metallic catalyst. Within a certain interval of partial pressures of oxygen, the average reaction rate over a period of oscillation may be over five times that of the steady-state reaction.

  2. Phase-Separated Polyaniline/Graphene Composite Electrodes for High-Rate Electrochemical Supercapacitors.

    Science.gov (United States)

    Wu, Jifeng; Zhang, Qin'e; Zhou, An'an; Huang, Zhifeng; Bai, Hua; Li, Lei

    2016-12-01

    Polyaniline/graphene hydrogel composites with a macroscopically phase-separated structure are prepared. The composites show high specific capacitance and excellent rate performance. Further investigation demonstrates that polyaniline inside the graphene hydrogel has low rate performance, thus a phase-separated structure, in which polyaniline is mainly outside the graphene hydrogel matrix, can enhance the rate performance of the composites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Manogaran, Lavaneesvari; Sek, Siok Kun

    2017-04-01

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

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

    Science.gov (United States)

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

    2010-01-01

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

  5. Multiphasic Reaction Modeling for Polypropylene Production in a Pilot-Scale Catalytic Reactor

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-06-01

    Full Text Available In this study, a novel multiphasic model for the calculation of the polypropylene production in a complicated hydrodynamic and the physiochemical environments has been formulated, confirmed and validated. This is a first research attempt that describes the development of the dual-phasic phenomena, the impact of the optimal process conditions on the production rate of polypropylene and the fluidized bed dynamic details which could be concurrently obtained after solving the model coupled with the CFD (computational fluid dynamics model, the basic mathematical model and the moment equations. Furthermore, we have established the quantitative relationship between the operational condition and the dynamic gas–solid behavior in actual reaction environments. Our results state that the proposed model could be applied for generalizing the production rate of the polymer from a chemical procedure to pilot-scale chemical reaction engineering. However, it was assumed that the solids present in the bubble phase and the reactant gas present in the emulsion phase improved the multiphasic model, thus taking into account that the polymerization took place mutually in the emulsion besides the bubble phase. It was observed that with respect to the experimental extent of the superficial gas velocity and the Ziegler-Natta feed rate, the ratio of the polymer produced as compared to the overall rate of production was approximately in the range of 9%–11%. This is a significant amount and it should not be ignored. We also carried out the simulation studies for comparing the data of the CFD-dependent dual-phasic model, the emulsion phase model, the dynamic bubble model and the experimental results. It was noted that the improved dual-phasic model and the CFD model were able to predict more constricted and safer windows at similar conditions as compared to the experimental results. Our work is unique, as the integrated developed model is able to offer clearer ideas

  6. Rate Constants for the Reactions of OH with CO, NO and NO2, and of HO2 with NO2 in the Presence of Water Vapour at Lower-Tropospheric Conditions

    Science.gov (United States)

    Rolletter, Michael; Fuchs, Hendrik; Novelli, Anna; Ehlers, Christian; Hofzumahaus, Andreas

    2016-04-01

    Recent studies have shown that the chemistry of gaseous nitrous acid (HONO) in the lower troposphere is not fully understood. Aside from heterogenous reactions, the daytime HONO formation in the gas-phase is not well understood (Li et al., Science, 2014). For a better understanding of HONO in the gas-phase, we have reinvestigated the reaction rate constants of important tropospheric reactions of the HOx radical family (OH and HO2) with nitrogen oxides at realistic conditions of the lower troposphere (at ambient temperature/pressure and in humid air). In this study we apply a direct pump and probe technique with high accuracy, using small radical concentrations to avoid secondary chemistry. Pulsed laser photolysis/laser-induced fluorescence (LP/LIF) was used to investigate the reaction rate constants of OH with CO, NO, NO2, and HO2 with NO2 in synthetic air at different water vapor concentrations (up to 5 x 1017 molecules cm-3). Photolysis of ozone in the presence of gaseous water was the source of OH. The reactions took place in a flow-tube at room temperature and atmospheric pressure. The chemical decay of the radicals was monitored by laser-induced fluorescence detection in a low-pressure cell, which sampled air continuously from the end of the flow-tube. Knowing the reactant concentrations subsequently allowed to calculate the bimolecular reaction rate constants at 1 atm from the pseudo-first-order decays. In order to observe HO2 reactions, OH was converted into HO2 with an excess of CO in the flow-tube. The newly measured rate constants for OH with CO, NO and NO2 agree very well with current recommendations by NASA/JPL and IUPAC and have an improved accuracy (uncertainty < 5%). These rate coefficients are independent of the presence of water vapour. The measured rate constant of HO2 with NO2 was found to depend significantly on the water-vapour concentration (probably due to formation of HO2*H2O complexes) and to exceed current recommendations by NASA/JPL and

  7. Bunsen Reaction using a HIx Solution (HI-I2-H2O with Countercurrent Flow for Sulfur-Iodine Hydrogen Production Process

    Directory of Open Access Journals (Sweden)

    Kim Hyo-Sub

    2016-01-01

    Full Text Available In the sulfur-iodine hydrogen production process, the Bunsen reaction is a crucial section because of the linkage with the H2SO4 and HI decomposition sections. The HIx solution (HI-I2-H2O mixture was fed to the Bunsen reaction section as a reactant from the HI decomposition section. In this study, the Bunsen reaction using the HIx solution with countercurrent flow was performed. The production rate of HIx phase solution increased while that of H2SO4 phase solution was maintained constant when increasing the flow rate of HIx solution. As the SO2 flow rate increased, the production rates of H2SO4 and HIx phase solutions increased. The amount of resultant H2SO4 phase was very lower than that of resultant HIx phase under the conditions examined in this study.

  8. Influence of the medium on the reaction rate of the t-butoxyl radical with iron(II)

    International Nuclear Information System (INIS)

    Mihaljevic, B.; Razem, D.

    2002-01-01

    Complete text of publication follows. Tert-butoxyl radicals (t-BuO.) were generated by homolytic photodecomposition of di-tert-butylperoxide using ruby laser flashes at 347 nm. The reaction of t-BuO. radicals with Fe 2+ was studied under pseudo-first order conditions. The quantum yield Φ(Fe 3+ ) was determined by measuring the absorbance of Fe 3+ ion as [FeCl] 2+ complex at 360 nm 2 μs after the flash. According to the equation derived from the reaction scheme, the rate constant k 3 was obtained from the relative rate constant k r (k r =k 0 /k 3 ) and the value of k 0 ; the latter refers to the overall rate of the competing disappearance of t-BuO. radicals from the system (reaction 2), including the highest contribution of β-cleavage. The rate constant k 0 was determined using diphenylmethanol instead of Fe 2+ . The known rate constant of the reaction of t-BuO. radical with diphenylmethanol giving ketyl radicals (6.9 x 10 6 dm 3 mol -1 s -1 ) was applied. The quantum yield of ketyl radicals was determined by measuring the maximum of absorbance at 535 nm. At acid concentration of 0.023 mol dm -3 HCl the rate constant k 3 = 3.4 x 10 8 dm 3 mol -1 s -1 was determined. The relative rate constant increased with an increase of the hydrochloric acid concentration which has been ascribed to the lower stability of t-BuO. radical at higher acidity of the medium. The effect of polarity of the medium on the reaction rate was also determined. Decreasing k 3 in media of increasing polarity were explained by increasing of the β-scission rate of t-BuO. radical with increasing polarity of the medium

  9. Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

    KAUST Repository

    Song, Hyon Min

    2012-01-01

    The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions that are not limited to conventional Pd-related reactions. Four different Au@Pd core-shell NPs in this study were prepared at room temperature with help from the emulsion phase surrounding the Au core NPs. Au-Pd alloy NPs were prepared over 90 °C, and underwent phase transfer to aqueous medium for their catalytic use. Au@Pd core-shell NPs show catalytic activity in ethanol oxidation reactions as electrocatalysts, and both core-shell and alloy NPs are good to excellent catalysts in various Suzuki-Miyaura and Heck reactions as heterogeneous catalysts. Specifically, Au@Pd core-shell NPs with sharp branched arms show the highest yield in the reactions tested in this study. A relatively small amount (0.25 mol%) was used throughout the catalytic reactions. © 2012 The Royal Society of Chemistry.

  10. Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

    International Nuclear Information System (INIS)

    Janev, R.K.; Kato, T.; Wang, J.G.

    2001-05-01

    The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C x H y charge exchange reactions from thermal energies up to several hundreds keV for all C x H y molecules with x=1, 2, 3 and 1 ≤ y ≤ 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

  11. Enhancement in extraction rates by addition of organic acids to aqueous phase in solvent extraction of rare earth metals in presence of diethylenetriaminepentaacetic acid

    International Nuclear Information System (INIS)

    Matsuyama, Hideto; Azis, A.; Fujita, Mamoru; Teramoto, Masaaki.

