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.

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.

Study on reduction reactions of neptunium(V) on magnetite surface

International Nuclear Information System (INIS)

Kitamura, Akira; Kamei, Gento; Nakata, Kotaro; Tanaka, Satoru; Tomura, Tsutomu

2004-01-01

Redox reactions between neptunium(V) (Np(V)) and magnetite (Fe(II) 1 Fe(III) 2 O 4 ) surface were investigated in N 2 gas atmosphere. A batch method was applied to the experiment. A magnetite sample and a 0.1 M NaCl solution were mixed in a polypropylene tube, and pH, redox potential and concentration of dissolved neptunium were measured as a function of shaking time, temperature and liquid/solid ratio. The concentration of dissolved neptunium was reduced rapidly within a day, due to the reducing reaction of Np(V) to Np(IV) and the precipitation of Np(IV). The rate constant of the redox reaction and the activation energy for the rate constant were preliminarily obtained. On the other hand, redox reactions between Np(V) and aqueous Fe(II) were hardly observed. Considering the number of transferred electrons, it was suggested that the redox reaction was promoted by not only Fe(II) on the magnetite surface, but also Fe(II) inside the magnetite. (author)

Theoretical Study of Sodium-Water Surface Reaction Mechanism

Science.gov (United States)

Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).

Theoretical study of sodium-water surface reaction mechanism

International Nuclear Information System (INIS)

Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

2012-01-01

Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

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.

Rate and extent of aqueous perchlorate removal by iron surfaces.

Science.gov (United States)

Moore, Angela M; De Leon, Corinne H; Young, Thomas M

2003-07-15

The rate and extent of perchlorate reduction on several types of iron metal was studied in batch and column reactors. Mass balances performed on the batch experiments indicate that perchlorate is initially sorbed to the iron surface, followed by a reduction to chloride. Perchlorate removal was proportional to the iron dosage in the batch reactors, with up to 66% removal in 336 h in the highest dosage system (1.25 g mL(-1)). Surface-normalized reaction rates among three commercial sources of iron filings were similar for acid-washed samples. The most significant perchlorate removal occurred in solutions with slightly acidic or near-neutral initial pH values. Surface mediation of the reaction is supported by the absence of reduction in batch experiments with soluble Fe2+ and also by the similarity in specific reaction rate constants (kSA) determined for three different iron types. Elevated soluble chloride concentrations significantly inhibited perchlorate reduction, and lower removal rates were observed for iron samples with higher amounts of background chloride contamination. Perchlorate reduction was not observed on electrolytic sources of iron or on a mixed-phase oxide (Fe3O4), suggesting that the reactive iron phase is neither pure zerovalent iron nor the mixed oxide alone. A mixed valence iron hydr(oxide) coating or a sorbed Fe2+ surface complex represent the most likely sites for the reaction. The observed reaction rates are too slow for immediate use in remediation system design, but the findings may provide a basis for future development of cost-effective abiotic perchlorate removal techniques.

Dominant rate process of silicon surface etching by hydrogen chloride gas

International Nuclear Information System (INIS)

Habuka, Hitoshi; Suzuki, Takahiro; Yamamoto, Sunao; Nakamura, Akio; Takeuchi, Takashi; Aihara, Masahiko

2005-01-01

Silicon surface etching and its dominant rate process are studied using hydrogen chloride gas in a wide concentration range of 1-100% in ambient hydrogen at atmospheric pressure in a temperature range of 1023-1423 K, linked with the numerical calculation accounting for the transport phenomena and the surface chemical reaction in the entire reactor. The etch rate, the gaseous products and the surface morphology are experimentally evaluated. The dominant rate equation accounting for the first-order successive reactions at silicon surface by hydrogen chloride gas is shown to be valid. The activation energy of the dominant surface process is evaluated to be 1.5 x 10 5 J mol - 1 . The silicon deposition by the gaseous by-product, trichlorosilane, is shown to have a negligible influence on the silicon etch rate

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.

Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

Science.gov (United States)

Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

2016-09-01

It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

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

Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

International Nuclear Information System (INIS)

Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

2009-01-01

A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

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…

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

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.

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.

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.

Capability of LEP-type surfaces to describe noncollinear reactions 2 - Polyatomic systems

CERN Document Server

Espinosa-Garcia, Joaquin

2001-01-01

In this second article of the series, the popular LEP-type surface for collinear reaction paths and a "bent" surface, which involves a saddle point geometry with a nonlinear central angle, were used to examine the capacity of LEP-type surfaces to describe the kinetics and dynamics of noncollinear reaction paths in polyatomic systems. Analyzing the geometries, vibrational frequencies, curvature along the reaction path (to estimate the tunneling effect and the reaction coordinate-bound modes coupling), and the variational transition- state theory thermal rate constants for the NH//3 + O(**3P) reaction, we found that the "collinear" LEP-type and the "bent" surfaces for this polyatomic system show similar behavior, thus allowing a considerable saving in time and computational effort. This agreement is especially encouraging for this polyatomic system because in the Cs symmetry the reaction proceeds via two electronic states of symmetries **3A prime and **3A double prime , which had to be independently calibrated....

Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

Science.gov (United States)

Li, Jun; Guo, Hua

2018-03-15

Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

Chemical reaction on solid surface observed through isotope tracer technique

International Nuclear Information System (INIS)

Tanaka, Ken-ichi

1983-01-01

In order to know the role of atoms and ions on solid surfaces as the partners participating in elementary processes, the literatures related to the isomerization and hydrogen exchanging reaction of olefines, the hydrogenation of olefines, the metathesis reaction and homologation of olefines based on solid catalysts were reviewed. Various olefines, of which the hydrogen atoms were substituted with deuterium at desired positions, were reacted using various solid catalysts such as ZnO, K 2 CO 3 on C, MoS 2 (single crystal and powder) and molybdenum oxide (with various carriers), and the infra-red spectra of adsorbed olefines on catalysts, the isotope composition of reaction products and the production rate of the reaction products were measured. From the results, the bonding mode of reactant with the atoms and ions on solid surfaces, and the mechanism of the elementary process were considered. The author emphasized that the mechanism of the chemical reaction on solid surfaces and the role of active points or catalysts can be made clear to the considerable extent by combining isotopes suitably. (Yoshitake, I.)

Small leak detection by measuring surface oscillation during sodium-water reaction in steam generator

International Nuclear Information System (INIS)

Nei, Hiromichi; Hori, Masao

1977-01-01

Small leak sodium-water reaction tests were conducted to develop various kinds of leak detectors for the sodium-heated steam generator in FBR. The super-heated steam was injected into sodium in a reaction vessel having a sodium free surface, simulating the steam generator. The level gauge in the reaction vessel generated the most reliable signal among detectors, as long as the leak rates were relatively high. The level gauge signal was estimated to be the sodium surface oscillation caused by hydrogen bubbles produced in sodium-water reaction. Experimental correlation was derived, predicting the amplitude as a function of leak rate, hydrogen dissolution ratio, bubble rise velocity and other parameters concerned, assuming that the surface oscillation is in proportion to the gas hold-up. The noise amplitude under normal operation without water leak was increased with sodium flow rate and found to be well correlated with Froud number. These two correlations predict that a water leak in a ''MONJU'' class (300 MWe) steam generator could possibly be detected by level gauges at a leak rate above 2 g/sec. (auth.)

Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Chen Li [Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Goettingen (Germany); Ueta, Hirokazu; Beck, Rainer D. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Federale de Lausanne (Switzerland); Bisson, Regis [Aix-Marseille Universite, PIIM, CNRS, UMR 7345, 13397 Marseille (France)

2013-05-15

We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S({theta}). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

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)

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.

Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

Science.gov (United States)

Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

1994-01-01

Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

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)

Surface area-burnoff correlation for the steam--graphite reaction

International Nuclear Information System (INIS)

Stark, W.A. Jr.; Malinauskas, A.P.

1977-01-01

The oxidation of core graphite by steam of air represents a problem area of significant concern in safety analyses for the high temperature gas cooled reactor (HTGR). Core and core-support graphite integrity and strength deteriorate with oxidation of the graphite, and oxidation furthermore could affect the rate of fission product release under upset conditions. Consequently, modeling of core response during steam or air ingress conditions requires an expression for the rate of graphite interaction with those impurities. The steam--graphite reaction in particular is a complex interaction of mass transport within the graphite with chemi-sorption and reaction on accessible surfaces; experimental results from graphite to graphite are highly variable, and the description of the reaction is not yet completely consistent. A simple etch pit model relating surface area to burnoff has been proposed and shown to provide reasonable correlation with experimental data obtained from steam oxidation studies of nuclear grade H-327 graphite. Unaccounted differences between theory and experiment arise at burnoffs exceeding 3 to 5 percent. The model, while not complete nor comprehensive, is consistent with experimental observations of graphite oxidation by O 2 (air), CO 2 , or H 2 O, and could have some utility in safety analysis

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.

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…

On surface reactions of iron tungstate with ethane

International Nuclear Information System (INIS)

Obrubov, V.A.; Shchukin, V.P.; Averbukh, A.Ya.

1980-01-01

Results of investigation of ethane oxidation reaction upon iron tungstate are presented. It is shown that catalytic oxidation of ethane is accompanied by the surface reaction of the catalyst reduction. Maximum reduction of surface depends upon temperature and considerably affects the direction of ethane oxidation process. Activation energies of ethane oxidation reactions and surface reaction of iron tungstate reduction depend on the surface actual state and at its reduction up to 5% from monolayer change in the limits 36.0-46.0 and 53.0-66.0 kcal/mol respectively

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

Theory of the reaction dynamics of small molecules on metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

2016-09-09

The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H₂, H₂O and CH₄ on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

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

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.

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.

Low temperature rate coefficients of the H + CH(+) → C(+) + H2 reaction: New potential energy surface and time-independent quantum scattering.

Science.gov (United States)

Werfelli, Ghofran; Halvick, Philippe; Honvault, Pascal; Kerkeni, Boutheïna; Stoecklin, Thierry

2015-09-21

The observed abundances of the methylidyne cation, CH(+), in diffuse molecular clouds can be two orders of magnitude higher than the prediction of the standard gas-phase models which, in turn, predict rather well the abundances of neutral CH. It is therefore necessary to investigate all the possible formation and destruction processes of CH(+) in the interstellar medium with the most abundant species H, H2, and e(-). In this work, we address the destruction process of CH(+) by hydrogen abstraction. We report a new calculation of the low temperature rate coefficients for the abstraction reaction, using accurate time-independent quantum scattering and a new high-level ab initio global potential energy surface including a realistic model of the long-range interaction between the reactants H and CH(+). The calculated thermal rate coefficient is in good agreement with the experimental data in the range 50 K-800 K. However, at lower temperatures, the experimental rate coefficient takes exceedingly small values which are not reproduced by the calculated rate coefficient. Instead, the latter rate coefficient is close to the one given by the Langevin capture model, as expected for a reaction involving an ion and a neutral species. Several recent theoretical works have reported a seemingly good agreement with the experiment below 50 K, but an analysis of these works show that they are based on potential energy surfaces with incorrect long-range behavior. The experimental results were explained by a loss of reactivity of the lowest rotational states of the reactant; however, the quantum scattering calculations show the opposite, namely, a reactivity enhancement with rotational excitation.

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

Bond-selective control of a gas-surface reaction

Science.gov (United States)

Killelea, Daniel R.

The prospect of using light to selectively control chemical reactions has tantalized chemists since the development of the laser. Unfortunately, the realization of laser-directed chemistry is frequently thwarted by the randomization of energy within the molecule through intramolecular vibrational energy distribution (IVR). However, recent results showing vibrational mode-specific reactivity on metal surfaces suggest that IVR may not always be complete for gas-surface reactions. Here, we combine molecular beam techniques and direct laser excitation to characterize the bond-specific reactivity of trideuteromethane on a Ni(111) surface. Our results reveal important details about how vibrational energy is distributed in the reactive molecule. We use a molecular beam to direct state-selected trideuteromethane (CHD 3) molecules onto a nickel single crystal sample and use the results we obtain to describe the flow of vibrational energy in the methane-surface reaction complex. We show that CHD3 molecules initially excited to v=1, J=2, K=0 of the v 1 symmetric C-H stretching mode will dissociate exclusively via C-H cleavage on Ni(111). This result highlights the localization of vibrational energy in the reaction complex, despite the presence of many energy exchange channels with the high state-density surface. We demonstrate, for the first time, highly parallel bond-selective control of a heterogeneously catalyzed reaction. We place our results in the context of recent experiments investigating IVR for molecules in both the gas phase and liquid solutions. If IVR is fast on the reaction timescale, vibrational energy would be randomly distributed throughout the nascent methane-surface reaction complex and vibrational mode-specific behavior would not occur. The short timescale of a direct gas-surface collision may explain how the exchange of energy via IVR is limited to only a small subset of the energetic configurations available to the reaction complex. This framework

Surface chemical reactions probed with scanning force microscopy

NARCIS (Netherlands)

Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

1997-01-01

In this letter we report the study of surface chemical reactions with scanning force microscopy (SFM) with chemical specificity. Using chemically modified SFM probes, we can determine the local surface reaction conversion during a chemical surface modification. The adhesion forces between a

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

Studies of the surface of titanium dioxide. IV. The hydrogen-deuterium equilibration reaction

International Nuclear Information System (INIS)

Iwaki, T.; Katsuta, K.; Miura, M.