    1996-01-01

    It is well known that the selectivity of rare earth metals by solvent extraction is increased by the addition of a chelating agent such as diethylenetriaminepentaacetic acid (DTPA) in the aqueous phase. One of the disadvantages of this method is the decrease in extraction rates due to complexation in the aqueous phase. In this paper, further addition of organic acids to the aqueous phase was examined for the purpose of enhancing the extraction rates in solvent extraction with DTPA. The addition of several kind of organic acids such as formic acid, acetic acid, malonic acid, lactic acid and citric acid was investigated for a Er/Y separation system. A remarkable enhancement in extraction rates was observed with a slight decrease in the selectivity by the addition of citric acid or lactic acid. Extraction rates in the presence of both DTPA and citric acid increased with the increase in citric acid concentration and with the increase in proton concentration. A 150 times enhancement in extraction rates was found in the low proton concentration condition. In order to analyze the extraction rates and selectivities obtained, mass transfer equations were presented by considering both the dissociation reaction of rare earth metal-DTPA complexes and the complex formation between rare earth metal and organic acid in the aqueous phase. The experimental data were analyzed by these equations. (author)

  12. The TDF System for Thermonuclear Plasma Reaction Rates, Mean Energies and Two-Body Final State Particle Spectra

    International Nuclear Information System (INIS)

    Warshaw, S I

    2001-01-01

    The rate of thermonuclear reactions in hot plasmas as a function of local plasma temperature determines the way in which thermonuclear ignition and burning proceeds in the plasma. The conventional model approach to calculating these rates is to assume that the reacting nuclei in the plasma are in Maxwellian equilibrium at some well-defined plasma temperature, over which the statistical average of the reaction rate quantity σv is calculated, where σ is the cross-section for the reaction to proceed at the relative velocity v between the reacting particles. This approach is well-understood and is the basis for much nuclear fusion and astrophysical nuclear reaction rate data. The Thermonuclear Data File (TDF) system developed at the Lawrence Livermore National Laboratory (Warshaw 1991), which is the topic of this report, contains data on the Maxwellian-averaged thermonuclear reaction rates for various light nuclear reactions and the correspondingly Maxwellian-averaged energy spectra of the particles in the final state of those reactions as well. This spectral information closely models the output particle and energy distributions in a burning plasma, and therefore leads to more accurate computational treatments of thermonuclear burn, output particle energy deposition and diagnostics, in various contexts. In this report we review and derive the theoretical basis for calculating Maxwellian-averaged thermonuclear reaction rates, mean particle energies, and output particle spectral energy distributions for these reactions in the TDF system. The treatment of the kinematics is non-relativistic. The current version of the TDF system provides exit particle energy spectrum distributions for two-body final state reactions only. In a future report we will discuss and describe how output particle energy spectra for three- and four-body final states can be developed for the TDF system. We also include in this report a description of the algorithmic implementation of the TDF

  13. Verification of dosimetry cross sections above 10 MeV based on measurement of activation reaction rates in fission neutron field

    International Nuclear Information System (INIS)

    Odano, Naoteru; Miura, Toshimasa; Yamaji, Akio.

    1996-01-01

    To validate the dosimetry cross sections in fast neutron energy range, activation reaction rates were measured for 5 types of dosimetry cross sections which have sensitivity in the energy rage above 10 MeV utilizing JRR-4 reactor of JAERI. The measured reaction rates were compared with the calculations reaction rates by a continuous energy monte carlo code MVP. The calculated reaction rates were based on two dosimetry files, JENDL Dosimetry File and IRDF-90.2. (author)

  14. Enhancing gas-phase reaction in a plasma using high intensity and high power ultrasonic acoustic waves

    DEFF Research Database (Denmark)

    2010-01-01

    is absorbed into said plasma (104), and where a sound pressure level of said generated ultrasonic high intensity and high power acoustic waves (102) is at least substantially 140 dB and where an acoustic power of said generated ultrasonic high intensity and high power acoustic waves (102); is at least...... substantially 100 W. In this way, a high sound intensity and power are obtained that efficiently enhances a gas-phase reaction in the plasma, which enhances the plasma process, e.g. enabling more efficient ozone or hydrogen generation using plasma in relation to reaction speed and/or obtained concentration......This invention relates to enhancing a gas-phase reaction in a plasma comprising: creating plasma (104) by at least one plasma source (106), and wherein that the method further comprises: generating ultrasonic high intensity and high power acoustic waves (102) having a predetermined amount...

  15. Pulse radiolysis of alkanes in the gas-phase, ion-molecule reactions and neutralization mechanisms of hydrocarbon ions

    International Nuclear Information System (INIS)

    Ausloos, P.

    1975-01-01

    A discussion is presented of the fate of unreactive hydrocarbon ions in various selected gaseous systems. It is shown that experiments performed with the high radiation dose rates obtained in pulse radiolysis experiments have several advantages over conventional low dose rate experiments for the elucidation of the mechanism of homogeneous neutralization of unreactive hydrocarbon ions. This is so because the charged species has a much shorter lifetime with respect to neutralization under high dose rate (pulse radiolysis) conditions, so that the reaction of the ions with minor impurities or accumulated products is much less probable than in low dose rate experiments. It is further shown through a few examples, that quantitative information about the rate contants of neutralization events and ion-molecule reactions can be obtained when the dose rate is high enough for neutralization and chemical reaction to be in competition. Once reliable rate constants for neutralization and ion-molecule reactions are derived, one can obtain a quantitative evaluation of the products which will by formed in the pulse radiolysis of a hydrocarbon gas mixture from a computer calculation. (author)

  16. Comparison of measured and calculated reaction rate distributions in an scwr-like test lattice

    Energy Technology Data Exchange (ETDEWEB)

    Raetz, Dominik, E-mail: dominik.raetz@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Jordan, Kelly A., E-mail: kelly.jordan@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Murphy, Michael F., E-mail: mike.murphy@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Perret, Gregory, E-mail: gregory.perret@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Chawla, Rakesh, E-mail: rakesh.chawla@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 Lausanne, EPFL (Switzerland)

    2011-04-15

    High resolution gamma-ray spectroscopy measurements were performed on 61 rods of an SCWR-like fuel lattice, after irradiation in the central test zone of the PROTEUS zero-power research reactor at the Paul Scherrer Institute in Switzerland. The derived reaction rates are the capture rate in {sup 238}U (C{sub 8}) and the total fission rate (F{sub tot}), and also the reaction rate ratio C{sub 8}/F{sub tot}. Each of these has been mapped rod-wise on the lattice and compared to calculated results from whole-reactor Monte Carlo simulations with MCNPX. Ratios of calculated to experimental values (C/E's) have been assessed for the C{sub 8}, F{sub tot} and C{sub 8}/F{sub tot} distributions across the lattice. These C/E's show excellent agreement between the calculations and the measurements. For the {sup 238}U capture rate distribution, the 1{sigma} level in the comparisons corresponds to an uncertainty of {+-}0.8%, while for the total fission rate the corresponding value is {+-}0.4%. The uncertainty for C{sub 8}/F{sub tot}, assessed as a reaction rate ratio characterizing each individual rod position in the test lattice, is significantly higher at {+-}2.2%. To determine the reproducibility of these results, the measurements were performed twice, once in 2006 and again in 2009. The agreement between these two measurement sets is within the respective statistical uncertainties.

  17. A study on the isotopic exchange between hydrogen and water on a catalyst in the liquid phase; Etude de l'echange isotopique entre l'hydrogene et l'eau sur catalyseur en phase liquide

    Energy Technology Data Exchange (ETDEWEB)

    Dirian, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Montarnal, R; Balaceanu, J C [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France)

    1958-07-01

    It is well known that catalytic exchange in the liquid phase offers many advantages over exchange in the gaseous phase; however the rate of reaction is much smaller in the former case. The object of the following work is to study the influence of the various parameters on which the reaction rate depends (pressure, temperature, concentration, agitation), to classify catalysts according to their activity and to determine the economic possibility of liquid phase exchange. (author) [French] Il est un fait bien connu que l'echange catalytique en phase liquide presente divers avantages, compare a l'echange en phase gazeuse; la vitesse de reaction est toute fois beaucoup plus faible que dans le premier cas. L'objet du present rapport est d'etudier l'influence des differents parametres agissant sur la vitesse de reaction (pression, temperature, concentration, agitation), de classer les catalyseurs en fonction de leur activite et d'evaluer les possibilites economiques de l'echange en phase liquide. (auteur)

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

    Science.gov (United States)

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

    2006-12-01

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

  19. Program BETA for simulation of particle decays and reactions

    International Nuclear Information System (INIS)

    Takhtamyshev, G.G.; Merkulova, T.A.

    1997-01-01

    Program BETA is designed for simulation of particle decays and reactions. The program also produces integration over the phase space and decay rate or the reaction cross section are calculated as a result of such integration. At the simulation process the adaptive random number generator SMART may be used, what is found to be useful for some difficult cases

  20. Addition and spin exchange rate constants by longitudinal field μSR: the Mu + NO reaction

    International Nuclear Information System (INIS)

    Senba, Masayoshi; Gonzalez, A.C.; Kempton, J.R.; Arseneau, D.J.; Pan, J.J.; Tempelmann, A.; Fleming, D.G.