1981-01-01

The interaction of hydrogen with the surface of titanium dioxide has been studied in connection with the hydrogen-reduction mechanism of titanium dioxide, by means of such measurements as weight decrease, magnetic susceptibility, hydrogen uptake, and electrical conductance. It was postulated in the previous study that the rate-determining step of the hydrogen-reduction reaction may be the formation of surface hydroxyl groups, followed by the rapid removal of water molecules from the surface. In this study, the interactions between hydrogen and the surface of titanium dioxide were investigated by measuring the hydrogen-deuterium equilibration reaction, H 2 + D 2 = 2HD, at temperatures above 200 0 C on both surfaces before and after hydrogen reduction to compare the differences in the reactivities

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.

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

Specifications for surface reaction analysis apparatus

International Nuclear Information System (INIS)

Teraoka, Yuden; Yoshigoe, Akitaka

2001-03-01

A surface reaction analysis apparatus was installed at the JAERI soft x-ray beamline in the SPring-8 as an experimental end-station for the study of surface chemistry. The apparatus is devoted to the study concerning the influence of translational kinetic energy of incident molecules to chemical reactions on solid surfaces with gas molecules. In order to achieve the research purpose, reactive molecular scattering experiments and photoemission spectroscopic measurements using synchrotron radiation are performed in that apparatus via a supersonic molecular beam generator, an electron energy analyzer and a quadrupole mass analyzer. The detail specifications for the apparatus are described in this report. (author)

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)

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

Electronic dissipation processes during chemical reactions on surfaces

CERN Document Server

Stella, Kevin

2012-01-01

Hauptbeschreibung Every day in our life is larded with a huge number of chemical reactions on surfaces. Some reactions occur immediately, for others an activation energy has to be supplied. Thus it happens that though a reaction should thermodynamically run off, it is kinetically hindered. Meaning the partners react only to the thermodynamically more stable product state within a mentionable time if the activation energy of the reaction is supplied. With the help of catalysts the activation energy of a reaction can be lowered. Such catalytic processes on surfaces are widely used in industry. A

Numerical simulation of hydrogen-air reacting flows in rectangular channels with catalytic surface reactions

Science.gov (United States)

Amano, Ryoichi S.; Abou-Ellail, Mohsen M.; Elhaw, Samer; Saeed Ibrahim, Mohamed

2013-09-01

In this work a prediction was numerically modeled for a catalytically stabilized thermal combustion of a lean homogeneous mixture of air and hydrogen. The mixture flows in a narrow rectangular channel lined with a thin coating of platinum catalyst. The solution using an in-house code is based on the steady state partial differential continuity, momentum and energy conservation equations for the mixture and species involved in the reactions. A marching technique is used along the streamwise direction to solve the 2-D plane-symmetric laminar flow of the gas. Two chemical kinetic reaction mechanisms were included; one for the gas phase reactions consisting of 17 elementary reactions; of which 7 are forward-backward reactions while the other mechanism is for the surface reactions—which are the prime mover of the combustion under a lean mixture condition—consisting of 16 elementary reactions. The results were compared with a former congruent experimental work where temperature was measured using thermocouples, while using PLIF laser for measuring water and hydrogen mole fractions. The comparison showed good agreement. More results for the velocities, mole fractions of other species were carried out across the transverse and along the streamwise directions providing a complete picture of overall mechanism—gas and surface—and on the production, consumptions and travel of the different species. The variations of the average OH mole fraction with the streamwise direction showed a sudden increase in the region where the ignition occurred. Also the rate of reactions of the entire surface species were calculated along the streamwise direction and a surface water production flux equation was derived by calculating the law of mass action's constants from the concentrations of hydrogen, oxygen and the rate of formation of water near the surface.

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)

Molecular-dynamics analysis of mobile helium cluster reactions near surfaces of plasma-exposed tungsten

Energy Technology Data Exchange (ETDEWEB)

Hu, Lin; Maroudas, Dimitrios, E-mail: maroudas@ecs.umass.edu [Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003-9303 (United States); Hammond, Karl D. [Department of Chemical Engineering, University of Missouri, Columbia, Missouri 65211 (United States); Wirth, Brian D. [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States)

2015-10-28

We report the results of a systematic atomic-scale analysis of the reactions of small mobile helium clusters (He{sub n}, 4 ≤ n ≤ 7) near low-Miller-index tungsten (W) surfaces, aiming at a fundamental understanding of the near-surface dynamics of helium-carrying species in plasma-exposed tungsten. These small mobile helium clusters are attracted to the surface and migrate to the surface by Fickian diffusion and drift due to the thermodynamic driving force for surface segregation. As the clusters migrate toward the surface, trap mutation (TM) and cluster dissociation reactions are activated at rates higher than in the bulk. TM produces W adatoms and immobile complexes of helium clusters surrounding W vacancies located within the lattice planes at a short distance from the surface. These reactions are identified and characterized in detail based on the analysis of a large number of molecular-dynamics trajectories for each such mobile cluster near W(100), W(110), and W(111) surfaces. TM is found to be the dominant cluster reaction for all cluster and surface combinations, except for the He{sub 4} and He{sub 5} clusters near W(100) where cluster partial dissociation following TM dominates. We find that there exists a critical cluster size, n = 4 near W(100) and W(111) and n = 5 near W(110), beyond which the formation of multiple W adatoms and vacancies in the TM reactions is observed. The identified cluster reactions are responsible for important structural, morphological, and compositional features in the plasma-exposed tungsten, including surface adatom populations, near-surface immobile helium-vacancy complexes, and retained helium content, which are expected to influence the amount of hydrogen re-cycling and tritium retention in fusion tokamaks.

Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

Science.gov (United States)

Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

1994-01-01

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

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).

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.

Supersonic molecular beam experiments on surface chemical reactions.

Science.gov (United States)

Okada, Michio

2014-10-01

The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of growth conditions and surface reaction byproducts on GaN grown via metal organic molecular beam epitaxy: Toward an understanding of surface reaction chemistry

Science.gov (United States)

Pritchett, David; Henderson, Walter; Burnham, Shawn D.; Doolittle, W. Alan

2006-04-01

The surface reaction byproducts during the growth of GaN films via metal organic molecular beam epitaxy (MOMBE) were investigated as a means to optimize material properties. Ethylene and ethane were identified as the dominant surface reaction hydrocarbon byproducts, averaging 27.63% and 7.15% of the total gas content present during growth. Intense ultraviolet (UV) photoexcitation during growth was found to significantly increase the abundance of ethylene and ethane while reducing the presence of H2 and N2. At 920°C, UV excitation was shown to enhance growth rate and crystalline quality while reducing carbon incorporation. Over a limited growth condition range, a 4.5×1019-3.4×1020 cm-3 variation in carbon incorporation was achieved at constant high vacuum. Coupled with growth rate gains, UV excitation yielded films with ˜58% less integrated carbon content. Structural material property variations are reported for various ammonia flows and growth temperatures. The results suggest that high carbon incorporation can be achieved and regulated during MOMBE growth and that in-situ optimization through hydrocarbon analysis may provide further enhancement in the allowable carbon concentration range.

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.

Surface oxidization-reduction reactions in Columbia Plateau basalts

International Nuclear Information System (INIS)

White, A.F.; Yee, A.

1984-01-01

Results are presented which define principal oxidation-reduction reactions expected between ground water and iron in the Umtanum and Cohassett basalt flows of south central Washington. Data include kinetics of aqueous iron speciation, rates of O 2 uptake and nature of oxyhydroxide precipitates. Such data are important in predicting behavior of radionuclides in basalt aquifers including determination of valence states, speciation, solubility, sorption, and coprecipitation on iron oxyhydroxide substrates and colloids. Analyses of the basalt by XPS indicates that ferrous iron is oxidized to ferric iron on the surface and that the total iron decreases as a function of pH during experimental weathering. Iron oxyhydroxide phases did not form surface coating on basalt surfaces but rather nucleated as separate plases in solution. No significant increases in Cs or Sr sorption were observed with increased weathering of the basalt. Concurrent increases in Fe(II) and decreases in Fe(III) in slightly to moderately acid solutions indicated continued oxidization of ferrous iron in the basalt. At neutral to basic pH, Fe(II) was strongly sorbed onto the basalt surface (Kd = 6.5 x 10 -3 1 x m 2 ) resulting in low dissolved concentrations even under anoxic conditions. The rate of O 2 uptake increased with decreasing pH. Diffusion rates (-- 10 -14 cm 2 x s -1 ), calculated using a one-dimensional analytical model, indicate grain boundary diffusion. Comparisons of Eh values calculated by Pt electrode, dissolved O 2 and Fe(II)/Fe(III) measurements showed considerable divergence, with the ferric-ferrous couple being the preferred method of estimating Eh

Formation of the prebiotic molecule NH2CHO on astronomical amorphous solid water surfaces: accurate tunneling rate calculations.

Science.gov (United States)

Song, Lei; Kästner, Johannes

2016-10-26

Investigating how formamide forms in the interstellar medium is a hot topic in astrochemistry, which can contribute to our understanding of the origin of life on Earth. We have constructed a QM/MM model to simulate the hydrogenation of isocyanic acid on amorphous solid water surfaces to form formamide. The binding energy of HNCO on the ASW surface varies significantly between different binding sites, we found values between ∼0 and 100 kJ mol -1 . The barrier for the hydrogenation reaction is almost independent of the binding energy, though. We calculated tunneling rate constants of H + HNCO → NH 2 CO at temperatures down to 103 K combining QM/MM with instanton theory. Tunneling dominates the reaction at such low temperatures. The tunneling reaction is hardly accelerated by the amorphous solid water surface compared to the gas phase for this system, even though the activation energy of the surface reaction is lower than the one of the gas-phase reaction. Both the height and width of the barrier affect the tunneling rate in practice. Strong kinetic isotope effects were observed by comparing to rate constants of D + HNCO → NHDCO. At 103 K we found a KIE of 231 on the surface and 146 in the gas phase. Furthermore, we investigated the gas-phase reaction NH 2 + H 2 CO → NH 2 CHO + H and found it unlikely to occur at cryogenic temperatures. The data of our tunneling rate constants are expected to significantly influence astrochemical models.

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.

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)

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)

Basic reactions of osteoblasts on structured material surfaces

Directory of Open Access Journals (Sweden)

U. Meyer

2005-04-01

Full Text Available In order to assess how bone substitute materials determine bone formation in vivo it is useful to understand the mechanisms of the material surface/tissue interaction on a cellular level. Artificial materials are used in two applications, as biomaterials alone or as a scaffold for osteoblasts in a tissue engineering approach. Recently, many efforts have been undertaken to improve bone regeneration by the use of structured material surfaces. In vitro studies of bone cell responses to artificial materials are the basic tool to determine these interactions. Surface properties of materials surfaces as well as biophysical constraints at the biomaterial surface are of major importance since these features will direct the cell responses. Studies on osteoblast-like cell reactivity towards materials will have to focus on the different steps of protein and cell reactions towards defined surface properties. The introduction of new techniques allows nowadays the fabrication of materials with ordered surface structures. This paper gives a review of present knowledge on the various stages of osteoblast reactions on material surfaces, focused on basic cell events under in vitro conditions. Special emphasis is given to cellular reactions towards ordered nano-sized topographies.

The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

Energy Technology Data Exchange (ETDEWEB)

Tully, John C. [Yale Univ., New Haven, CT (United States)

2017-06-10

Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

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)

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.

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

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…

Non-thermal desorption from interstellar dust grains via exothermic surface reactions

Science.gov (United States)

Garrod, R. T.; Wakelam, V.; Herbst, E.

2007-06-01

Aims:The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely constrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 106 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

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.

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.

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.

Reaction mechanisms for on-surface synthesis of covalent nanostructures

International Nuclear Information System (INIS)

Björk, J

2016-01-01

In recent years, on-surface synthesis has become an increasingly popular strategy to form covalent nanostructures. The approach has great prospects for facilitating the manufacture of a range of fascinating materials with atomic precision. However, the on-surface reactions are enigmatic to control, currently restricting its bright perspectives and there is a great need to explore how the reactions are governed. The objective of this topical review is to summarize theoretical work that has focused on comprehending on-surface synthesis protocols through studies of reaction mechanisms. (topical review)

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

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.

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.)

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).