    1991-01-01

    The addition reaction Mu + NO + M → MuNO + M and the spin exchange reaction Mu(↑) + NO(↓)→Mu(↓)+NO(↑) have been measured by longitudinal field μSR at room temperature in the presence of up to 58 atm of N 2 as inert collider. The pressure dependence of the longitudinal relaxation rate due to the addition reaction (λ c ) demonstrates that the system is still in the low pressure regime in this pressure range. The corresponding termolecular rate constant has been determined as k 0.Mu =(1.10±0.25)x10 -32 cm 6 molecules -2 s -1 , almost 4 times smaller than the corresponding H atom reaction k 0,H =3.90x10 -32 cm 6 molecules -2 s -1 . The average value of the spin exchange rate constants in the 2.5-58 atm pressure range, k SE = (3.16±0.06)x10 -10 cm 3 molecule -1 s -1 , is in good agreement with previous values obtained by transverse field μSR. (orig.)

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

    International Nuclear Information System (INIS)

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-01-01

    Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: 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, N 2 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. Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach

    Energy Technology Data Exchange (ETDEWEB)

    Kustova, Elena V., E-mail: e.kustova@spbu.ru [Department of Mathematics and Mechanics, Saint Petersburg State University, 198504 Universitetskiy pr. 28, Saint Petersburg (Russian Federation); Kremer, Gilberto M., E-mail: kremer@fisica.ufpr.br [Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, 81531-980 Curitiba (Brazil)

    2014-12-05

    Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: 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, N{sub 2} 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.

  3. Metal-silicon reaction rates - The effects of capping

    Science.gov (United States)

    Weizer, Victor G.; Fatemi, Navid S.

    1989-01-01

    Evidence is presented showing that the presence of the commonly used anti-reflection coating material Ta2O5 on the free surface of contact metallization can either suppress or enhance, depending on the system, the interaction that takes place at elevated temperatures between the metallization and the underlying Si. The cap layer is shown to suppress both the generation and annihilation of vacancies at the free surface of the metal which are necessary to support metal-Si interactons. Evidence is also presented indicating that the mechanical condition of the free metal surface has a significant effect on the metal-silicon reaction rate.

  4. AN UPDATED 6Li(p, α)3He REACTION RATE AT ASTROPHYSICAL ENERGIES WITH THE TROJAN HORSE METHOD

    International Nuclear Information System (INIS)

    Lamia, L.; Spitaleri, C.; Sergi, M. L.; Pizzone, R. G.; Tumino, A.; La Cognata, M.; Tognelli, E.; Degl'Innocenti, S.; Prada Moroni, P. G.; Pappalardo, L.

    2013-01-01

    The lithium problem influencing primordial and stellar nucleosynthesis is one of the most interesting unsolved issues in astrophysics. 6 Li is the most fragile of lithium's stable isotopes and is largely destroyed in most stars during the pre-main-sequence (PMS) phase. For these stars, the convective envelope easily reaches, at least at its bottom, the relatively low 6 Li ignition temperature. Thus, gaining an understanding of 6 Li depletion also gives hints about the extent of convective regions. For this reason, charged-particle-induced reactions in lithium have been the subject of several studies. Low-energy extrapolations of these studies provide information about both the zero-energy astrophysical S(E) factor and the electron screening potential, U e . Thanks to recent direct measurements, new estimates of the 6 Li(p, α) 3 He bare-nucleus S(E) factor and the corresponding U e value have been obtained by applying the Trojan Horse method to the 2 H( 6 Li, α 3 He)n reaction in quasi-free kinematics. The calculated reaction rate covers the temperature window 0.01 to 2T 9 and its impact on the surface lithium depletion in PMS models with different masses and metallicities has been evaluated in detail by adopting an updated version of the FRANEC evolutionary code.

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

    Science.gov (United States)

    Grima, R

    2010-07-21

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

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

    Science.gov (United States)

    Bertulani, C. A.

    2018-01-01

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

  7. Geometric phase effects in ultracold chemistry

    Science.gov (United States)

    Hazra, Jisha; Naduvalath, Balakrishnan; Kendrick, Brian K.

    2016-05-01

    In molecules, the geometric phase, also known as Berry's phase, originates from the adiabatic transport of the electronic wavefunction when the nuclei follow a closed path encircling a conical intersection between two electronic potential energy surfaces. It is demonstrated that the inclusion of the geometric phase has an important effect on ultracold chemical reaction rates. The effect appears in rotationally and vibrationally resolved integral cross sections as well as cross sections summed over all product quantum states. It arises from interference between scattering amplitudes of two reaction pathways: a direct path and a looping path that encircle the conical intersection between the two lowest adiabatic electronic potential energy surfaces. Illustrative results are presented for the O+ OH --> H+ O2 reaction and for hydrogen exchange in H+ H2 and D+HD reactions. It is also qualitatively demonstrated that the geometric phase effect can be modulated by applying an external electric field allowing the possibility of quantum control of chemical reactions in the ultracold regime. This work was supported in part by NSF Grant PHY-1505557 (N.B.) and ARO MURI Grant No. W911NF-12-1-0476 (N.B.).

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

    Science.gov (United States)

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

    2018-03-12

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

  9. Gas-phase reactions of glycine, alanine, valine and their N-methyl derivatives with the nitrosonium ion, NO+.

    Science.gov (United States)

    Freitas, M A; O'Hair, R A; Schmidt, J A; Tichy, S E; Plashko, B E; Williams, T D

    1996-10-01

    The gas-phase reactions of the nitrosonium ion, NO+ with the amino acids glycine, alanine and valine and their N-methyl derivatives were investigated under chemical ionization mass spectrometric (CIMS) conditions. Two products were observed in all cases: the formation of the iminium ion and the formation of an [M-H]+ ion. The latter product is consistent with a reaction channel involving hydride abstraction by NO+, and was confirmed by (i) examining the Ar+CI mass spectra of the same amino acids under similar source conditions and (ii) examining the unimolecular fragmentation reactions of the [M + H]+ ions of the N-nitroso-N-methyl derivatives of each of the amino acids in a tandem mass spectrometer. Further insights into the reaction of glycine with NO+ were obtained by performing ab initio calculations (at the MP2/6-31G* parallel HF/6-31G* level). These results indicate that four reactions are thermodynamically viable for glycine: (i) hydride abstraction; (ii) iminium ion formation (with concomitant loss of HONO and CO); (iii) diazonium ion formation; and (iv) diazonium ion formation followed by loss of N2. Possible reasons why reactions (iii) and (iv) are not observed are discussed, and comparisons with solution reactivity and the gas-phase reactivity of NO+ are also made.

  10. Generic Model-Based Tailor-Made Design and Analysis of Biphasic Reaction Systems

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata

    systems have a broad range of application, such as the manufacture of petroleum based chemicals, pharmaceuticals, and agro-bio products. Major considerations in the design and analysis of biphasic reaction systems are physical and chemical equilibria, kinetic mechanisms, and reaction rates. The primary...... contribution of this thesis is the development of a systematic modelling framework for the biphasic reaction system. The developed framework consists of three modules describing phase equilibria, reactions and mass transfer, and material balances of such processes. Correlative and predictive thermodynamic......Biphasic reaction systems are composed of immiscible aqueous and organic liquid phases where reactants, products, and catalysts are partitioned. These biphasic conditions point to novel synthesis paths, higher yields, and faster reactions, as well as facilitate product separation. The biphasic...

  11. Prediction of turbulent mixing rates of both gas and liquid phases between adjacent subchannels in a two-phase slug-churn flow

    International Nuclear Information System (INIS)

    Kawahara, A.; Sadatomi, M.; Tomino, T.; Sato, Y.

    1998-01-01

    This paper presents a slug-churn flow model for predicting turbulent mixing rates of both gas and liquid phase between adjacent subchannels in a BWR fuel rod bundle. In the model, the mixing rate of the liquid phase is calculated as the sum of the three components, i.e., turbulent diffusion, convective transfer and pressure difference fluctuations between the subchannels. The compenents of turbulent diffusion and convective transfer are calculated from Sadatomi et al.'s (1996) method, applicable to single-phase turbulent mixing by considering the effect of the increment of liquid velocity due to the presence of gas phase. The component of the pressure difference fluctuations is evaluated from a newly developed correlations. The mixing rate of the gas phase, on the other side, is calculated from a simple relation of mixing rate between gas and liquid phases. The validity of the proposed model has been confirmed with the turbulent mixing rates data of Rudzinski et al. as well as the present authors

  12. Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Kato, T. [National Inst. for Fusion Science, Toki, Gifu (Japan); Wang, J.G. [Department of Physics and Astronomy, University of Georgia, Athens (United States)

    2001-05-01

    The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C{sub x}H{sub y} charge exchange reactions from thermal energies up to several hundreds keV for all C{sub x}H{sub y} molecules with x=1, 2, 3 and 1 {<=} y {<=} 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

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

    Science.gov (United States)

    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.