Reactions between monolayer Fe and Si(001) surfaces

Energy Technology Data Exchange (ETDEWEB)

Hasegawa, M; Kobayashi, N; Hayashi, N [Electrotechnical Lab., Tsukuba, Ibaraki (Japan)

1997-03-01

Reactions between 1.5 monolayer(ML) Fe deposited on Si(001)-2x1 and -dihydride surfaces were studied in situ by reflection high-energy electron diffraction and time-of-flight ion scattering spectrometry with the use of 25 keV H ions. The reactions between Fe and Si which were successively deposited on Si(001)-dihydride surface were also studied. After the room temperature deposition Fe reacted with Si(001)-2x1 substrate resulting in the formation of polycrystalline Fe5Si3. By annealing to 560-650degC composite heteroepitaxial layer of both type A and type B {beta}-FeSi2 was formed. On the dihydride surface polycrystalline Fe was observed after 1.5ML Fe deposition at room temperature, and reaction between Fe and Si(001)-dihydride surface is not likely at room temperature. We observed 3D rough surface when we deposited only Fe layer on the dihydride surface and annealed above 700degC. The hydrogen termination of Si(001) surface prevents the deposited Fe from diffusing into the substrate below 500degC, however the annealing above 710degC leads to the diffusion. We obtained 2D ordered surface, which showed 3x3 RHEED pattern as referenced to the primitive unreconstructed Si(001) surface net, when we deposited 2.5ML Fe and 5.8ML Si successively onto Si(001)-dihydride surface and annealed to 470degC. (author)

Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

Science.gov (United States)

Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

2018-03-06

To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

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

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.

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

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.)

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.

Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

Science.gov (United States)

Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco Bolivar Correto; Hase, William Louis

2018-04-26

The reaction of 3CH2 with 3O2 is of fundamental importance in combustion and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH2OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H2CO + O(3P), while the singlet surface leads to 8 product channels with their relative importance as: CO + H2O > CO + OH + H ~ H2CO + O(1D) > HCO + OH ~ CO2 + H2 ~ CO + H2 + O(1D) > CO2 + H + H > HCO + O(1D) + H. Reaction on the singlet PES is barrierless, consistent with experiment and the total rate constant on the singlet surface is 0.93 ± 0.22 x 10-12 cm3molecule-1s-1 in comparison to the recommended experimental rate constant of 3.3 x 10-12 cm3molecule-1s-1. The simulation product yields for the singlet PES are compared with experiment and the most significant differences are for H, CO2, and H2O. Reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address the: (1) barrier on the triplet PES for 3CH2 + 3O2 → 3CH2OO; (2) temperature dependence of the 3CH2 + 3O2 reaction rate constant and product branching ratios; and (3) possible non-RRKM dynamics of the 1CH2OO Criegee intermediate.

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.

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,

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.

Pd-catalyzed coupling reaction on the organic monolayer: Sonogashira reaction on the silicon (1 1 1) surfaces

International Nuclear Information System (INIS)

Qu Mengnan; Zhang Yuan; He Jinmei; Cao Xiaoping; Zhang Junyan

2008-01-01

Iodophenyl-terminated organic monolayers were prepared by thermally induced hydrosilylation on hydrogen-terminated silicon (1 1 1) surfaces. The films were characterized by ellipsometry, contact-angle goniometry, and X-ray photoelectron spectroscopy (XPS). To modify the surface chemistry and the structure of the monolayers, the Sonogashira coupling reaction was performed on the as-prepared monolayers. The iodophenyl groups on the film surfaces reacted with 1-ethynyl-4-fluorobenzene or the 1-chloro-4-ethynylbenzene under the standard Sonogashira reaction conditions for attaching conjugated molecules via the formation of C-C bonds. It is expected that this surface coupling reaction will present a new method to modify the surface chemistry and the structure of monolayers

Surface controlled dissolution rates of gypsum in aqueous solutions exhibit nonlinear dissolution kinetics

Science.gov (United States)

Jeschke, Alexander A.; Vosbeck, Katrin; Dreybrodt, Wolfgang

2001-01-01

The effective dissolution rates of gypsum are determined by mixed kinetics, where the rate constants of dissolution at the surface and the transport constant of molecular diffusion of dissolved material are similar. To obtain the surface reaction rate law it is necessary to know the transport constant. We have determined the surface rate law for monocrystalline selenite by using a rotating disc set-up, where the transport coefficients are well known. As a result, up to a calcium concentration of 0.6 · ceq, we find a nearly linear rate law Rs = ksl (1- cs/ ceq) n1, where cs is the total calcium concentration at the surface and ceq the equilibrium concentration with respect to gypsum, n1 = 1.2 ± 0.2, and ksl = 1.1 · 10 -4 mmol cm -2 s -1 ± 15%. We also employed batch-experiments for selenite, alabaster and gypsum rock samples. The result of these experiments were interpreted by using a transport constant determined by NaCl dissolution experiments under similar physical conditions. The batch experiments reveal a dissolution rate law Rs = ksl (1- cs/ ceq) n1, ksl = 1.3 · 10 -4 mmol · cm -2 s -1, n1 = 1.2 ± 0.2 for c ≤ 0.94 · ceq. Close to equilibrium a nonlinear rate law, Rs = ks2 (1- cs/ ceq) n2, is observed, where ks2 is in the order of 10 mmol · cm -2 s -1 and n2 ≈ 4.5. The experimentally observed gypsum dissolution rates from the batch experiments could be accurately fitted, with only minor variations of the surface reaction constant obtained from the rotating disk experiment and the transport coefficient from the NaCl dissolution batch experiment. Batch experiments on pure synthetic gypsum, reveal a linear rate law up to equilibrium. This indicates inhibition of dissolution in natural samples close to equilibrium, as is known also for calcite minerals.

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

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)

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)

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.

Variational RRKM calculation of thermal rate constant for C–H bond fission reaction of nitro methane

Directory of Open Access Journals (Sweden)

Afshin Taghva Manesh

2017-02-01

Full Text Available The present work provides quantitative results for the rate constants of unimolecular C–H bond fission reactions in the nitro methane at elevated temperatures up to 2000 K. In fact, there are three different hydrogen atoms in the nitro methane. The potential energy surface for each C–H bond fission reaction of nitro methane was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C–H bond fission channel is a barrierless reaction, we have used variational RRKM theory to predict rate coefficients. By means of calculated rate coefficients at different temperatures, the Arrhenius expression of the channel over the temperature range of 100–2000 K is k(T = 5.9E19∗exp(−56274.6/T.

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.

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

Energy Technology Data Exchange (ETDEWEB)

Stoerzinger, Kelsey A. [Physical; Favaro, Marco [Advanced; Joint; Chemical; Ross, Philip N. [Materials; Yano, Junko [Joint; Molecular; Liu, Zhi [State; Division; Hussain, Zahid [Advanced; Crumlin, Ethan J. [Advanced; Joint Center

2017-11-02

Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assess the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.

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)

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.

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 ...

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.

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.

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.

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.

Rate equation analysis of hydrogen uptake on Si (100) surfaces

International Nuclear Information System (INIS)

Inanaga, S.; Rahman, F.; Khanom, F.; Namiki, A.

2005-01-01

We have studied the uptake process of H on Si (100) surfaces by means of rate equation analysis. Flowers' quasiequilibrium model for adsorption and desorption of H [M. C. Flowers, N. B. H. Jonathan, A. Morris, and S. Wright, Surf. Sci. 396, 227 (1998)] is extended so that in addition to the H abstraction (ABS) and β 2 -channel thermal desorption (TD) the proposed rate equation further includes the adsorption-induced desorption (AID) and β 1 -TD. The validity of the model is tested by the experiments of ABS and AID rates in the reaction system H+D/Si (100). Consequently, we find it can well reproduce the experimental results, validating the proposed model. We find the AID rate curve as a function of surface temperature T s exhibits a clear anti-correlation with the bulk dangling bond density versus T s curve reported in the plasma-enhanced chemical vapor deposition (CVD) for amorphous Si films. The significance of the H chemistry in plasma-enhanced CVD is discussed

Understanding the mechanisms of solid-water reactions through analysis of surface topography.

Science.gov (United States)

Bandstra, Joel Z; Brantley, Susan L

2015-12-01

The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic

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...

First-order dissolution rate law and the role of surface layers in glass performance assessment

Science.gov (United States)

Grambow, B.; Müller, R.

2001-09-01

The first-order dissolution rate law is used for nuclear waste glass performance predictions since 1984. A first discussion of the role of saturation effects was initiated at the MRS conference that year. In paper (1) it was stated that "For glass dissolution A* (the reaction affinity) cannot become zero since saturation only involves the reacting surface while soluble elements still might be extracted from the glass" [B. Grambow, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 15]. Saturation of silica at the surface and condensation of surface silanol groups was considered as being responsible for the slow down of reaction rates by as much as a factor of 1000. Precipitation of Si containing secondary phases such as quartz was invoked as a mechanism for keeping final dissolution affinities higher than zero. Another (2) paper [A.B. Barkatt, P.B. Macedo, B.C. Gibson, C.J. Montrose, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 3] stated that "… under repository conditions the extent of glass dissolution will be moderate due to saturation with respect to certain major elements (in particular, Si, Al and Ca). Consequently, the concentration levels of the more soluble glass constituents in the aqueous medium are expected to fall appreciable below their solubility limit." The formation of dense surface layers was considered responsible for explaining the saturation effect. The mathematical model assumed stop of reaction in closed systems, once solubility limits were achieved. For more than 15 years the question of the correctness of one or the other concept has seldom been posed and has not yet been resolved. The need of repository performance assessment for validated rate laws demands a solution, particularly since the consequences of the two concepts and research requirements for the long-term glass behavior are quite different. In concept (1) the stability of the `equilibrium surface region' is not relevant because, by definition, this region is stable chemically and after a

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

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.

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.

The role of high temperature heterogeneous reaction kinetics in the rate of radionuclide vaporisation during core-concrete interactions

International Nuclear Information System (INIS)

Raymond, D.P.; Clough, P.N.

1989-09-01

Heterogeneous reactions may cause enhanced release of radionuclides during the core-concrete interaction (CCl) stage of a PWR severe accident. The VANESA computer code models these CCI releases using chemical equilibrium assumptions; however, the possibility that chemical kinetics could prevent equilibrium from being achieved is considered in this report. Direct experimental evidence is lacking on these reactions. Therefore, some analogues studies are reviewed, including examples of Eyring's surface reaction rate theory; sequential vaporisation-oxidation processes; iron and steelmaking chemistry; radionuclide evaporation from solid UO 2 . This circumstantial evidence appeared to agree with the current assumptions, in VANESA and some UK modelling studies, that mass transfer, rather than chemical kinetics will limit the rate at which equilibrium is attained. (author)

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.

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

Energy Technology Data Exchange (ETDEWEB)

Peters, Catherine A

2013-02-28

mineral accessible surface area, and should not be used in reactive transport modeling. Our work showed that reaction rates would be overestimated by three to five times.

CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

Directory of Open Access Journals (Sweden)

P.P.Kostrobii

2003-01-01

Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

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.

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

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.

Cheap but accurate calculation of chemical reaction rate constants from ab initio data, via system-specific, black-box force fields.

Science.gov (United States)

Steffen, Julien; Hartke, Bernd

2017-10-28

Building on the recently published quantum-mechanically derived force field (QMDFF) and its empirical valence bond extension, EVB-QMDFF, it is now possible to generate a reliable potential energy surface for any given elementary reaction step in an essentially black box manner. This requires a limited and pre-defined set of reference data near the reaction path and generates an accurate approximation of the reference potential energy surface, on and off the reaction path. This intermediate representation can be used to generate reaction rate data, with far better accuracy and reliability than with traditional approaches based on transition state theory (TST) or variational extensions thereof (VTST), even if those include sophisticated tunneling corrections. However, the additional expense at the reference level remains very modest. We demonstrate all this for three arbitrarily chosen example reactions.

Evaluation of surface dose rate on C-14 scrubber and gas bag

International Nuclear Information System (INIS)

Gang, D. W.; Lee, H. S.; Lee, D. H.

2003-01-01

In CANDU(Canadian Deuterium Uranium) reactors, purge and discharge of moderator cover gas has been performed via vapor recovery system. The methods employed in C-14 removal are mainly based on reactions of CO 2 with absorber of adsorbent. In order to choose an optimum process, we should consider the characteristics of the process, such as, temperature, pressure, humidity etc. and surface dose rate on C-14 scrubber and gas bag to estimate job-related personnel doses. Assuming that the whole C-14 scrubber was completely replaced after one-cycle operation, and that its C-14 activity for one-cycle operation was 40 mCi, we calculated the surface dose rate at the six points of the C-14 scrubber. This calculation showed that the dose rate on the surface of cartridge was only 1.25μSυ/hγ because of low energy of β ray. It is concluded, therefore, that the cartridge change-out is safe because the operation of C-14 removal system causes only a small increase in dose rate

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

International Nuclear Information System (INIS)

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

2017-01-01

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

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.)

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.

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.

The chemistry of the carbothermal synthesis of β-SiC : reaction mechanism, reaction rate and grain growth

NARCIS (Netherlands)

van Dijen, F.K.; Metselaar, R.