  14. Density Functional Theory Study of Competitive Reaction Pathways of Ti+ with Fluorinated Acetone in the Gas Phase

    International Nuclear Information System (INIS)

    Hong, Kiryong; Kim, Tae Kyu

    2012-01-01

    We investigate the doublet and quartet potential energy surfaces associated with the gas-phase reaction between Ti + and CF 3 COCH 3 for two plausible reaction pathways, TiF 2 + and TiO + formation pathways by using the density functional theory (DFT) method. The molecular structures of intermediates and transition states involved in these reaction pathways are optimized at the DFT level by using the PBE0 functional. All transition states are identified by using the intrinsic reaction coordinate (IRC) method, and the resulting reaction coordinates describe how Ti + activates CF 3 COCH 3 and produces TiF 2 + and TiO + as products. On the basis of presented results, we propose the most favorable reaction pathway in the reaction between Ti + and CF 3 COCH 3

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

    Science.gov (United States)

    Herbst, E.; Woon, D. E.

    1997-01-01

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

  16. Reactions of stabilized Criegee Intermediates

    Science.gov (United States)

    Vereecken, Luc; Harder, Hartwig; Novelli, Anna

    2014-05-01

    Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

  17. Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

    International Nuclear Information System (INIS)

    Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

    2015-01-01

    The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

  18. The Forward-Reverse Algorithm for Stochastic Reaction Networks

    KAUST Repository

    Bayer, Christian

    2015-01-07

    In this work, we present an extension of the forward-reverse algorithm by Bayer and Schoenmakers [2] to the context of stochastic reaction networks (SRNs). We then apply this bridge-generation technique to the statistical inference problem of approximating the reaction coefficients based on discretely observed data. To this end, we introduce a two-phase iterative inference method in which we solve a set of deterministic optimization problems where the SRNs are replaced by the classical ODE rates; then, during the second phase, the Monte Carlo version of the EM algorithm is applied starting from the output of the previous phase. Starting from a set of over-dispersed seeds, the output of our two-phase method is a cluster of maximum likelihood estimates obtained by using convergence assessment techniques from the theory of Markov chain Monte Carlo.

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

    Science.gov (United States)

    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.

  20. Atmospheric chemistry of cyc-CF2CF2CF2CH=CH-: Kinetics, products, and mechanism of gas-phase reaction with OH radicals, and atmospheric implications

    Science.gov (United States)

    Guo, Qin; Zhang, Ni; Uchimaru, Tadafumi; Chen, Liang; Quan, Hengdao; Mizukado, Junji

    2018-04-01

    The rate constants for the gas-phase reactions of cyc-CF2CF2CF2CH=CH- with OH radicals were determined by a relative rate method between 253 and 328 K. The rate constant k1 at 298 K was measured to be (1.08 ± 0.04) × 10-13 cm3 molecule-1 s-1, and the Arrhenius expression was k1 = (3.72 ± 0.14) × 10-13 exp [(-370 ± 12)/T]. The atmospheric lifetime of cyc-CF2CF2CF2CH=CH- was calculated to be 107 d. The products and mechanism for the reaction of cyc-CF2CF2CF2CH=CH- with OH radicals were also investigated. CO, CO2, and COF2 were identified as the main carbon-containing products following the OH-initiated reaction. Moreover, the radiative efficiency (RE) was determined to be 0.143 W m-2 ppb-1, and the global warming potentials (GWPs) for 20, 100, and 500 yr were 54, 15, and 4, respectively. The photochemical ozone creation potential of the title compound was estimated to be 1.3.

  1. Process Intensification. Continuous Two-Phase Catalytic Reactions in a Table-Top Centrifugal Contact Separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Schuur, Boelo; van Zwol, Floris; Haak, Robert M.; Minnaard, Adriaan J.; Feringa, Ben L.; Heeres, Hero J.; de Vries, Johannes G.; Prunier, ML

    2009-01-01

    Production of fine chemicals is mostly performed in batch reactors. Use of continuous processes has many advantages which may reduce the cost of production. We have developed the use of centrifugal contact separators (CCSs) for continuous two-phase catalytic reactions. This equipment has previously

  2. Experimental determination of the high-temperature rate constant for the reaction of OH with sec-butanol.

    Science.gov (United States)

    Pang, Genny A; Hanson, Ronald K; Golden, David M; Bowman, Craig T

    2012-10-04

    The overall rate constant for the reaction of OH with sec-butanol [CH(3)CH(OH)CH(2)CH(3)] was determined from measurements of the near-first-order OH decay in shock-heated mixtures of tert-butylhydroperoxide (as a fast source of OH) with sec-butanol in excess. Three kinetic mechanisms from the literature describing sec-butanol combustion were used to examine the sensitivity of the rate constant determination to secondary kinetics. The overall rate constant determined can be described by the Arrhenius expression 6.97 × 10(-11) exp(-1550/T[K]) cm(3) molecule(-1) s(-1), valid over the temperature range of 888-1178 K. Uncertainty bounds of ±30% were found to adequately account for the uncertainty in secondary kinetics. To our knowledge, the current data represent the first efforts toward an experimentally determined rate constant for the overall reaction of OH with sec-butanol at combustion-relevant temperatures. A rate constant predicted using a structure-activity relationship from the literature was compared to the current data and previous rate constant measurements for the title reaction at atmospheric-relevant temperatures. The structure-activity relationship was found to be unable to correctly predict the measured rate constant at all temperatures where experimental data exist. We found that the three-parameter fit of 4.95 × 10(-20)T(2.66) exp(+1123/T[K]) cm(3) molecule(-1) s(-1) better describes the overall rate constant for the reaction of OH with sec-butanol from 263 to 1178 K.

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

    Science.gov (United States)

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

    2018-05-01

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

  4. A review of the rates of reaction of unirradiated uranium in gaseous atmospheres

    International Nuclear Information System (INIS)

    Pearce, R.J.

    1989-10-01

    The review collates available quantitative rate data for the reaction of unirradiated uranium in dry and moist air, steam and carbon dioxide based atmospheres at temperatures ranging from room temperature to above the melting point of uranium. Reactions in nitrogen and carbon monoxide are also considered. The aim of the review is to provide a compilation of base data for the hazard analysis of fault conditions relating to Magnox fuel. (author)

  5. Dissociative attachment reactions of electrons with gas phase superacids

    International Nuclear Information System (INIS)

    Liu, X.

    1992-01-01

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients β for reactions of electrons with gas phase superacids HCo(PF 3 ) 4 , HRh(PF 3 ) 4 and carbonyl hydride complexes HMn(CO) 5 , HRe(CO) 5 have been determined under thermal conditions over the approximate temperature range 300∼550 K. The superacids react relatively slowly ( max ) with free electrons in a thermal plasma, and the values of β obtained this far do not show a correlation between acidity and β. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF 3 ) 4 was found to be independent of temperature even though the β[HCo(PF 3 ) 4 ] increases with temperature. This proposes that the electron attachment process occurs well before the excited complex dissociates. In addition, the activation energy of HCo(PF 3 ) 4 for electron attachment has been derived from the Arrhenius plots. The carbonyl hydride complexes, HMn(CO) 5 and HRe(CO) 5 , react relatively rapidly (>1/4 of β max ) with free electrons in thermal plasma. This indicates that these reactions cannot be significantly endothermic. Observation of rapid attachment for these non-superacids shows that the Mn-CO and Re-CO bonds are weaker than the Mn-H and Re-H bonds, respectively. Comparisons between the carbonyl and trifluorophosphine cases implies that fast electron capture is related more to the CO ligand than to the transition-metal species

  6. Polyoxyethylene/styrene - a model system for studying reaction-induced phase separation (RIPS)

    International Nuclear Information System (INIS)

    Sutton, D.; Stanford, J.L.; Ryan, A.J.

    2003-01-01

    Full text: Reaction-induced, phase-separation has been studied in polymer blends. A model crystalline-amorphous system consisted of semi-crystalline polyoxyethylene (POE) dissolved in the monomer styrene, which was employed as a reactive solvent to ease processing. When the styrene was polymerised to polystyrene (PS) in the mould, phase-separation and phase-inversion are induced, and a polymer blend was formed. POE was selected with a molar mass, Mn = 8578 g mol -1 and a polydispersity of 1.19 as determined using GPC. The polymerisation of styrene was initiated using 1 wt-% benzoin methyl ether (BME) and 0.2 wt-% 2,2'-azobisisobutyronitrile (AIBN) under ultra-violet (UV) light. The polymerisation kinetics were determined by monitoring the reduction in the intensity of the C=C stretching vibration band at 1631 cm -1 in the Raman spectrum of styrene. The onset times for the liquid-solid (L-S) phase-separation and crystallisation of POE from styrene/PS were observed using simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). Onset times for L-S phase-separation determined from the SAXS data were combined with the styrene polymerisation kinetics to plot the L-S phase-separation data onto a ternary phase diagram for the reactive system POE/styrene/PS at 45 and 50 deg C

  7. Transcriptional dynamics with time-dependent reaction rates

    Science.gov (United States)

    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.

  8. Transcriptional dynamics with time-dependent reaction rates

    International Nuclear Information System (INIS)

    Nandi, Shubhendu; Ghosh, Anandamohan

    2015-01-01

    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. (paper)

  9. Estimating reaction rate constants from a two-step reaction: a comparison between two-way and three-way methods

    NARCIS (Netherlands)

    Bijlsma, S.; Smilde, A. K.

    2000-01-01

    In this paper, two different spectral datasets are used in order to estimate reaction rate constants using different algorithms. Dataset 1 consists of short-wavelength near-infrared (SW NIR) spectra taken in time of the two-step epoxidation of 2,5-di-tert-butyl-1,4-benzoquinone using tert-butyl

  10. Experimental determination of nuclear reaction rates (n,γ) by the gamma-rays capture spectrometry technique

    International Nuclear Information System (INIS)

    Lucatero, M.A.

    1976-01-01

    The technique of the gamma-rays capture spectrometry was used in the experimental determination of nuclear reaction rates of the type (n,γ). This technique consists in the incidence of a thermal neutrons collimated beam upon a sample, detecting the capture spectrum of gamma rays emitted at a solid fixed angle. In the determination of the efficiency curve intrinsic to the detection electronic system the reactions 199 Hg(n,γ) 200 Hg, 56 Fe(n,γ) 57 Fe and 63 Cu(n,γ) 64 Cu were used with the energy of the gamma rays capture of 5.976, 7.635 and 7.915 Mev respectively, through the irradiation of standard samples of Hg(175.3g), Fe(110.4g) and Cu(108.5g) of cylindrical geometry the two former and parallelepiped the latter. The problem concerning the corrections due to the thermal neutrons flux depression, the gammas auto-attenuation, and the geometric factor due to the cylindrical and parallelepiped geometry are involved in the data process. The experimental determination of the reaction 35 Cl(n,γ) 36 Cl rate was made through the observation of the gamma caputre of 6.111 Mev when a sample of CaCl 2 of cylindrical geometry was irradiated. This rate can be favorably compared with the reaction rate determined theoretically. (author)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2018-02-01

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

  13. Hospitalization due to Adverse Drug Reactions and Drug Interactions before and after HAART

    Directory of Open Access Journals (Sweden)

    Michelle M Foisy

    2000-01-01

    Full Text Available OBJECTIVE: To characterize and compare the rates of adverse drug reactions (ADRs and interactions on admission in two, one-year periods: pre-highly active antiretroviral therapy (HAART (phase 1 and post-HAART (phase 2.

  14. Safety confirmation study of TRUEX solvent by accelerating rate calorimeter (ARC)

    International Nuclear Information System (INIS)

    Sato, Yoshihiko; Hirumachi, Suguru; Takeda, Shinso; Kanazawa, Yoshito; Sasaya, Shinji

    1999-02-01

    In order to confirm the engineering safety on the TRUEX solvent (mixed solvent of CMPO/TBP/n-dodecane) for separating the transuranics from high-level activity liquid waste in advanced nuclear fuel recycling technological R and D, thermal behavior and pressure behavior in heating PUREX solvent (mixed solvent of 30% TBP-n-dodecane), TRUEX solvent and in the exothermic reaction of TRUEX solvent etc. and nitric acid in sealed adiabatic system which was severer condition than actual plant were measured by using accelerating rate calorimeter (ARC). The Arrhenius parameters (activation energy and frequency factor) which are necessary for the evaluation of reaction rate was examined from the measurement data in ARC. Analytical method and analysis condition of reaction products were examined in order to clarify chemical form of reaction products in exothermic reaction between solvent and nitric acid in ARC, and the qualitative evaluation was carried out. Main results are shown in the following. 1) TBP, CMPO, n-dodecane and 10 M nitric acid hardly exothermed in the simple substance. 2) On the solvent phase after the solvent contacted with 10 M nitric acid and the equilibrium has been attained (single-phase sample), the heat quantity per unit sample weight of the TRUEX solvent tended to be bigger than that of the PUREX solvent when heat quantity was evaluated in ARC. However, on the mixed sample of solvent and 10 M nitric acid enclosed in a sample container simultaneously (two phase system sample), the heat quantity per unit solvent weight was almost equivalent for PUREX solvent and TRUEX solvent. 3) The kinetic analysis was carried out, and on the TBP-10 M nitric acid single-phase sample, the activation energy of the reaction was evaluated to be 118 kJ/mol. Its activation energy was approximately equal to 112 kJ/mol by Nichols. The reaction rate constant was calculated, and it was shown that reaction rate constants of PUREX solvent-10 M nitric acid single-phase sample and

  15. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  16. A mathematical analysis of Prx2-STAT3 disulfide exchange rate constants for a bimolecular reaction mechanism.

    Science.gov (United States)

    Langford, Troy F; Deen, William M; Sikes, Hadley D

    2018-03-22

    Appreciation of peroxiredoxins as the major regulators of H 2 O 2 concentrations in human cells has led to a new understanding of redox signaling. In addition to their status as the primary reducers of H 2 O 2 to water, the oxidized peroxiredoxin byproduct of this reaction has recently been shown capable of participation in H 2 O 2 -mediated signaling pathways through disulfide exchange reactions with the transcription factor STAT3. The dynamics of peroxidase-transcription factor disulfide exchange reactions have not yet been considered in detail with respect to how these reactions fit into the larger network of competing reactions in human cells. In this study, we used a kinetic model of oxidation and reduction reactions related to H 2 O 2 metabolism in the cytosol of human cells to study the dynamics of peroxiredoxin-2 mediated oxidation of the redox-regulated transcription factor STAT3. In combination with previously reported experimental data, the model was used to estimate the rate coefficient of a biomolecular reaction between Prx2 and STAT3 for two sets of assumptions that constitute lower and upper bound cases. Using these estimates, we calculated the relative rates of the reaction of oxidized peroxiredoxin-2 and STAT3 and other competing reactions in the cytosol. These calculations revealed that peroxiredoxin-2-mediated oxidation of STAT3 likely occurs at a much slower rate than competing reactions in the cytosol. This analysis suggests the existence of more complex mechanisms, potentially involving currently unknown protein-protein recognition partners, which facilitate disulfide exchange reactions between peroxiredoxin-2 and STAT3. Copyright © 2018 Elsevier Inc. All rights reserved.

  17. Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment

    Science.gov (United States)

    Marcus, R. A.

    1964-01-01

    In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.

  18. Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Ponomarev, DA; Nielsen, OJ

    2001-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms with iodobenzene (C6H5I) in 20-700 Torr of N-2, air, or O-2 diluent at 296 K. The reaction proceeds with a rate constant k(Cl + QH(5)I) = (3.3 +/- 0.7) x 10(-11) cm(3) molecule(-1) s(-1) to give...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Naine, Tarun Bharath; Gundawar, Manoj Kumar

    2017-09-01

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

  1. Evolution of Fe based intermetallic phases in Al–Si hypoeutectic casting alloys: Influence of the Si and Fe concentrations, and solidification rate

    International Nuclear Information System (INIS)

    Gorny, Anton; Manickaraj, Jeyakumar; Cai, Zhonghou; Shankar, Sumanth

    2013-01-01

    Highlights: •Anomalous evolution of Fe based intermetallic phases in Al–Si–Fe alloys. •XRF coupled with nano-diffraction to confirm the nano-size Fe intermetallic phases. •Crystallography of the θ-Al 13 Fe 4 , τ 5 -Al 8 Fe 2 Si and τ 6 -Al 9 Fe 2 Si 2 phases. •Peritectic reactions involving the Fe intermetallic phases in Al–Si–Fe alloys. -- Abstract: Al–Si–Fe hypoeutectic cast alloy system is very complex and reported to produce numerous Fe based intermetallic phases in conjunction with Al and Si. This publication will address the anomalies of phase evolution in the Al–Si–Fe hypoeutectic casting alloy system; the anomaly lies in the peculiarities in the evolution and nature of the intermetallic phases when compared to the thermodynamic phase diagram predictions and past publications of the same. The influence of the following parameters, in various combinations, on the evolution and nature of the intermetallic phases were analyzed and reported: concentration of Si between 2 and 12.6 wt%, Fe between 0.05 and 0.5 wt% and solidification rates of 0.1, 1, 5 and 50 K s −1 . Two intermetallic phases are observed to evolve in these alloys under these solidification conditions: the τ 5 -Al 8 SiFe 2 and τ 6 -Al 9 Fe 2 Si 2 . The τ 5 -Al 8 SiFe 2 phase evolves at all levels of the parameters during solidification and subsequently transforms into the τ 6 -Al 9 Fe 2 Si 2 through a peritectic reaction when promoted by certain combinations of solidification parameters such as higher Fe level, lower Si level and slower solidification rates. Further, it is also hypothesized from experimental evidences that the θ-Al 13 Fe 4 binary phase precludes the evolution of the τ 5 during solidification and subsequently transforms into the τ 6 phase during solidification. These observations are anomalous to the publications as prior art and simulation predictions of thermodynamic phase diagrams of these alloys, wherein, only one intermetallic phases in the

  2. Liquid-liquid transfer phenomena studies coupled with redox reactions: back-extraction of nitrous acid in the presence of scavengers in aqueous phase

    International Nuclear Information System (INIS)

    K'zerho, R.