1991-01-01

Evidence is given that in the present case the reaction mechanism of ß-SiC formation from silica and carbon is a direct solid-state reaction in which silica migrates over the silicon carbide surface to the carbon. A high value (440 kJ/mol) of activation energy is obtained for this reaction. This

Self-activated, self-limiting reactions on Si surfaces

DEFF Research Database (Denmark)

Morgen, Per; Hvam, Jeanette; Bahari, Ali

The direct thermally activated reactions of oxygen and ammonia with Si surfaces in furnaces have been used for a very long time in the semiconductor industry for the growth of thick oxides and nitride layers respectively. The oxidation mechanism was described in the Deal-Grove model as a diffusion...... mechanism for the direct growth of ultrathin films (0-3 nm) of oxides and nitrides under ultrahigh vacuum conditions. Neutral oxygen and a microwave excited nitrogen plasma interact directly with Si surfaces kept at different temperatures during the reaction. The gas pressures are around 10-6 Torr...... energy of an oxide system, which happened for an ordered structure, at a thickness of 0.7-0.8 nm. Thus this thin oxide structure has definite crystalline features. We have closely monitored the reaction kinetics with normal x-ray induced photoelectron spectroscopies, and also the structure, composition...

A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters.

Science.gov (United States)

Ciampi, Simone; Guan, Bin; Darwish, Nadim A; Zhu, Ying; Reece, Peter J; Gooding, J Justin

2012-12-21

Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.

Chemical Reactions at Surfaces. Final Progress Report

Energy Technology Data Exchange (ETDEWEB)

Freud, Hans-Joachim [Max-Planck-Gesellschaft, Berlin (Germany). Fritz-Haber-Inst.

2003-02-21

The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

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.

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.

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

Adsorption and surface reaction of bis-diethylaminosilane as a Si precursor on an OH-terminated Si (0 0 1) surface

International Nuclear Information System (INIS)

Baek, Seung-Bin; Kim, Dae-Hee; Kim, Yeong-Cheol

2012-01-01

The adsorption and the surface reaction of bis-diethylaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 , BDEAS) as a Si precursor on an OH-terminated Si (0 0 1) surface were investigated to understand the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory. The bond dissociation energies between two atoms in BDEAS increased in the order of Si-H, Si-N, and the rest of the bonds. Therefore, the relatively weak Si-H and Si-N bonds were considered for bond breaking during the surface reaction. Optimum locations of BDEAS for the Si-H and Si-N bond breaking were determined on the surface, and adsorption energies of 0.43 and 0.60 eV, respectively, were obtained. The Si-H bond dissociation energy of the adsorbed BDEAS on the surface did not decrease, so that a high reaction energy barrier of 1.60 eV was required. On the other hand, the Si-N bond dissociation energy did decrease, so that a relatively low reaction energy barrier of 0.52 eV was required. When the surface reaction energy barrier was higher than the adsorption energy, BDEAS would be desorbed from the surface instead of being reacted. Therefore, the Si-N bond breaking would be dominantly involved during the surface reaction, and the result is in good agreement with the experimental data in the literature.

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.

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

Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

International Nuclear Information System (INIS)

Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

2011-01-01

The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

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)

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

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.

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)

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

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

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

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

First-Principles Computed Rate Constant for the O + O2 Isotopic Exchange Reaction Now Matches Experiment.

Science.gov (United States)

Guillon, Grégoire; Honvault, Pascal; Kochanov, Roman; Tyuterev, Vladimir

2018-04-19

We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18 O + 32 O 2 , motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three research domains, advanced electronic structure calculations, ultrasensitive spectroscopy, and quantum scattering calculations, has therefore permitted a breakthrough in the theoretical modeling of this crucial collision process from first principles.

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

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.)

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.

Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to H + CH(4) H(2) + CH(3).

Science.gov (United States)

Banks, Simon T; Clary, David C

2009-01-14

We consider the general problem of vibrational analysis at nonglobally optimized points on a reduced dimensional reaction surface. We discuss the importance of the use of curvilinear internal coordinates to describe molecular motion and derive a curvilinear projection operator to remove the contribution of nonzero gradients from the Hessian matrix. Our projection scheme is tested in the context of a two-dimensional quantum scattering calculation for the reaction H + CH(4) --> H(2) + CH(3) and its reverse H(2) + CH(3) --> H + CH(4). Using zero-point energies calculated via rectilinear and curvilinear projections we construct two two-dimensional, adiabatically corrected, ab initio reaction surfaces for this system. It is shown that the use of curvilinear coordinates removes unphysical imaginary frequencies observed with rectilinear projection and leads to significantly improved thermal rate constants for both the forward and reverse reactions.

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)

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

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

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…

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

Nonmonotonic Temperature Dependence of the Pressure-Dependent Reaction Rate Constant and Kinetic Isotope Effect of Hydrogen Radical Reaction with Benzene Calculated by Variational Transition-State Theory.

Science.gov (United States)

Zhang, Hui; Zhang, Xin; Truhlar, Donald G; Xu, Xuefei

2017-11-30

The reaction between H and benzene is a prototype for reactions of radicals with aromatic hydrocarbons. Here we report calculations of the reaction rate constants and the branching ratios of the two channels of the reaction (H addition and H abstraction) over a wide temperature and pressure range. Our calculations, obtained with an accurate potential energy surface, are based on variational transition-state theory for the high-pressure limit of the addition reaction and for the abstraction reaction and on system-specific quantum Rice-Ramsperger-Kassel theory calibrated by variational transition-state theory for pressure effects on the addition reaction. The latter is a very convenient way to include variational effects, corner-cutting tunneling, and anharmonicity in falloff calculations. Our results are in very good agreement with the limited experimental data and show the importance of including pressure effects in the temperature interval where the mechanism changes from addition to abstraction. We found a negative temperature effect of the total reaction rate constants at 1 atm pressure in the temperature region where experimental data are missing and accurate theoretical data were previously missing as well. We also calculated the H + C 6 H 6 /C 6 D 6 and D + C 6 H 6 /C 6 D 6 kinetic isotope effects, and we compared our H + C 6 H 6 results to previous theoretical data for H + toluene. We report a very novel nonmonotonic dependence of the kinetic isotope effect on temperature. A particularly striking effect is the prediction of a negative temperature dependence of the total rate constant over 300-500 K wide temperature ranges, depending on the pressure but generally in the range from 600 to 1700 K, which includes the temperature range of ignition in gasoline engines, which is important because aromatics are important components of common fuels.

Reaction of ethane with deuterium over platinum(111) single-crystal surfaces

International Nuclear Information System (INIS)

Zaera, F.; Somorhai, G.A.

1985-01-01

Deuterium exchange and hydrogenolysis of ethane were studied over (111) platinum surfaces under atmospheric pressures and a temperature range of 475-625 K. Activation energies of 19 kcal/mol for exchange and 34 kcal/mol for hydrogenolysis were obtained. The exchange reaction rates displayed kinetic orders with respect to deuterium and ethane partial pressures of -0.55 and 1.2, respectively. The exchange production distribution was U-shaped, peaking at one and six deuterium atoms per ethane molecule, similar to results reported for other forms of platinum, e.g., supported, films, and foils. The pressure of ethylidyne moieties on the surface was inferred from low-energy electron diffraction and thermal desorption spectroscopy. A mechanism is proposed to explain the experimental results, in which ethylidyne constitutes an intermediate in one of two competitive pathways. 31 references, 9 figures, 3 tables

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

Surface applicators for high dose rate brachytherapy in AIDS-related kaposi's sarcoma

International Nuclear Information System (INIS)

Evans, Michael D.C.; Yassa, Mariam; Podgorsak, Ervin B.; Roman, Ted N.; Schreiner, L. John; Souhami, Luis

1997-01-01

Purpose: The development of commercially available surface applicators using high dose rate remote afterloading devices has enabled radiotherapy centers to treat selected superficial lesions using a remote afterloading brachytherapy unit. The dosimetric parameters of these applicators, the clinical implementation of this technique, and a review of the initial patient treatment regimes are presented. Methods and Materials: A set of six fixed-diameter (1, 2, and 3 cm), tungsten/steel surface applicators is available for use with a single stepping-source (Ir-192, 370 GBq) high dose rate afterloader. The source can be positioned either in a parallel or perpendicular orientation to the treatment plane at the center of a conical aperture that sits at an SSD of approximately 15 mm and is used with a 1-mm thick removable plastic cap. The surface dose rates, percent depth dose, and off-axis ratios were measured. A custom-built, ceiling-mounted immobilization device secures the applicator on the surface of the patient's lesion during treatment. Results: Between November 1994, and September 1996, 16 AIDS-related Kaposi's sarcoma patients having a total of 120 lesions have been treated with palliative intent. Treatment sites were distributed between the head and neck, extremity, and torso. Doses ranged from 8 to 20 Gy, with a median dose of 10 Gy delivered in a single fraction. Treatments were well tolerated with minimal skin reaction, except for patients with lesions treated to 20 Gy who developed moderate/severe desquamation. Conclusion: Radiotherapy centers equipped with a high dose rate remote afterloading unit may treat small selected surface lesions with commercially available surface applicators. These surface applicators must be used with a protective cap to eliminate electron contamination. The optimal surface dose appears to be either 10 or 15 Gy depending upon the height of the lesion

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.)

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....

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

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

Science.gov (United States)

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

2018-01-01

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

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.

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.)

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)

One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

Energy Technology Data Exchange (ETDEWEB)

Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J., E-mail: lwebb@cm.utexas.edu

2017-02-01

Highlights: • One-pot synthesis of α-helical-terminated self-assembled monolayers on Au(111). • Synthesis of high density, structured, and covalently bound α-helices on Au(111). • Characterization by surface-averaged and single molecule techniques. • Peptide-terminated surfaces for fabrication of biomaterials and sensors. - Abstract: The Huisgen cycloaddition reaction (“click” chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

Photocatalytic surface reactions on indoor wall paint.

Science.gov (United States)

Salthammer, T; Fuhrmann, F

2007-09-15

The reduction of indoor air pollutants by air cleaning systems has received considerable interest, and a number of techniques are now available. So far, the method of photocatalysis was mainly applied by use of titanium dioxide (TiO2) in flow reactors under UV light of high intensity. Nowadays, indoor wall paints are equipped with modified TiO2 to work as a catalyst under indoor daylight or artificial light. In chamber experiments carried out under indoor related conditions itwas shown thatthe method works for nitrogen dioxide with air exchange and for formaldehyde without air exchange at high concentrations. In further experiments with volatile organic compounds (VOCs), a small effect was found for terpenoids with high kOH rate constants. For other VOCs and carbon monoxide there was no degradation at all or the surface acted as a reversible sink. Secondary emissions from the reaction of paint constituents were observed on exposure to light. From the results it is concluded that recipes of photocatalytic wall paints need to be optimized for better efficiency under indoor conditions.

Exploring Reaction Mechanism on Generalized Force Modified Potential Energy Surfaces (G-FMPES) for Diels-Alder Reaction

Science.gov (United States)

Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

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.

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.

Time-Dependent Quantum Wave Packet Study of the Si + OH → SiO + H Reaction: Cross Sections and Rate Constants.

Science.gov (United States)

Rivero Santamaría, Alejandro; Dayou, Fabrice; Rubayo-Soneira, Jesus; Monnerville, Maurice

2017-03-02

The dynamics of the Si( 3 P) + OH(X 2 Π) → SiO(X 1 Σ + ) + H( 2 S) reaction is investigated by means of the time-dependent wave packet (TDWP) approach using an ab initio potential energy surface recently developed by Dayou et al. ( J. Chem. Phys. 2013 , 139 , 204305 ) for the ground X 2 A' electronic state. Total reaction probabilities have been calculated for the first 15 rotational states j = 0-14 of OH(v=0,j) at a total angular momentum J = 0 up to a collision energy of 1 eV. Integral cross sections and state-selected rate constants for the temperature range 10-500 K were obtained within the J-shifting approximation. The reaction probabilities display highly oscillatory structures indicating the contribution of long-lived quasibound states supported by the deep SiOH/HSiO wells. The cross sections behave with collision energies as expected for a barrierless reaction and are slightly sensitive to the initial rotational excitation of OH. The thermal rate constants show a marked temperature dependence below 200 K with a maximum value around 15 K. The TDWP results globally agree with the results of earlier quasi-classical trajectory (QCT) calculations carried out by Rivero-Santamaria et al. ( Chem. Phys. Lett. 2014 , 610-611 , 335 - 340 ) with the same potential energy surface. In particular, the thermal rate constants display a similar temperature dependence, with TDWP values smaller than the QCT ones over the whole temperature range.

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

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045 (United States)

2016-06-15

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

International Nuclear Information System (INIS)

Nguyen, Luan; Tao, Franklin

2016-01-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

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.

Application of atomic mutations included in nuclear reactions, 40Ar(γ, p)39Cl(β decay)39Ar, to surface study

International Nuclear Information System (INIS)

Ohkuma, Juzo

1987-01-01

It has been found that the nuclear transformation processes which are initiated by photonuclear reactions can be used for studying the adsorption and chemical reactions taking place on solid surfaces. Chemically reactive 39 Cl was produced by irradiating 40 Ar with high-energy bremsstrahlung, and its blow was directed onto several material surfaces. The amount of chlorine adsorption was ascertained by detecting its radioactivity. Desorption without heating the adsorber samples inevitably occurred owing to the nuclear decay of 39 Cl. The adsorption and desorption rates were compared for several elements. A fast growth of oxide islands on sample surfaces was observed during the adsorption-desorption process. (author)

Surface reactivity and layer analysis of chemisorbed reaction films in ...

Indian Academy of Sciences (India)

Administrator

Surface reactivity and layer analysis of chemisorbed reaction films in ... in the nitrogen environment. Keywords. Surface reactivity ... sium (Na–K) compounds in the coating or core of the ..... Barkshire I R, Pruton M and Smith G C 1995 Appl. Sur.

Ab initio calculation of transition state normal mode properties and rate constants for the H(T)+CH4(CD4) abstraction and exchange reactions

International Nuclear Information System (INIS)

Schatz, G.C.; Walch, S.P.; Wagner, A.F.

1980-01-01

We present ab initio (GVB--POL--CI) calculations for enough of the region about the abstraction and exchange saddle points for H(T)+CH 4 (CD 4 ) to perform a full normal mode analysis of the transition states. The resulting normal mode frequencies are compared to four other published surfaces: an ab initio UHF--SCF calculation by Carsky and Zahradnik, a semiempirical surface by Raff, and two semiempirical surfaces by Kurylo, Hollinden, and Timmons. Significant quantitative and qualitative differences exist between the POL--CI results and those of the other surfaces. Transition state theory rate constants and vibrationally adiabatic reaction threshold energies were computed for all surfaces and compared to available experimental values. For abstraction, the POL--CI rates are in good agreement with experimental rates and in better agreement than are the rates of any of the other surfaces. For exchange, uncertainties in the experimental values and in the importance of vibrationally nonadiabatic effects cloud the comparison of theory to experiment. Tentative conclusions are that the POL--CI barrier is too low by several kcal. Unless vibrationaly nonadiabatic effects are severe, the POL--CI surface is still in better agreement with experiment than are the other surfaces. The rates for a simple 3-atom transition state theory model (where CH 3 is treated as an atom) are compared to the rates for the full 6-atom model. The kinetic energy coupling of reaction coordinate modes to methyl group modes is identified as being of primary importance in determining the accuracy of the 3-atom model for this system. Substantial coupling in abstraction, but not exchange, causes the model to fail for abstraction but succeed for exchange

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.

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 ...

Surface Defect Passivation and Reaction of c-Si in H2S.

Science.gov (United States)

Liu, Hsiang-Yu; Das, Ujjwal K; Birkmire, Robert W

2017-12-26

A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H 2 S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τ eff ) of >2000 μs corresponding to a surface recombination velocity of passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H 2 O and O 2 . This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

Neural network approach to time-dependent dividing surfaces in classical reaction dynamics

Science.gov (United States)

Schraft, Philippe; Junginger, Andrej; Feldmaier, Matthias; Bardakcioglu, Robin; Main, Jörg; Wunner, Günter; Hernandez, Rigoberto

2018-04-01

In a dynamical system, the transition between reactants and products is typically mediated by an energy barrier whose properties determine the corresponding pathways and rates. The latter is the flux through a dividing surface (DS) between the two corresponding regions, and it is exact only if it is free of recrossings. For time-independent barriers, the DS can be attached to the top of the corresponding saddle point of the potential energy surface, and in time-dependent systems, the DS is a moving object. The precise determination of these direct reaction rates, e.g., using transition state theory, requires the actual construction of a DS for a given saddle geometry, which is in general a demanding methodical and computational task, especially in high-dimensional systems. In this paper, we demonstrate how such time-dependent, global, and recrossing-free DSs can be constructed using neural networks. In our approach, the neural network uses the bath coordinates and time as input, and it is trained in a way that its output provides the position of the DS along the reaction coordinate. An advantage of this procedure is that, once the neural network is trained, the complete information about the dynamical phase space separation is stored in the network's parameters, and a precise distinction between reactants and products can be made for all possible system configurations, all times, and with little computational effort. We demonstrate this general method for two- and three-dimensional systems and explain its straightforward extension to even more degrees of freedom.

The Effectiveness of Surface Coatings on Preventing Interfacial Reaction During Ultrasonic Welding of Aluminum to Magnesium

Science.gov (United States)

Panteli, Alexandria; Robson, Joseph D.; Chen, Ying-Chun; Prangnell, Philip B.

2013-12-01

High power ultrasonic spot welding (USW) is a solid-state joining process that is advantageous for welding difficult dissimilar material couples, like magnesium to aluminum. USW is also a useful technique for testing methods of controlling interfacial reaction in welding as the interface is not greatly displaced by the process. However, the high strain rate deformation in USW has been found to accelerate intermetallic compound (IMC) formation and a thick Al12Mg17 and Al3Mg2 reaction layer forms after relatively short welding times. In this work, we have investigated the potential of two approaches for reducing the IMC reaction rate in dissimilar Al-Mg ultrasonic welds, both involving coatings on the Mg sheet surface to (i) separate the join line from the weld interface, using a 100- μm-thick Al cold spray coating, and (ii) provide a diffusion barrier layer, using a thin manganese physical vapor deposition (PVD) coating. Both methods were found to reduce the level of reaction and increase the failure energy of the welds, but their effectiveness was limited due to issues with coating attachment and survivability during the welding cycle. The effect of the coatings on the joint's interface microstructure, and the fracture behavior have been investigated in detail. Kinetic modeling has been used to show that the benefit of the cold spray coating can be attributed to the reaction rate reverting to that expected under static conditions. This reduces the IMC growth rate by over 50 pct because at the weld line, the high strain rate dynamic deformation in USW normally enhances diffusion through the IMC layer. In comparison, the thin PVD barrier coating was found to rapidly break up early in USW and become dispersed throughout the deformation layer reducing its effectiveness.

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.

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.

[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.

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

An investigation of the effect of pore scale flow on average geochemical reaction rates using direct numerical simulation

Energy Technology Data Exchange (ETDEWEB)

Molins, Sergi [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division; Trebotich, David [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Steefel, Carl I. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division; Shen, Chaopeng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division

2012-03-30

The scale-dependence of geochemical reaction rates hinders their use in continuum scale models intended for the interpretation and prediction of chemical fate and transport in subsurface environments such as those considered for geologic sequestration of CO₂. Processes that take place at the pore scale, especially those involving mass transport limitations to reactive surfaces, may contribute to the discrepancy commonly observed between laboratory-determined and continuum-scale or field rates. In this study we investigate the dependence of mineral dissolution rates on the pore structure of the porous media by means of pore scale modeling of flow and multicomponent reactive transport. The pore scale model is composed of high-performance simulation tools and algorithms for incompressible flow and conservative transport combined with a general-purpose multicomponent geochemical reaction code. The model performs direct numerical simulation of reactive transport based on an operator-splitting approach to coupling transport and reactions. The approach is validated with a Poiseuille flow single-pore experiment and verified with an equivalent 1-D continuum-scale model of a capillary tube packed with calcite spheres. Using the case of calcite dissolution as an example, the high-resolution model is used to demonstrate that nonuniformity in the flow field at the pore scale has the effect of decreasing the overall reactivity of the system, even when systems with identical reactive surface area are considered. In conclusion, the effect becomes more pronounced as the heterogeneity of the reactive grain packing increases, particularly where the flow slows sufficiently such that the solution approaches equilibrium locally and the average rate becomes transport-limited.

Effects of combined radiation-burn injury on survival rate of allogeneic skin grafts and immune reaction in rats

International Nuclear Information System (INIS)

Ran Xinze; Yan Yongtang; Cheng Tianmin; Li Yuan; Wei Shuqing

1996-01-01

The effects of combined radiation-burn injury on survival rate of allogeneic skin grafts and immune reaction were studied in rats with combined injury of 3-8 Gy 60 Co γ-ray irradiation plus 15% total body surface area full thickness burn induced by exposure to a 5 kw bromotungsten lamp. The allogeneic skin was transplanted 24 hours after injury. It was found that all the skin grafts failed to survive in 10 days and the immune reaction significantly increased in the early stage of burn injury. But the immune reaction was obviously suppressed by the combined radiation-burn injury. The survival rates of skin grafts were 20% and 30% in the combined injury of burn plus 3 and 4 Gy irradiation respectively. When the radiation doses increased to 5,6 and 8 Gy, the survival rates elevated to 69%, 88% and 100% respectively (in the group of 8 Gy, bone marrow transplantation was conducted before receiving skin graft). At day 30 post-transplantation the survival rates were still 36%, 42% and 100% respectively. Compared with burn group, there was a significant difference in survival rate when the radiation doses were higher than 5 Gy. These results indicate that the survival rate of the allogeneic skin graft increases concurrently with the increase in radiation dose and decreases with the elapse of the post-transplantation time

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

Science.gov (United States)

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

Pulsed laser-assisted focused electron-beam-induced etching of titanium with XeF2: enhanced reaction rate and precursor transport.

Science.gov (United States)

Noh, J H; Fowlkes, J D; Timilsina, R; Stanford, M G; Lewis, B B; Rack, P D

2015-02-25

In order to enhance the etch rate of electron-beam-induced etching, we introduce a laser-assisted focused electron-beam-induced etching (LA-FEBIE) process which is a versatile, direct write nanofabrication method that allows nanoscale patterning and editing. The results demonstrate that the titanium electron stimulated etch rate via the XeF2 precursor can be enhanced up to a factor of 6 times with an intermittent pulsed laser assist. The evolution of the etching process is correlated to in situ stage current measurements and scanning electron micrographs as a function of time. The increased etch rate is attributed to photothermally enhanced Ti-F reaction and TiF4 desorption and in some regimes enhanced XeF2 surface diffusion to the reaction zone.

Reactions of BBr(n)(+) (n = 0--2) at fluorinated and hydrocarbon self-assembled monolayer surfaces: observations of chemical selectivity in ion--surface scattering.

Science.gov (United States)

Wade, N; Shen, J; Koskinen, J; Cooks, R G

2001-07-01

Ion-surface reactions involving BBr(n)(+) (n = 0--2) with a fluorinated self-assembled monolayer (F-SAM) surface were investigated using a multi-sector scattering mass spectrometer. Collisions of the B(+) ion yield BF(2)(+) at threshold energy with the simpler product ion BF(+)* appearing at higher collision energies and remaining of lower abundance than BF(2)(+) at all energies examined. In addition, the reactively sputtered ion CF(+) accompanies the formation of BF(2)(+) at low collision energies. These results stand in contrast with previous data on the ion-surface reactions of atomic ions with the F-SAM surface in that the threshold and most abundant reaction products in those cases involved the abstraction of a single fluorine atom. Gas-phase enthalpy data are consistent with BF(2)(+) being the thermodynamically favored product. The fact that the abundance of BF(2)(+) is relatively low and relatively insensitive to changes in collision energy suggests that this reaction proceeds through an entropically demanding intermediate at the vacuum--surface interface, one which involves interaction of the B(+) ion simultaneously with two fluorine atoms. By contrast with the reaction of B(+), the odd-electron species BBr(+)* reacts with the F-SAM surface to yield an abundant single-fluorine abstraction product, BBrF(+). Corresponding gas-phase ion--molecule experiments involving B(+) and BBr(+)* with C(6)F(14) also yield the products BF(+)* and BF(2)(+), but only in extremely low abundances and with no preference for double fluorine abstraction. Ion--surface reactions were also investigated for BBr(n)(+) (n = 0-2) with a hydrocarbon self-assembled monolayer (H-SAM) surface. Reaction of the B(+) ion and dissociative reactions of BBr(+)* result in the formation of BH(2)(+), while the thermodynamically less favorable product BH(+)* is not observed. Collisions of BBr(2)(+) with the H-SAM surface yield the dissociative ion-surface reaction products, BBrH(+) and BBrCH(3

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.

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

Vibrational Mode-Specific Reaction of Methane on a Nickel Surface

Science.gov (United States)

Beck, Rainer D.; Maroni, Plinio; Papageorgopoulos, Dimitrios C.; Dang, Tung T.; Schmid, Mathieu P.; Rizzo, Thomas R.

2003-10-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

Low-Temperature Experimental and Theoretical Rate Constants for the O(1D) + H2 Reaction.

Science.gov (United States)

Hickson, Kevin M; Suleimanov, Yury V

2017-03-09

In the present joint experimental and theoretical study, we report thermal rate constants for the O( 1 D) + H 2 reaction within the 50-300 K temperature range. Experimental kinetics measurements were performed using a continuous supersonic flow reactor coupled with pulsed laser photolysis for O( 1 D) production and pulsed laser-induced fluorescence in the vacuum ultraviolet wavelength range (VUV LIF) for O( 1 D) detection. Theoretical rate constants were obtained using the ring polymer molecular dynamics (RPMD) approach over the two lowest potential energy surfaces 1 1 A' and 1 1 A″, which possess barrierless and thermally activated energy profiles, respectively. Both the experimental and theoretical rate constants exhibit a weak temperature dependence. The theoretical results show the dominant role of the 1 1 A' ground state and that contribution of the 1 1 A″ excited state to the total thermal rate decreases dramatically at lower temperature. Agreement between the experimental and theoretical results is good, and the discrepancy does not exceed 25%. It is argued that these differences are likely to be due to nonadiabatic couplings between the 1 1 A' and 2 1 A' surfaces.