    1998-01-01

    This work deals with the investigation of redox reaction contribution to the kinetics of liquid-liquid transfer, in relation with PUREX reprocessing of spent nuclear fuel. The chemical system chosen concerns the tripping of nitrous acid from tributylphosphate organic phase into a nitric acid aqueous solution containing an 'anti-nitrous' component, namely hydrazinium nitrate. According to the abundant literature, a major attention is devoted to the very important role of interfacial phenomena on the kinetics of solvent extraction with tributylphosphate. Although, a suitable experimental technique is chosen, using a constant interfacial area cell of the ARMOLLEX-type. Furthermore, the effects of the hydrodynamical and the physico-chemical parameters on the extraction rate led to the identification of the extraction regime nature: diffusional, then chemical limitation. When no 'anti-nitrous' component is used, the diffusional resistance is found to be mainly located in the aqueous diffusion layer. The presence of hydrazinium nitrate into the aqueous solution has an overall accelerating effect on the rate of extraction, related to both a complete suppression of the aqueous diffusional resistance, and a very significant enhancement of the interfacial transfer of the nitrous acid, as a function of hydrazinium concentration. If the first effect could be expected because of the well known fast redox reaction in aqueous phase, the second phenomenon represents a quite original and new result which has never been explored before, to the best of our knowledge. A reaction mechanism is postulated and validated, taking into account the reactive effect of hydrazinium on the interfacial step. In order to support the drawn general patterns, different complementary studies were attempted. When hydroxyl-ammonium nitrate is used, a surprising interfacial transfer blockage is observed, pointing out the extreme performance and specificity of the common hydrazinium component. (author)

  3. Numerical Analysis Of Hooke Jeeves-Runge Kutta To Determine Reaction Rate Equation In Pyrrole Polymerization

    International Nuclear Information System (INIS)

    Gunawan, Indra; Sulistyo, Harry; Rochmad

    2001-01-01

    The numerical analysis of Hooke Jeeves Methods combined with Runge Kutta Methods is used to determine the exact model of reaction rate equation of pyrrole polymerization. Chemical polymerization of pyrrole was conducted with FeCI 3 / pyrrole solution at concentration ratio of 1.62 mole / mole and 2.18 mole / mole with varrying temperature of 28, 40, 50, and 60 o C. FeCl 3 acts as an oxidation agent to form pyrrole cation that will polymerize. The numerical analysis was done to examine the exact model of reaction rate equation which is derived from reaction equation of initiation, propagation, and termination. From its numerical analysis, it is found that the pyrrole polymerization follows third order of pyrrole cation concentration

  4. Measurements and calculations of 10B(n,He) reaction rates in a control rod in ZPPR

    International Nuclear Information System (INIS)

    Brumbach, S.B.; Collins, P.J.; Grasseschi, G.L.; Oliver, B.M.

    1986-01-01

    The helium accumulation fluence monitor (HAFM) technique has been used to measure the 10 B(n,He) reaction rate within B 4 C pellets in a control rod in ZPPR. Knowledge of this reaction rate is important to control rod design studies because helium production leads to control rod swelling, buildup of gas pressure and a reduction in thermal conductivity which can limit the lifetime of a control rod. We believe these to be the first measurements of boron capture within boron pins in a fast reactor spectrum. Previously reported measurements used 235 U foils to measure fission rates in a control rod, and to infer boron capture rates

  5. Measurements of activation reaction rate distributions on a mercury target bombarded with high-energy protons at AGS

    International Nuclear Information System (INIS)

    Takada, Hiroshi; Kasugai, Yoshimi; Nakashima, Hiroshi; Ikeda, Yujiro; Jerde, Eric; Glasgow, David

    2000-02-01

    A neutronics experiment was carried out using a thick mercury target at the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Reaction rate distributions around the target were measured by the activation technique at incident proton energies of 1.6, 12 and 24 GeV. Various activation detectors such as the 115 In(n,n') 115m In, 93 Nb(n,2n) 92m Nb, and 209 Bi(n,xn) reactions with threshold energies ranging from 0.3 to 70.5 MeV were employed to obtain the reaction rate data for estimating spallation source neutron characteristics of the mercury target. It was found from the measured 115 In(n,n') 115m In reaction rate distribution that the number of leakage neutrons becomes maximum at about 11 cm from the top of hemisphere of the mercury target for the 1.6-GeV proton incidence and the peak position moves towards forward direction with increase of the incident proton energy. The similar result was observed in the reaction rate distributions of other activation detectors. The experimental procedures and a full set of experimental data in numerical form are summarized in this report. (author)

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Science.gov (United States)

    Beniwal, Vijay; Manna, Arpan; Kumar, Anil

    2016-07-04

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

  8. Rate Constants and H-Atom Product Yields for the Reactions of O(1D) Atoms with Ethane and Acetylene from 50 to 296 K.

    Science.gov (United States)

    Nunez-Reyes, Dianailys; Hickson, Kevin M

    2018-05-01

    The gas phase reactions of atomic oxygen in its first excited state with ethane and acetylene have been investigated in a continuous supersonic flow reactor over the temperature range 50 K to 296 K. O(1D) atoms were produced by pulsed laser photolysis of ozone at 266 nm. Two different types of experiments, kinetics measurements and H-atom product yield determinations, were performed by detecting O(1D) atoms and H(2S) atoms respectively by vacuum ultraviolet laser induced fluorescence. The measured rate constants are in agreement with previous work at room temperature and little or no temperature dependence was observed as the temperature is decreased to 50 K. H-atoms yields were found to be independent of temperature for the reaction of O(1D) with ethane. These product yields are discussed in the context of earlier dynamics measurements at higher temperature. Due to the influence of secondary reactions, no H-atom yields could be obtained for the reaction of O(1D) with acetylene.

  9. A study of reactions of sulfur dioxide in the gaseous phase. Production and evolution of aerosols resulting from these reactions

    International Nuclear Information System (INIS)

    Boulaud, Denis

    1977-01-01

    The reactions of sulfur dioxide in the gaseous phase with atmospheric pollutants (NO x ; hydrocarbons) were studied. Experiments showed that NO 2 contribution was significant and suggested that SO 2 transformation into sulfuric acid and sulfates might occur through oxidising agents mainly hydroxyl (OH) and hydro-peroxyl (HO 2 ) radicals. The production and evolution of the resulting aerosols was also studied. It was demonstrated that the effect of water vapour on particle production was significant and that primary embryos were formed from the hetero-molecular homogeneous nucleation acting on water vapour and very likely on sulfuric acid. There was a semi-quantitative agreement between our experimental results and some theoretical investigations on nucleation rate of the system (H 2 O - H 2 SO 4 ). The subsequent growth of particles was studied in a simulation chamber. Finally a model of sulfuric acid vapour evolution in presence of atmospheric aerosols made it possible to extend the previous results as far as possible to the case of atmosphere and then to compare the importance of homogeneous and heterogeneous nucleation of the vapours according to atmospheric conditions. (author) [fr

  10. Rate-independent dissipation in phase-field modelling of displacive transformations

    Science.gov (United States)

    Tůma, K.; Stupkiewicz, S.; Petryk, H.

    2018-05-01

    In this paper, rate-independent dissipation is introduced into the phase-field framework for modelling of displacive transformations, such as martensitic phase transformation and twinning. The finite-strain phase-field model developed recently by the present authors is here extended beyond the limitations of purely viscous dissipation. The variational formulation, in which the evolution problem is formulated as a constrained minimization problem for a global rate-potential, is enhanced by including a mixed-type dissipation potential that combines viscous and rate-independent contributions. Effective computational treatment of the resulting incremental problem of non-smooth optimization is developed by employing the augmented Lagrangian method. It is demonstrated that a single Lagrange multiplier field suffices to handle the dissipation potential vertex and simultaneously to enforce physical constraints on the order parameter. In this way, the initially non-smooth problem of evolution is converted into a smooth stationarity problem. The model is implemented in a finite-element code and applied to solve two- and three-dimensional boundary value problems representative for shape memory alloys.

  11. Characterization of ionic liquid‐based biocatalytic two‐phase reaction system for production of biodiesel

    DEFF Research Database (Denmark)

    Prabhavathi Devi, Bethala Lakshmi Anu; Guo, Zheng; Xu, Xuebing

    2011-01-01

    The property of a variety of ionic liquids (ILs) as reaction media was evaluated for the production of biodiesel by enzymatic methanolysis of rapeseed oil. The IL Ammoeng 102, containing tetraaminum cation with C18 acyl and oligoethyleneglycol units, was found to be capable of forming oil....../IL biphasic reaction system by mixing with substrates, which is highly effective for the production of biodiesel with more than 98% biodiesel yield and nearly 100% conversion of oil. Conductor‐like screening model for real solvent (COSMO‐RS) in silico prediction of substrate solubility and simulation...... of partition coefficient change vs. reaction evolution indicated that the amphiphilic property of Ammoeng 102 might be responsible for creating efficient interaction of immiscible substrates; while big difference of partition coefficients of generated biodiesel and glycerol between the two phases suggests...

  12. Mass transfer with complex chemical reactions in gas–liquid systems : two-step reversible reactions with unit stoichiometric and kinetic orders

    NARCIS (Netherlands)

    Vas Bhat, R.D.; Kuipers, J.A.M.; Versteeg, G.F.

    2000-01-01

    An absorption model to study gas–liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

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

    Science.gov (United States)

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

    2018-05-01

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

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

    Science.gov (United States)

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

    2016-03-03

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

  15. Closure of the condensed-phase organic-nitrate reaction unreviewed safety question at Hanford site

    International Nuclear Information System (INIS)

    COWLEY, W.L.

    1999-01-01

    A discovery Unreviewed Safety Question (USQ) was declared on the underground waste storage tanks at the Hanford Site in May 1996. The USQ was for condensed-phase organic-nitrate reactions (sometimes called organic complexant reactions) in the tanks. This paper outlines the steps taken to close the USQ, and resolve the related safety issue. Several processes were used at the Hanford Site to extract and/or process plutonium. These processes resulted in organic complexants (for chelating multivalent cations) and organic extraction solvents being sent to the underground waste storage tanks. This paper addresses the organic complexant hazard. The organic complexants are in waste matrices that include inert material, diluents, and potential oxidizers. In the presence of oxidizing material, the complexant salts can be made to react exothermically by heating to high temperatures or by applying an external ignition source of sufficient energy. The first organic complexant hazard assessments focused on determining whether a hulk runaway reaction could occur, similar to the 1957 accident at Kyshtm (a reprocessing plant in the former U.S.S.R.). Early analyses (1977 through 1994) examined organic-nitrate reaction onset temperatures and concluded that a bulk runaway reaction could not occur at the Hanford Site because tank temperatures were well below that necessary for bulk runaway. Therefore, it was believed that organic-nitrate reactions were adequately described in the then current Authorization Basis (AB). Subsequent studies examined a different accident scenario, propagation resulting from an external ignition source (e.g., lightning or welding slag) that initiates a combustion front that propagates through the organic waste. A USQ evaluation determined that localized high energy ignition sources were credible, and that point source ignition of organic complexant waste was not adequately addressed i n the then existing AB. Consequently, the USQ was declared on the

  16. Selected specific rates of reactions of transients from water in aqueous solution. II. Hydrogen atom

    International Nuclear Information System (INIS)

    Anbar, M.; Farhataziz; Ross, A.B.

    1975-05-01

    Rates of reactions of hydrogen atoms (from radiolysis of water and other sources) with organic and inorganic molecules, ions, and transients in aqueous solution were tabulated. Directly measured rates obtained by kinetic spectroscopy or conductimetric methods, and relative rates determined by competition kinetics are included. (U.S.)

  17. UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298-K

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Ellermann, T.; Bartkiewicz, E.

    1992-01-01

    The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm....... The measured cross section near the absorption maximum was sigma(CHF2O2)(240 nm) = (2.66 +/- 0.46) x 10(-18) cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 --> products, defined as d[R]/dt = 2k(1obs)[CHF2O2]2, k(1......obs) = (5.0 +/- 0.7) x 10(-12) cm3 molecule-1 s-1 (+/- 2-sigma). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals....

  18. Analysis of coupled mass transfer and sol-gel reaction in a two-phase system

    NARCIS (Netherlands)

    Castelijns, H.J.; Huinink, H.P.; Pel, L.; Zitha, P.L.J.

    2006-01-01

    The coupled mass transfer and chemical reactions of a gel-forming compound in a two-phase system were studied in detail. Tetra-methyl-ortho-silicate (TMOS) is often used as a precursor in sol-gel chemistry to produce silica gels in aqueous systems. TMOS can also be mixed with many hydrocarbons

  19. Rate constant measurements for the overall reaction of OH + 1-butanol → products from 900 to 1200 K.

    Science.gov (United States)

    Pang, Genny A; Hanson, Ronald K; Golden, David M; Bowman, Craig T

    2012-03-15

    The rate constant for the overall reaction OH + 1-butanol → products was determined in the temperature range 900 to 1200 K from measurements of OH concentration time histories in reflected shock wave experiments of tert-butyl hydroperoxide (TBHP) as a fast source of OH radicals with 1-butanol in excess. Narrow-linewidth laser absorption was employed for the quantitative OH concentration measurement. A detailed kinetic mechanism was constructed that includes updated rate constants for 1-butanol and TBHP kinetics that influence the near-first-order OH concentration decay under the present experimental conditions, and this mechanism was used to facilitate the rate constant determination. The current work improves upon previous experimental studies of the title rate constant by utilizing a rigorously generated kinetic model to describe secondary reactions. Additionally, the current work extends the temperature range of experimental data in the literature for the title reaction under combustion-relevant conditions, presenting the first measurements from 900 to 1000 K. Over the entire temperature range studied, the overall rate constant can be expressed in Arrhenius form as 3.24 × 10(-10) exp(-2505/T [K]) cm(3) molecule(-1) s(-1). The influence of secondary reactions on the overall OH decay rate is discussed, and a detailed uncertainty analysis is performed yielding an overall uncertainty in the measured rate constant of ±20% at 1197 K and ±23% at 925 K. The results are compared with previous experimental and theoretical studies on the rate constant for the title reaction and reasonable agreement is found when the earlier experimental data were reinterpreted.

  20. Optimization of phase analysis of refractory alloys in the gas-ion-reaction chamber

    International Nuclear Information System (INIS)

    Blumenkamp, H.J.; Hoven, H.; Koizlik, K.; Nickel, H.

    1980-04-01

    Reactor components outside the core which are under high thermal and mechanical stresses are made from refractory alloys. For basic research and for quality control, these materials are investigated by metallography, which is an independent group of characterization procedures as well as basis for many other methods. An important way of increasing the information about a material yielded by metallography is the expansions of phase contrast, in particular the phase contrasting in the gas-ion-reaction chamber. In this paper, the experimental procedure is described and the process of optimizing the procedure with respect to the Ni- and Fe-based refractory alloys examined in the IRW is discussed. (orig.) [de

  1. Hydrogen transfer reactions of interstellar Complex Organic Molecules

    Science.gov (United States)

    Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

    2018-06-01

    Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

  2. Crystal phase evolution of TiO2 nanoparticles with reaction time in acidic solutions studied via freeze-drying method

    International Nuclear Information System (INIS)

    Shin, Hyunho; Jung, Hyun Suk; Hong, Kug Sun; Lee, Jung-Kun

    2005-01-01

    The crystal phase evolution of TiO 2 nanoparticles, during hydrolysis and condensation of titanium tetraisopropoxide, was quenched at various reaction times by a freeze-drying method, followed by various characterizations. Three types of solutions with different acid input times were studied: (1) addition in infinite time (no addition) (2) addition at 24h after the hydrolysis/condensation reaction started, and (3) addition from the beginning of the reaction. The acid-free solution yielded amorphous TiO 2 , which transformed to anatase very slowly. The acid input in 24h resulted in a fast transformation of amorphous to a metastable anatase having a highly distorted atomic arrangement: thereby its transformation to a more stable phase, rutile, was suitable. The acid addition from the beginning of the reaction yielded the formation of a relatively stable anatase from the hydrolysis seed, thereby the subsequent transformation to rutile was sluggish

  3. The Reaction Mechanism and Rate Constants in the Radiolysis of Fe2+-Cu2+ Solutions

    DEFF Research Database (Denmark)

    Bjergbakke, Erling; Sehested, Knud; Rasmussen, O. Lang

    1976-01-01

    Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some ...... 10^{8}$ and $1.3\\times 10^{8}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$ in pH 2.1 H2 SO4 and HClO4, respectively.......Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...... of the reactions have been determined at different pH's. $k_{{\\rm Cu}^{+}+{\\rm O}_{2}}=4.6\\times 10^{5}$ and $1.0\\times 10^{6}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}^{+}+{\\rm Fe}^{3+}}=5.5\\times 10^{6}$ and $1.3\\times 10^{7}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}({\\rm III)}+{\\rm Fe}^{2+}}=3.3\\times...

  4. Effects of network dissolution changes on pore-to-core upscaled reaction rates for kaolinite and anorthite reactions under acidic conditions

    KAUST Repository

    Kim, Daesang; Lindquist, W. Brent

    2013-01-01

    new connections. The computed changes were based upon a mineral map from an X-ray computed tomography image of a sandstone core. We studied the effect of these changes on upscaled (pore-scale to core-scale) reaction rates and compared against

  5. Aerosol simulation including chemical and nuclear reactions

    International Nuclear Information System (INIS)

    Marwil, E.S.; Lemmon, E.C.