Comparisons of predicted steady-state levels in rooms with extended- and local-reaction bounding surfaces

Science.gov (United States)

Hodgson, Murray; Wareing, Andrew

2008-01-01

A combined beam-tracing and transfer-matrix model for predicting steady-state sound-pressure levels in rooms with multilayer bounding surfaces was used to compare the effect of extended- and local-reaction surfaces, and the accuracy of the local-reaction approximation. Three rooms—an office, a corridor and a workshop—with one or more multilayer test surfaces were considered. The test surfaces were a single-glass panel, a double-drywall panel, a carpeted floor, a suspended-acoustical ceiling, a double-steel panel, and glass fibre on a hard backing. Each test surface was modeled as of extended or of local reaction. Sound-pressure levels were predicted and compared to determine the significance of the surface-reaction assumption. The main conclusions were that the difference between modeling a room surface as of extended or of local reaction is not significant when the surface is a single plate or a single layer of material (solid or porous) with a hard backing. The difference is significant when the surface consists of multilayers of solid or porous material and includes a layer of fluid with a large thickness relative to the other layers. The results are partially explained by considering the surface-reflection coefficients at the first-reflection angles.

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…

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...

Quantum mechanical/molecular mechanical modeling finds Diels-Alder reactions are accelerated less on the surface of water than in water.

Science.gov (United States)

Thomas, Laura L; Tirado-Rives, Julian; Jorgensen, William L

2010-03-10

Quantum and molecular mechanics calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, "on water" conditions. The pure TIP4P water slab maintains the bulk density and hydrogen-bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5 A band with progressive diminution of the density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water; i.e., for the reaction with 1,4-naphthoquinone, the DeltaDeltaG(++) values relative to the gas phase are -3.6 and -7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and a dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5-1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface; e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of

Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

International Nuclear Information System (INIS)

Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

2002-01-01

Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy

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

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.

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.

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...

An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method

International Nuclear Information System (INIS)

Chen, Jun; Sun, Zhigang; Zhang, Dong H.

2015-01-01

A three dimensional potential energy surface for the F + H 2 → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2) Q ] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H 2 reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface

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.

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.

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

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

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

Science.gov (United States)

Bulut, Niyazi; Kłos, Jacek; Roncero, Octavio

2015-06-07

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

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

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.

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.

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.…

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

Investigations Of Surface-Catalyzed Reactions In A Mars Mixture

Science.gov (United States)

Dougherty, Max; Owens, W.; Meyers, J.; Fletcher, D. G.

2011-05-01

In the design of a thermal protection system (TPS) for a planetary entry vehicle, accurate modeling of the trajectory aero-heating poses a significant challenge owing to large uncertainties in chemical processes taking place at the surface. Even for surface-catalyzed reactions, which have been investigated extensively, there is no consensus on how they should be modeled; or, in some cases, on which reactions are likely to occur. Current TPS designs for Mars missions rely on a super-catalytic boundary condition, which assumes that all dissociated species recombine to the free stream composition.While this is recognized to be the the most conservative approach, discrepancies in aero-heating measurements in ground test facilities preclude less conservative design options, resulting in an increased TPS mass at the expense of scientific pay- load.Using two-photon absorption laser induced fluorescence in a 30 kW inductively coupled plasma torch facility, preliminary studies have been performed to obtain spatially-resolved measurements of the dominant species in a plasma boundary layer for a Martian atmosphere mixture over catalytic and non-catalytic surfaces.

A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

Science.gov (United States)

Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

2017-09-01

Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

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.

Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

Science.gov (United States)

Beck, Rainer

2004-03-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.

Dynamic weakening of serpentinite gouges and bare surfaces at seismic slip rates

Science.gov (United States)

Proctor, B. P.; Mitchell, T. M.; Hirth, G.; Goldsby, D.; Zorzi, F.; Platt, J. D.; Di Toro, G.

2014-11-01

To investigate differences in the frictional behavior between initially bare rock surfaces of serpentinite and powdered serpentinite ("gouge") at subseismic to seismic slip rates, we conducted single-velocity step and multiple-velocity step friction experiments on an antigorite-rich and lizardite-rich serpentinite at slip rates (V) from 0.003 m/s to 6.5 m/s, sliding displacements up to 1.6 m, and normal stresses (σn) up to 22 MPa for gouge and 97 MPa for bare surfaces. Nominal steady state friction values (μnss) in gouge at V = 1 m/s are larger than in bare surfaces for all σn tested and demonstrate a strong σn dependence; μnss decreased from 0.51 at 4.0 MPa to 0.39 at 22.4 MPa. Conversely, μnss values for bare surfaces remained ~0.1 with increasing σn and V. Additionally, the velocity at the onset of frictional weakening and the amount of slip prior to weakening were orders of magnitude larger in gouge than in bare surfaces. Extrapolation of the normal stress dependence for μnss suggests that the behavior of antigorite gouge approaches that of bare surfaces at σn ≥ 60 MPa. X-ray diffraction revealed dehydration reaction products in samples that frictionally weakened. Microstructural analysis revealed highly localized slip zones with melt-like textures in some cases gouge experiments and in all bare surfaces experiments for V ≥ 1 m/s. One-dimensional thermal modeling indicates that flash heating causes frictional weakening in both bare surfaces and gouge. Friction values for gouge decrease at higher velocities and after longer displacements than bare surfaces because strain is more distributed.

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

"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)

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

Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

International Nuclear Information System (INIS)

Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

1998-01-01

The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

An accurate potential energy surface for the F + H{sub 2} → HF + H reaction by the coupled-cluster method

Energy Technology Data Exchange (ETDEWEB)

Chen, Jun; Sun, Zhigang, E-mail: zsun@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn; Zhang, Dong H., E-mail: zsun@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

2015-01-14

A three dimensional potential energy surface for the F + H{sub 2} → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2){sub Q}] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H{sub 2} reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface.

Investigation of heterogeneous reactions of NO2 on aqueous surfaces

International Nuclear Information System (INIS)

Mertes, S.

1992-01-01

A microjet apparatus was developed for the purpose of measuring the loss in the gaseous phase and the uptake in the liquid phase of nitrogen on the basis of heterogeneous processes on a liquid surface. The measurements were to provide information on the mass accomodation coefficient α and on assumed surface reactions of NO 2 . (orig./BBR) [de

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.

Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

International Nuclear Information System (INIS)

Osborn, David L.

2017-01-01

Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

Science.gov (United States)

Osborn, David L.

2017-05-01

Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

Reaction of water vapor with a clean liquid uranium surface

International Nuclear Information System (INIS)

Siekhaus, W.

1985-01-01

To study the reaction of water vapor with uranium, we have exposed clean liquid uranium surfaces to H 2 O under UHV conditions. We have measured the surface concentration of oxygen as a function of exposure, and determined the maximum attainable surface oxygen concentration X 0 /sup s/ as a function of temperature. We have used these measurements to estimate, close to the melting point, the solubility of oxygen (X 0 /sup b/, -4 ) and its surface segregation coefficient β/sup s/(> 10 3 ). 8 refs., 5 figs., 1 tab

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.

Recyclable surfaces for amine conjugation chemistry via redox reaction

Energy Technology Data Exchange (ETDEWEB)

Choi, Inseong; Yeo, Woon Seok [Dept. of Bioscience and Biotechnology, Bio/Molecular Informatics Center, Konkuk University, Seoul (Korea, Republic of); Bae, Se Won [Green Materials and Process Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

2017-02-15

In this study, we extended this strategy to present a switchable surface that allows surface functionalization and removal of functional groups repeatedly. The substrate presenting a benzoquinone acid group is first used to immobilize with an amine-containing (bio)molecule using well-known conjugation chemistry. The benzoquinone group is then converted to the corresponding hydroquinone by treating with a reducing agent. We have described a strategy for the dynamic control of surface properties with recyclability via a simple reduction/ oxidation reaction. A stimuli-responsive quinone derivative was harnessed for the repeated immobilization and release of (bio)molecules, and thus, for the repeated dynamic change of the surface properties according to the characteristics of the immobilized (bio)molecules.

Reaction of [3H]-taurine maleimide with platelet surface thiols

International Nuclear Information System (INIS)

Karl, D.W.; Mills, D.C.B.

1986-01-01

Taurine Maleimide (2-maleimidoethanesulfonate, TM) was synthesized from [2- 3 H]-taurine and methoxycarbonylmaleimide (MCM). The yield of a 1 μmol synthesis approached 100% (based on taurine) when MCM was used in 4-fold excess. The product (TM*) was purified by ion exchange chromatography. TM* reacted irreversibly with thiol groups on the surface of washed human platelets, leading to incorporation of radioactivity into platelet pellets. Incorporation was blocked by cysteine, mercuribenzenesulfonate (MBS), dithiobisnitrobenzoate, and N-ethylmaleimide, but not by taurine or by inhibitors of anion transport. Reaction of TM* with platelets showed the dependence on time and concentration characteristics of a bimolecular reaction. The number of reactive sites ranged from 1 to 5 x 10 5 /platelet, and the apparent rate constant from 1 to 3 x 10 3 /(M x min). TM was less effective than MBS as an inhibitor of platelet aggregation induced by several agents. TM had no effect on the uptake of serotonin, taurine, or phosphate by the platelets, processes which are sensitive to MBS. These differences, considered with the similarity in size and charge of TM and MBS, suggest that classes of thiols defined as exofacial by their accessibility to MBS can differ substantially in their reactivity with other impermeant reagents

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

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.

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)

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

On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

Science.gov (United States)

Resende, S F; Oliveira, B S; Augusti, R

2018-06-21

On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe 2+ / H 2 O 2 ) and Fenton-like (M n+ / H 2 O 2 ; M n+ = Fe 3+ , Co 2+ , Cu 2+ , Mn 2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe 2+ /H 2 O 2 > H 2 O 2 > Cu 2+ /H 2 O 2 > M n+ / H 2 O 2 (M n+ = Fe 3+ , Co 2+ , Mn 2+ ) ~ M n+ (M n+ = Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , Mn 2 . The superior capability of Fe 2+ /H 2 O 2 in causing the degradation of sildenafil indicates that Fe 2+ efficiently decomposes H 2 O 2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H 2 O 2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, i. e. Fe 3+ , Co 2+ , Cu 2+ and Mn 2+ . A unique oxidation by-product was detected in the reaction between Fe 2+ /H 2 O 2 with sildenafil and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shown to be a convenient platform to promptly monitor on-surface oxidation reactions. This article is protected by copyright. All rights reserved.

Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.

Science.gov (United States)

Lyu, Beier; Cha, Wenli; Mao, Tingting; Wu, Yuanzi; Qian, Hujun; Zhou, Yitian; Chen, Xiuli; Zhang, Shen; Liu, Lanying; Yang, Guang; Lu, Zhongyuan; Zhu, Qiang; Ma, Hongwei

2015-03-25

Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.

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.

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.

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.

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)

Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

Science.gov (United States)

Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

2014-05-22

Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

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...

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.

Chemical reactions in the presence of surface modulation and stirring

OpenAIRE

Kamhawi, Khalid; Náraigh, Lennon Ó

2009-01-01

We study the dynamics of simple reactions where the chemical species are confined on a general, time-modulated surface, and subjected to externally-imposed stirring. The study of these inhomogeneous effects requires a model based on a reaction-advection-diffusion equation, which we derive. We use homogenization methods to show that up to second order in a small scaling parameter, the modulation effects on the concentration field are asymptotically equivalent for systems with or without stirri...

Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

Science.gov (United States)

Dulnee, Siriwan; Scheinost, Andreas C

2014-08-19

To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

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.

Rate equation for creatine kinase predicts the in vivo reaction velocity: 31P NMR surface coil studies in brain, heart, and skeletal muscle of the living rat

International Nuclear Information System (INIS)

Bittl, J.A.; DeLayre, J.; Ingwall, J.S.

1987-01-01

Brain, heart, and skeletal muscle contain four different creatine kinase isozymes and various concentrations of substrates for the creatine kinase reaction. To identify if the velocity of the creatine kinase reaction under cellular conditions is regulated by enzyme activity and substrate concentrations as predicted by the rate equation, the authors used 31 P NMR and spectrophotometric techniques to measure reaction velocity, enzyme content, isozyme distribution, and concentrations of substrates in brain, heart, and skeletal muscle of living rat under basal or resting conditions. The total tissue activity of creatine kinase in the direction of MgATP synthesis provided an estimate for V/sub max/ and exceeded the NMR-determined in vivo reaction velocities by an order of magnitude. The isozyme composition varied among the three tissues: >99% BB for brain; 14% MB, 61% MM, and 25% mitochondrial for heart; and 98% MM and 2% mitochondrial for skeletal muscle. The NMR-determined reaction velocities agreed with predicted values from the creatine kinase rate equation. The concentrations of free creatine and cytosolic MgADP, being less than or equal to the dissociation constants for each isozyme, were dominant terms in the creatine kinase rate equation for predicting the in vivo reaction velocity. Thus, they observed that the velocity of the creatine kinase reaction is regulated by total tissue enzyme activity and by the concentrations of creatine and MgADP in a manner that is independent of isozyme distribution

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

Rate of volcanism on Venus

International Nuclear Information System (INIS)

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

1988-07-01

The maintenance of the global H 2 SO 4 clouds on Venus requires volcanism to replenish the atmospheric SO 2 which is continually being removed from the atmosphere by reaction with calcium minerals on the surface of Venus. The first laboratory measurements of the rate of one such reaction, between SO 2 and calcite (CaCO 3 ) to form anhydrite (CaSO 4 ), are reported. If the rate of this reaction is representative of the SO 2 reaction rate at the Venus surface, then we estimate that all SO 2 in the Venus atmosphere (and thus the H 2 SO 4 clouds) will be removed in 1.9 million years unless the lost SO 2 is replenished by volcanism. The required rate of volcanism ranges from about 0.4 to about 11 cu km of magma erupted per year, depending on the assumed sulfur content of the erupted material. If this material has the same composition as the Venus surface at the Venera 13, 14 and Vega 2 landing sites, then the required rate of volcanism is about 1 cu km per year. This independent geochemically estimated rate can be used to determine if either (or neither) of the two discordant (2 cu km/year vs. 200 to 300 cu km/year) geophysically estimated rates is correct. The geochemically estimated rate also suggests that Venus is less volcanically active than the Earth

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.

Modeling Electric Double-Layers Including Chemical Reaction Effects

DEFF Research Database (Denmark)

Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

2014-01-01

A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...... for symmetric and asymmetric multi-species electrolytes and is not limited to a range of surface potentials. Numerical simulations are presented, for the case of a CaCO3 electrolyte solution in contact with a surface with rate-controlled protonation/deprotonation reactions. The surface charge and potential...... are determined by the surface reactions, and therefore they depends on the bulk solution composition and concentration...

Reaction path analysis of sodium-water reaction phenomena in support of chemical reaction model development

International Nuclear Information System (INIS)

Kikuchi, Shin; Ohshima, Hiroyuki; Hashimoto, Kenro

2011-01-01

Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule to the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. The results are used as the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by JAEA toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

Surface-induced dissociation and chemical reactions of C2D4(+) on stainless steel, carbon (HOPG), and two different diamond surfaces.

Science.gov (United States)

Feketeová, Linda; Zabka, Jan; Zappa, Fabio; Grill, Verena; Scheier, Paul; Märk, Tilmann D; Herman, Zdenek

2009-06-01

Surface-induced interactions of the projectile ion C(2)D(4)(+) with room-temperature (hydrocarbon covered) stainless steel, carbon highly oriented pyrolytic graphite (HOPG), and two different types of diamond surfaces (O-terminated and H-terminated) were investigated over the range of incident energies from a few eV up to 50 eV. The relative abundance of the product ions in dependence on the incident energy of the projectile ion [collision-energy resolved mass spectra, (CERMS) curves] was determined. The product ion mass spectra contained ions resulting from direct dissociation of the projectile ions, from chemical reactions with the hydrocarbons on the surface, and (to a small extent) from sputtering of the surface material. Sputtering of the surface layer by low-energy Ar(+) ions (5-400 eV) indicated the presence of hydrocarbons on all studied surfaces. The CERMS curves of the product ions were analyzed to obtain both CERMS curves for the products of direct surface-induced dissociation of the projectile ion and CERMS curves of products of surface reactions. From the former, the fraction of energy converted in the surface collision into the internal excitation of the projectile ion was estimated as 10% of the incident energy. The internal energy of the surface-excited projectile ions was very similar for all studied surfaces. The H-terminated room-temperature diamond surface differed from the other surfaces only in the fraction of product ions formed in H-atom transfer surface reactions (45% of all product ions formed versus 70% on the other surfaces).

Challenge for real-time and real-space resolved spectroscopy of surface chemical reactions. Aiming at trace of irreversible and inhomogeneous reactions

International Nuclear Information System (INIS)

Amemiya, Kenta

2015-01-01

A novel experimental technique, time-resolved wavelength-dispersive soft X-ray imaging spectroscopy, is proposed in order to achieve real-time and real-space resolved spectroscopy for the observation of irreversible and inhomogeneous surface chemical reactions. By combining the wavelength-dispersed soft X rays, in which the X-ray wavelength (photon energy) changes as a function of position on the sample, with the photoelectron emission microscope, the soft X-ray absorption spectra are separately obtained at different positions on the sample without scanning the X-ray monochromator. Therefore, the real-time resolved measurement of site-selective soft X-ray absorption spectroscopy is realized in one event without repeating the chemical reaction. It is expected that the spatial distribution of different chemical species is traced during the surface chemical reaction, which is essential to understand the reaction mechanism. (author)

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.

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.

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.

Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method

Energy Technology Data Exchange (ETDEWEB)

Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung

1978-09-01

The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.

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

The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

CSIR Research Space (South Africa)

Motsoeneng, RG

2015-09-01

Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

Field and laboratory emission cell automation and control system for investigating surface chemistry reactions

Science.gov (United States)

Flemmer, Michael M.; Ham, Jason E.; Wells, J. R.

2007-01-01

A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with α-terpineol on a vinyl surface over 72h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with α-terpineol were collected from both zero and 100ppb(partsper109) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100ppb (over 339h) provided a pooled standard deviation of 1.65ppb and a 95% tolerance of 3.3ppb. Humidity data from 17 experiments at 50% relative humidity (over 664h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300ml/min (over 548h) provided a pooled standard deviation of 3.02ml/min and a 95% tolerance range of 6.03ml/min. Initial experimental results yielded long term emissions of ozone/α-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.

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.)

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

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.

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

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)

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.

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.

Isotope exchange reaction in Li2ZrO3 packed bed

International Nuclear Information System (INIS)

Kawamura, Y.; Enoeda, M.; Okuno, K.

1998-01-01

To understand the release behavior of bred tritium in a solid breeder blanket, the tritium transfer rate and tritium inventory for various mass transfer processes should be investigated. The contribution of the surface reactions (adsorption, desorption and two kinds of isotope exchange reactions) to the release process cannot be ignored. It is believed that two kinds of isotope exchange reactions (gaseous hydrogen-tritiated water and water vapor-tritiated water) occur on the surface of the solid breeder materials when hydrogen is added to the sweep gas to enhance the tritium release rate. The isotope exchange reaction study in H-D systems was carried out using a Li 2 ZrO 3 packed bed. The exchange reaction between gaseous hydrogen and water was the rate controlling step among the two kinds of exchange reactions. The reaction rate constants were quantified, and experimental equations were proposed. The equilibrium constant of the isotope exchange reaction in the H-D system was obtained from experimental data and was found to be 1.17. (orig.)

Thermal rate coefficients in collinear versus bent transition state reactions: the N+N{sub 2} case study

Energy Technology Data Exchange (ETDEWEB)

Lagana, Antonio; Faginas Lago, Noelia; Rampino, Sergio [Dipartimento di Chimica, Universita di Perugia, 06123 Perugia (Italy); Huarte-Larranaga, FermIn [Computer Simulation and Modeling Lab (CoSMoLab), Parc CientIfic de Barcelona, 08028 Barcelona (Spain); GarcIa, Ernesto [Departamento de Quimica Fisica, Universidad del PaIs Vasco, 01006 Vitoria (Spain)], E-mail: lagana05@gmail.com, E-mail: fhuarte@pcb.ub.es, E-mail: e.garcia@ehu.es

2008-10-15

Zero total angular momentum exact quantum calculations of the probabilities of the N+N{sub 2} reaction have been performed on the L3 potential energy surface having a bent transition state. This has allowed us to work out J-shifting estimates of the thermal rate coefficient based on the calculation of either detailed (state-to-state) or cumulative (multiconfiguration) probabilities. The results obtained are used to compare the numerical outcomes and the concurrent computational machineries of both quantum and semiclassical approaches as well as to exploit the potentialities of the J-shifting model. The implications of moving the barrier to reaction from the previously proposed collinear geometry of the LEPS to the bent one of L3 are also investigated by comparing the related detailed reactive probabilities.

SENSMG: First-Order Sensitivities of Neutron Reaction Rates, Reaction-Rate Ratios, Leakage, k_eff, 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, k_eff, 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.

Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

National Research Council Canada - National Science Library

Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

2000-01-01

... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

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.)

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.

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)

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.

Surface chemical reactions induced by molecules electronically-excited in the gas

DEFF Research Database (Denmark)

Petrunin, Victor V.

2011-01-01

and alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... be readily produced. Products of chemical adsorption and/or chemical reactions induced within adsorbates are aggregated on the surface and observed by light scattering. We will demonstrate how pressure and spectral dependencies of the chemical outcomes, polarization of the light and interference of two laser...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis....

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.

Analysis of the Deposit Layer from Electrolyte Side Reaction on the Anode of the Pouch Type Lithium Ion Polymer Batteries: The Effect of State of Charge and Charge Rate

International Nuclear Information System (INIS)

Agubra, Victor A.; Fergus, Jeffrey W.; Fu, Rujian; Choe, Song-yul

2014-01-01

Highlights: • Raising the battery cycling potential increased the rate of side reaction. • Growth of deposit layer thickness at the electrode/electrolyte interface at high SOC. • A significant amount of lithium was consumed in forming the deposit layer. • Some of the lithium were “trapped” in the graphite after the discharge cycle. - Abstract: The formation of the solid electrolyte interface (SEI) layer on the surface of the anode electrode of a lithium ion battery prevents further electrolyte decomposition reaction. However, at certain battery operating conditions, the SEI breakdown leading to more electrolyte decomposition reactions that form several species on the anode electrode surface. This paper focuses on the effect of battery potential and charge rate on the decomposition side reaction on the anode electrode of a lithium ion polymer battery, as a result of the breakdown of the SEI layer. The results from this study indicate that raising the state of charge (SOC) increases the rate of the electrolyte decomposition side reaction that resulted in formation of a thick deposit layer at the electrolyte/electrolyte interface. This deposit layer contains lithium that can no longer participate in the reversible electrochemical reaction. In addition, at high cycling potential and charge rates the amount of lithium in the graphite after complete cell discharge increased due to the entrapment of lithium in the graphite. The amount of irreversible capacity loss for the batteries cycled at high potential and current correlates with the amount of trapped lithium in the graphite and the growth of the deposit layer thickness at the electrode/electrolyte interface

Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

Directory of Open Access Journals (Sweden)

Ashraf Khademzadeh

2014-01-01

Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

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.))

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 ...

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.

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.)

The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

Science.gov (United States)

Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

1993-01-01

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

Science.gov (United States)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

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

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.

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.

Corrosion of ferritic steels by molten lithium: Influence of competing thermal gradient mass transfer and surface product reactions

International Nuclear Information System (INIS)

Tortorelli, P.F.

1987-10-01

An Fe-12Cr-1MoVW steel was exposed to thermally convective lithium for 6962 h. Results showed that the weight change profile of Fe-12Cr-1MoVW steel changed substantially as the maximum loop temperature was raised from 500 to 600 0 C. Furthermore, for a particular loop experiment, changes in the structure and composition of the exposed surfaces did not reflect typical thermal gradient mass transfer effects for all elements: the surface concentration of chromium was often a maximum at intermediate temperatures, while nickel (present at low concentrations in the starting material) tended to be transported to the coldest part of the loop. Such data were interpreted in terms of a qualitative model in which there are different dominant reactions or the various constituents of the ferritic steels (surface product formation involving nitrogen and/or carbon and solubility-driven elemental transport). This competition among different reactions is important in evaluating overall corrosion behavior and the effects of temperature. The overall corrosion rate of the 12Cr-1MoVW steel was relatively low when compared to that for austenitic stainless steel exposed under similar conditions

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

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)

Enhancement of isotope exchange reactions over ceramic breeder material by deposition of catalyst metal

International Nuclear Information System (INIS)

Narisato, Y.; Munakata, K.; Koga, A.; Yokoyama, Y.; Takata, T.; Okabe, H.