    1985-01-01

    The numerical simulation of aerosol transport, including the effects of chemical and nuclear reactions presents a challenging dynamic accounting problem. Particles of different sizes agglomerate and settle out due to various mechanisms, such as diffusion, diffusiophoresis, thermophoresis, gravitational settling, turbulent acceleration, and centrifugal acceleration. Particles also change size, due to the condensation and evaporation of materials on the particle. Heterogeneous chemical reactions occur at the interface between a particle and the suspending medium, or a surface and the gas in the aerosol. Homogeneous chemical reactions occur within the aersol suspending medium, within a particle, and on a surface. These reactions may include a phase change. Nuclear reactions occur in all locations. These spontaneous transmutations from one element form to another occur at greatly varying rates and may result in phase or chemical changes which complicate the accounting process. This paper presents an approach for inclusion of these effects on the transport of aerosols. The accounting system is very complex and results in a large set of stiff ordinary differential equations (ODEs). The techniques for numerical solution of these ODEs require special attention to achieve their solution in an efficient and affordable manner. 4 refs

  6. Theoretical Time Dependent Thermal Neutron Spectra and Reaction Rates in H2O and D2O

    International Nuclear Information System (INIS)

    Purohit, S.N.

    1966-04-01

    The early theoretical and experimental time dependent neutron thermalization studies were limited to the study of the transient spectrum in the diffusion period. The recent experimental measurements of the time dependent thermal neutron spectra and reaction rates, for a number of moderators, have generated considerable interest in the study of the time dependent Boltzmann equation. In this paper we present detailed results for the time dependent spectra and the reaction rates for resonance detectors using several scattering models of H 2 O and D 2 O. This study has been undertaken in order to interpret the integral time dependent neutron thermalization experiments in liquid moderators which have been performed at the AB Atomenergi. The proton gas and the deuteron gas models are inadequate to explain the measured reaction rates in H 2 O and D 2 O. The bound models of Nelkin for H 2 O and of Butler for D 2 O give much better agreement with the experimental results than the gas models. Nevertheless, some disagreement between theoretical and experimental results still persists. This study also indicates that the bound model of Butler and the effective mass 3. 6 gas model of Brown and St. John give almost identical reaction rates. It is also surprising to note that the calculated reaction rate for Cd for the Butler model appears to be in better agreement with the experimental results of D 2 O than of the Nelkin model with H 2 O experiments. The present reaction rate studies are sensitive enough so as to distinguish between the gas model and the bound model of a moderator. However, to investigate the details of a scattering law (such as the effect of the hindered rotations in H 2 O and D 2 O and the weights of different dynamical modes) with the help of these studies would require further theoretical as well as experimental investigations. Theoretical results can be further improved by improving the source for thermal neutrons, the group structure and the scattering

  7. Identification of secondary phases formed during unsaturated reaction of UO2 with EJ-13 water

    International Nuclear Information System (INIS)

    Bates, J.K.; Tani, B.S.; Veleckis, E.

    1989-01-01

    A set of experiments, wherein UO 2 has been contacted by dripping water, has been conducted over a period of 182.5 weeks. The experiments are being conducted to develop procedures to study spent fuel reaction under unsaturated conditions that are expected to exist over the lifetime of the proposed Yucca Mountain repository site. One half of the experiments have been terminated, while one half are ongoing. Analyses of solutions that have dripped from the reacted UO 2 have been performed for all experiments, while the reacted UO 2 surfaces have been examined for the terminated experiments. A pulse of uranium release from the UO 2 solid, combined with the formation of schoepite on the surface of the UO 2 , was observed between 39 and 96 weeks of reaction. Thereafter, the uranium release decreased and a second set of secondary phases was observed. The latter phases incorporated cations from the EJ-13 water and included boltwoodite, uranophane, sklodowskite, compreignacite, and schoepite. The experiments are continuing to monitor whether additional changes in solution chemistry or secondary phase formation occurs. 6 refs., 2 figs., 2 tabs

  8. Gas phase reactions of organic iodine in containment conditions

    International Nuclear Information System (INIS)

    Kaerkalae, T.; Holm, J.; Auvinen, A.; Zilliacus, R.; Kajolinna, T.; Tapper, U.; Gaenneskog, H.; Ekberg, C.

    2010-01-01

    In case of a hypothetical severe accident it is very likely that iodine at least partly deposits on painted walls of a reactor containment building. Iodine may react with painted surfaces to form organic iodine species. These organic species are a possible source of volatile iodine, which may increase the fraction of releasable iodine. Therefore, it is important to study the transport of organic iodine in containment conditions. Another question is, in which form are the organic iodides transported as gaseous molecules or as aerosol particles resulting from organic iodides reacting with radiolysis products. To answer this last question methyl iodide was fed into the EXSI facility in an air mixture. In some experiments the flow contained also humidity. The reactions took place in a quartz tube heated either to 50 deg. C, 90 deg. C or 120 deg. C. UV-light was used as a source of radiation to produce ozone from oxygen. A separate generator was also applied to reach higher ozone concentrations. Nucleated aerosol particles were collected on plane filters and gaseous iodine species were trapped in trapping bottles. Aerosol mass flow rate and size distribution as well as speciation of gaseous reaction products were measured with several on-line instruments. Collected aerosol particles were analysed with SEM. It was found that the formation of aerosol particles was very fast when ozone and methyl iodide were present in the facility. Even a very low concentration of ozone produced high number concentration of particles. The measured aerosol mass concentration increased with increasing temperature and ozone concentration. Because the particle diameter was quite small (<180 nm), their settling velocity is low. Therefore, iodine containing aerosols may exist in containment atmosphere for a long period of time. Part of methyl iodide was always transported through the facility regardless of experimental conditions. All ozone was consumed in the reactions when only UV-light was

  9. Reaction Rate Distributions and Ratios in FR0 Assemblies 1, 2 and 3

    Energy Technology Data Exchange (ETDEWEB)

    Andersson, T L

    1966-06-15

    The spatial distribution of different reaction rates and reaction ratios in Assemblies 1, 2 and 3 of the fast reactor FR0 was measured by fission chamber scans and foil activation technique. Assemblies 1 and 2 had cores of undiluted fuel (uranium metal enriched to 20 % U{sup 235}) while the core of Assembly 3 was diluted with about 30 vol. % graphite. All the systems had a thick copper reflector, The experimental results were compared with calculated values obtained from DSN and TDC multigroup spectra and group cross-section sets for the reactions. Good agreement between experiment and calculations is generally obtained in the core region but in the reflector the neutron spectrum is calculated too hard.

  10. Liquid-liquid transfer phenomena studies coupled with redox reactions: back-extraction of nitrous acid in the presence of scavengers in aqueous phase; Etude de reactions d`oxydoreduction couplees a des phenomenes de transfert liquide-liquide: cas de la desextraction de l`acide nitreux en presence de composes antinitreux en phase aqueuse

    Energy Technology Data Exchange (ETDEWEB)

    K`zerho, R

    1998-12-31

    This work deals with the investigation of redox reaction contribution to the kinetics of liquid-liquid transfer, in relation with PUREX reprocessing of spent nuclear fuel. The chemical system chosen concerns the tripping of nitrous acid from tributylphosphate organic phase into a nitric acid aqueous solution containing an `anti-nitrous` component, namely hydrazinium nitrate. According to the abundant literature, a major attention is devoted to the very important role of interfacial phenomena on the kinetics of solvent extraction with tributylphosphate. Although, a suitable experimental technique is chosen, using a constant interfacial area cell of the ARMOLLEX-type. Furthermore, the effects of the hydrodynamical and the physico-chemical parameters on the extraction rate led to the identification of the extraction regime nature: diffusional, then chemical limitation. When no `anti-nitrous` component is used, the diffusional resistance is found to be mainly located in the aqueous diffusion layer. The presence of hydrazinium nitrate into the aqueous solution has an overall accelerating effect on the rate of extraction, related to both a complete suppression of the aqueous diffusional resistance, and a very significant enhancement of the interfacial transfer of the nitrous acid, as a function of hydrazinium concentration. If the first effect could be expected because of the well known fast redox reaction in aqueous phase, the second phenomenon represents a quite original and new result which has never been explored before, to the best of our knowledge. A reaction mechanism is postulated and validated, taking into account the reactive effect of hydrazinium on the interfacial step. In order to support the drawn general patterns, different complementary studies were attempted. When hydroxyl-ammonium nitrate is used, a surprising interfacial transfer blockage is observed, pointing out the extreme performance and specificity of the common hydrazinium component. (author) 99

  11. Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

    Science.gov (United States)

    Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

    2018-06-04

    In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

  12. Mass transfer with complex chemical reactions in gas-liquid systems: two-step revers