2004-01-01

The deposition of catalyst metals in ceramic breeders could enhance the release rate of tritium due to the promotion of isotope exchange reactions taking place at the interface of the breeder surface and the sweep gas. In this work, the authors examined the effects of catalytic active metal deposited on lithium titanate on the isotope exchange reactions. With respect to the virgin lithium titanate, it was found that the rate of the isotope exchange reactions taking place on the surface is quite low. However, the deposition of palladium greatly increased the exchange reaction rate. The effect of the amounts of deposited palladium on the isotope exchange reaction rate was also investigated. The results indicate that the exchange reactions are still enhanced even if the amounts of deposited palladium are as low as 0.04%

Sequential charged particle reaction

International Nuclear Information System (INIS)

Hori, Jun-ichi; Ochiai, Kentaro; Sato, Satoshi; Yamauchi, Michinori; Nishitani, Takeo

2004-01-01

The effective cross sections for producing the sequential reaction products in F82H, pure vanadium and LiF with respect to the 14.9-MeV neutron were obtained and compared with the estimation ones. Since the sequential reactions depend on the secondary charged particles behavior, the effective cross sections are corresponding to the target nuclei and the material composition. The effective cross sections were also estimated by using the EAF-libraries and compared with the experimental ones. There were large discrepancies between estimated and experimental values. Additionally, we showed the contribution of the sequential reaction on the induced activity and dose rate in the boundary region with water. From the present study, it has been clarified that the sequential reactions are of great importance to evaluate the dose rates around the surface of cooling pipe and the activated corrosion products. (author)

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.

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.)

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.

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.

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.

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.

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

Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

Science.gov (United States)

He, Xin; Kim, Seong H

2018-02-20

Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

Surface photo reaction processes using synchrotron radiation; Hoshako reiki ni yoru hyomenko hanno process

Energy Technology Data Exchange (ETDEWEB)

Imaizumi, Y. [Tohoku University, Sendai (Japan). Institute for Materials Research; Yoshigoe, A. [Toyohashi University of Technology, Aichi (Japan); Urisu, T. [Toyohashi University of Technology, Aichi (Japan). Institute for Molecular Science

1997-08-20

This paper introduces the surface photo reaction processes using synchrotron radiation, and its application. A synchrotron radiation process using soft X-rays contained in electron synchrotron radiated light as an excited light source has a possibility of high-resolution processing because of its short wave length. The radiated light can excite efficiently the electronic state of a substance, and can induce a variety of photochemical reactions. In addition, it can excite inner shell electrons efficiently. In the aspect of its application, it has been found that, if radiated light is irradiated on surfaces of solids under fluorine-based reaction gas or Cl2, the surfaces can be etched. This technology is utilized practically. With regard to radiated light excited CVD process, it may be said that anything that can be deposited by the ordinary plasma CVD process can be deposited. Its application to epitaxial crystal growth may be said a nano processing application in thickness direction, such as forming an ultra-lattice structure, the application being subjected to expectation. In micromachine fabricating technologies, a possibility is searched on application of a photo reaction process of the radiated light. 5 refs., 6 figs.

Computerized infrared spectroscopic study of surface reactions on selected lanthanide oxides

International Nuclear Information System (INIS)

Dellisante, G.N.

1982-01-01

The natures of adsorption sites on La 2 O 3 , Nd 2 O 3 , and selected praseodymium oxides were investigated by examining surface reactions of probe molecules using computerized transmission ir spectroscopy on unsupported samples. Additionally, the rehydration/dehydration behavior and crystallographic phase transitions of these oxides were examined in pretreatment temperature experiments involving rehydration of the sesquioxides to hydroxides by water exposure. Following rehydration of La 2 O 3 to La(OH) 3 , the effect of increasing vacuum pretreatment temperature (350 to 1000 0 C) is to gradually remove surface hydroxyl and carbonate entities (up to 650 0 C), and increase the degree of A-type crystallinity. Increasing crystallinity causes a concomitant decrease in surface oxide basicity. The removal of hydroxyl and carbonate species, as well as increases in oxide basicity, strongly correlated to increases in certain catalytic activities. The adsorption of NH 3 , CO 2 , mixtures of NH 3 and CO 2 , formic acid, acetic acid, acetaldehyde, and ethanol on the oxides was determined to weakly coordinate in Ln 3 + sites, and the surface reactions are discussed. Heating was found to desorb the adsorbed compounds and/or causes changes of the originally adsorbed form into other compounds. The effects of temperature on both adsorption and desorption are reported

The effect of coadsorbed oxygen on the reaction of methanol on Rh(111) and on a rhodium/vanadium surface alloy

International Nuclear Information System (INIS)

Schennach, R.; Krenn, G.; Rendulic, K.D.

2002-01-01

Full text: Molecular adsorption of methanol can be observed on all transition metal surfaces at low temperatures. Methanol is adsorbed on Rh (111) at 98 K. With increasing methanol exposure first a mono-layer and then multi-layers of methanol are formed at this surface temperature. During heating, desorption of the methanol from physisorbed multi-layers is detected at about 120 K, followed by desorption of methanol from a chemisorbed mono-layer at 170 K. About 50 % of the adsorbed methanol undergoes a dehydrogenation reaction to form hydrogen and carbon monoxide adsorbed on the surface. These reaction products desorb at 300 K and 480 K, respectively. Less than 0.05 monolayers of coadsorbed oxygen increases the amount of methanol that reacts on the surface to about 80 %. Experiments using a Rh/V surface alloy were performed, in order to distinguish between steric and electronic effects in the adsorption and reaction processes. Deposition of 0.3 monolayers of V on the Rh (111) surface leads to the formation of a subsurface alloy, with V atoms in the second atomic layer only. The initial reaction probability was measured as a function of surface temperature and molecular beam energy. A marked difference was found between the two surfaces. On the clean surface methanol adsorption and reaction stops above 198 K, whereas on the alloy surface adsorption and subsequent reaction occurs up to 473 K. The effects of coadsorbed oxygen are similar on both surfaces. The results are discussed in terms of the possible reactions of the adsorbed methanol on the surface. (author)

Collisional Dissociation of CO: ab initio Potential Energy Surfaces and Quasiclassical Trajectory Rate Coefficients

Science.gov (United States)

Schwenke, David W.; Jaffe, Richard L.; Chaban, Galina M.

2016-01-01

We have generated accurate global potential energy surfaces for CO+Ar and CO+O that correlate with atom-diatom pairs in their ground electronic states based on extensive ab initio electronic structure calculations and used these potentials in quasi-classical trajectory nuclear dynamics calculations to predict the thermal dissociation rate coefficients over 5000- 35000 K. Our results are not compatible with the 20-45 year old experimental results. For CO + Ar we obtain fairly good agreement with the experimental rate coefficients of Appleton et al. (1970) and Mick and Roth (1993), but our computed rate coefficients exhibit a stronger temperature dependence. For CO + O our dissociation rate coefficient is in close agreement with the value from the Park model, which is an empirical adjustment of older experimental results. However, we find the rate coefficient for CO + O is only 1.5 to 3.3 times larger than CO + Ar over the temperature range of the shock tube experiments (8000-15,000 K). The previously accepted value for this rate coefficient ratio is 15, independent of temperature. We also computed the rate coefficient for the CO + O ex- change reaction which forms C + O2. We find this reaction is much faster than previously believed and is the dominant process in the removal of CO at temperatures up to 16,000 K. As a result, the dissociation of CO is accomplished in two steps (react to form C+O2 and then O2 dissociates) that are endothermic by 6.1 and 5.1 eV, instead of one step that requires 11.2 eV to break the CO bond.

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.

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

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

Energy Technology Data Exchange (ETDEWEB)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

2016-11-15

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

International Nuclear Information System (INIS)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

2016-01-01

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

Reaction Coordinate, Free Energy, and Rate of Intramolecular Proton Transfer in Human Carbonic Anhydrase II.

Science.gov (United States)

Paul, Sanjib; Paul, Tanmoy Kumar; Taraphder, Srabani

2018-03-22

The role of structure and dynamics of an enzyme has been investigated at three different stages of its function including the chemical event it catalyzes. A one-pot computational method has been designed for each of these stages on the basis of classical and/or quantum mechanical-molecular mechanical molecular dynamics and transition path sampling simulations. For a pair of initial and final states A and B separated by a high free-energy barrier, using a two-stage selection process, several collective variables (CVs) are identified that can delineate A and B. However, these CVs are found to exhibit strong cross-coupling over the transition paths. A set of mutually orthogonal order parameters is then derived from these CVs and an optimal reaction coordinate, r, determined applying half-trajectory likelihood maximization along with a Bayesian information criterion. The transition paths are also used to project the multidimensional free energy surface and barrier crossing dynamics along r. The proposed scheme has been applied to the rate-determining intramolecular proton transfer reaction of the well-known enzyme human carbonic anhydrase II. The potential of mean force, F( r), in the absence of the chemical step is found to reproduce earlier results on the equilibrium population of two side-chain orientations of key residue His-64. Estimation of rate constants, k, from mean first passage times for the three different stages of catalysis shows that the rate-determining step of intramolecular proton transfer occurs with k ≃ 1.0 × 10 6 s -1 , in close agreement with known experimental results.

Identifying Reaction Pathways and their Environments

DEFF Research Database (Denmark)

Maronsson, Jon Bergmann

Finding the mechanisms and estimating the rate of chemical reactions is an essential part of modern research of atomic scale systems. In this thesis, the application of well established methods for reaction rates and paths to important systems for hydrogen storage is considered before developing...... extensions to further identify the reaction environment for a more accurate rate. Complex borohydrides are materials of high hydrogen storage capacity and high thermodynamic stability (too high for hydrogen storage). In an effort to gain insight into the structural transitions of two such materials, Ca(BH4......-interstitial defects. In good agreement with the experiments, C3-type rotations activate at lower temperature than C2-type rotations. In order to investigate the environment of reaction pathways, a method for finding the ridge between first order saddle points on a multidimensional surface was developed...

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%

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.

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)

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.

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)

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

XPS study on the surface reaction of uranium metal in H2 and H2-CO atmospheres

International Nuclear Information System (INIS)

Wang Xiaolin; Fu Yibei; Xie Renshou

1996-04-01

The surface reactions of uranium metal in H 2 and H 2 -CO atmospheres and the effects of temperature and CO on the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between commercial H 2 and uranium metal at 25 degree C leads mainly to the further oxidation of surface layer of metal due to traces of water vapour. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing the exposure of H 2 . Investigation indicates CO inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmospheres. (13 refs., 10 figs.)

Mechanistic study of the isotopic-exchange reaction between gaseous hydrogen and palladium hydride powder

International Nuclear Information System (INIS)

Outka, D.A.; Foltz, G.W.

1991-01-01

A detailed mechanism for the isotopic-exchange reaction between gaseous hydrogen and solid palladium hydride is developed which extends previous model for this reaction by specifically including surface reactions. The modeling indicates that there are two surface-related processes that contribute to the overall rate of exchange: the desorption of hydrogen from the surface and the exchange between surface hydrogen and bulk hydrogen. This conclusion is based upon measurements examining the effect of small concentrations of carbon monoxide were helpful in elucidating the mechanism. Carbon monoxide reversibly inhibits certain steps in the exchange; this slows the overall rate of exchange and changes the distribution of products from the reactor

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].

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.

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

Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

International Nuclear Information System (INIS)

Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

2015-01-01

Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

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

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.

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...

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.

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.

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

Isotope exchange reaction on solid breeder materials

International Nuclear Information System (INIS)

Baba, A.; Nishikawa, M.; Eguchi, T.; Kawagoe, T.

2000-01-01

Lithium ceramic materials such as Li 2 O, LiAlO 2 , Li 2 ZrO 3 , Li 2 TiO 3 and Li 4 SiO 4 are considered to be as candidate for the tritium breeding material in a deuterium-tritium (D-T) fusion reactor. In the recent blanket designs, helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas to reduce tritium inventory and promote tritium release from the breeding material. In addition, the rate of isotope exchange reaction between hydrogen isotopes in the purge gas and tritium on the surface of the breeding material is necessary to analyze the tritium release behavior from the breeding materials. However, the rate of isotope exchange reactions between hydrogen isotopes in the purge gas and tritium on the surface of those materials has not been quantified until recently. Recently, the present authors quantified the rate of isotope exchange reaction on Li 2 O and Li 2 ZrO 3 . The overall mass transfer coefficients representing the isotope exchange reaction between H 2 and D 2 O on breeding materials or the same between D 2 and H 2 O are experimentally obtained in this study. Comparison to isotope exchange reaction rates on various breeding materials is also performed in this study. Discussions about the effects of temperature, concentration of hydrogen in the purge gas or flow rate of the purge gas on the conversion of tritiated water to tritium gas are also performed

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.

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

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

Waste dissolution with chemical reaction, diffusion and advection

International Nuclear Information System (INIS)

Chambre, P.L.; Kang, C.H.; Lee, W.W.L.; Pigford, T.H.

1987-06-01

This paper extends the mass-transfer analysis to include the effect of advective transport in predicting the steady-state dissolution rate, with a chemical-reaction-rate boundary condition at the surface of a waste form of arbitrary shape. This new theory provides an analytic means of predicting the ground-water velocities at which dissolution rate in a geologic environment will be governed entirely to the chemical reaction rate. As an illustration, we consider the steady-state potential flow of ground water in porous rock surrounding a spherical waste solid. 3 refs., 2 figs

Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

Science.gov (United States)

Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

2012-01-01

Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

Directory of Open Access Journals (Sweden)

Ziya Kalay

Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

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.