WorldWideScience

Sample records for surface reaction products

  1. Low Energy Nuclear Reaction Products at Surfaces

    Science.gov (United States)

    Nagel, David J.

    2008-03-01

    This paper examines the evidence for LENR occurring on or very near to the surface of materials. Several types of experimental indications for LENR surface reactions have been reported and will be reviewed. LENR result in two types of products, energy and the appearance of new elements. The level of instantaneous power production can be written as the product of four factors: (1) the total area of the surface on which the reactions can occur, (2) the fraction of the area that is active at any time, (3) the reaction rate, that is, the number of reactions per unit active area per second, and (4) the energy produced per reaction. Each of these factors, and their limits, are reviewed. A graphical means of relating these four factors over their wide variations has been devised. The instantaneous generation of atoms of new elements can also be written as the product of the first three factors and the new elemental mass produced per reaction. Again, a graphical means of presenting the factors and their results over many orders of magnitude has been developed.

  2. Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

    Science.gov (United States)

    Hopkins, Frances; Bell, Thomas; Yang, Mingxi

    2017-04-01

    Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

  3. Production of specific structured lipids by enzymatic interesterification: optimization of the reaction by response surface design

    DEFF Research Database (Denmark)

    Xu, Xuebing; Skands, Anja Rebecca Havegaard; Adler-Nissen, Jens

    1998-01-01

    Rapeseed oil and capric acid were interesterified in solvent-free media catalyzed by Lipozyme IM (Rhizomucor miehei) to produce specific-structured lipids (SSLs). The process was optimized by response surface design concerning the effects of acyl migration and the by-products of diacylglycerols...

  4. Assessment Of Surface-Catalyzed Reaction Products From High Temperature Materials In Plasmas

    Science.gov (United States)

    Allen, Luke Daniel

    Current simulations of atmospheric entry into both Mars and Earth atmospheres for the design of thermal protections systems (TPS) typically invoke conservative assumptions regarding surface-catalyzed recombination and the amount of energy deposited on the surface. The need to invoke such assumptions derives in part from lack of adequate experimental data on gas-surface interactions at trajectory relevant conditions. Addressing this issue, the University of Vermont's Plasma Test and Diagnostics Laboratory has done extensive work to measure atomic specie consumption by measuring the concentration gradient over various material surfaces. This thesis extends this work by attempting to directly diagnose molecular species production in air plasmas. A series of spectral models for the A-X and B-X systems of nitric oxide (NO), and the B-X system of boron monoxide (BO) have been developed. These models aim to predict line positions and strengths for the respective molecules in a way that is best suited for the diagnostic needs of the UVM facility. From the NO models, laser induced fluorescence strategies have been adapted with the intent of characterizing the relative quantity and thermodynamic state of NO produced bysurface-catalyzed recombination, while the BO model adds a diagnostic tool for the testing of diboride-based TPS materials. Boundary layer surveys of atomic nitrogen and NO have been carried out over water-cooled copper and nickel surfaces in air/argon plasmas. Translation temperatures and relative number densities throughout the boundary layer are reported. Additional tests were also conducted over a water-cooled copper surface to detect evidence of highly non-equilibrium effects in the form of excess population in elevated vibrational levels of the A-X system of NO. The tests showed that near the sample surface there is a much greater population in the upsilon'' = 1ground state than is predicted by a Boltzmann distribution.

  5. Colour and surface fluorescence development and their relationship with Maillard reaction markers as influenced by structural changes during cornflakes production.

    Science.gov (United States)

    Farroni, Abel; Buera, María Del Pilar

    2012-12-01

    The aim of this work was to study colour and surface fluorescence development in relation to the chemical markers for the Maillard reaction at the cooking, flaking and toasting stages of cornflake production process. Colour was measured by a calibrated computer vision system. Surface fluorescence was measured on compressed samples. Aqueous extracted Maillard reaction markers (hydroxymethylfurfural, carboxymethyl-lysine, absorbance at 420nm and total fluorescence) were measured on protease hydrolyzed samples. Sample microstructure was observed by scanning electron microscopy. During cooking the colour coordinates L(∗) and b(∗) decreased and a(∗) increased. After flaking, the samples appeared lighter, while the pigment concentration, fluorescence and hydroxymethylfurfural did not change. Toasting generated bubbles in the matrix and L(∗) apparently increased, although brown pigment concentration increased. Pigment concentration did not correlate with surface colour due to the destruction or generation of interfaces. Surface and microstructure effects can be avoided by milling and compressing the samples. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. 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

  7. Surface-Activated Coupling Reactions Confined on a Surface.

    Science.gov (United States)

    Dong, Lei; Liu, Pei Nian; Lin, Nian

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

  8. Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2011-01-01

    When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  9. Mass Spectral Investigation of Laboratory Made Tholins and Their Reaction Products: Implications to Tholin Surface Chemistry on Titan

    Science.gov (United States)

    Somogyi, Arpad; Smith, M. A.

    2006-09-01

    The success of the Huygens mission does not overshadow the importance of laboratory simulations of gas-phase and surface reactions that might occur in Titan's atmosphere and surface, respectively. We present here our latest results on chemical reactions (hydrolysis, peroxidation and hydrogenation) of laboratory made tholins obtained by FT-ICR mass spectrometry. The laboratory synthesis of tholins has been described in our earlier papers [1,2]. Overall, we conclude that our laboratory tholins are reactive materials that undergo fast hydrolysis, oxidation and reduction. Thus, if the tholin on Titan's surface resemble our laboratory made tholins, it can be considered as a potential starting material for several synthetic processes that can provide organic compounds of pre-biotic interest. Hydrolysis reactions occur with rate constants of 2-10 hour-1 at room temperature. Formal water addition to several species of CxHyNz has been observed by detecting the formation of CxHy+2NzO species. MS/MS fragmentation of the oxygen containing ions leads to the loss of water, ammonia, HCN, acetonitrile, etc. This suggests that tholin hydrolysis may occur in temporary melted ponds of water/ammonia ice on Titan. Peroxidation, which can be considered as a very harsh oxidation, leads to mono-, and multiple oxygenated compounds within a few minutes. The MS/MS fragmentation of these compounds suggests the presence of organic amides and, presumably, amino acid like compounds. Hydrogenation leads to compounds in which the originally present carbon-carbon or carbon-nitrogen double and triple bonds are saturated. H/D exchange experiments show different kinetics depending on the degree of unsaturation/saturation and the number of N atoms. [1] Sarker, N.; Somogyi, A.; Lunine, J. I.; Smith, M. A. Astrobiology, 2003, 3, 719-726. [2] Somogyi, A.; Oh, C-H.; Lunine, J. I.; Smith, M. A. J. Am. Soc. Mass Spectrom. 2005, 16, 850-859.

  10. Reaction product imaging

    Energy Technology Data Exchange (ETDEWEB)

    Chandler, D.W. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    Over the past few years the author has investigated the photochemistry of small molecules using the photofragment imaging technique. Bond energies, spectroscopy of radicals, dissociation dynamics and branching ratios are examples of information obtained by this technique. Along with extending the technique to the study of bimolecular reactions, efforts to make the technique as quantitative as possible have been the focus of the research effort. To this end, the author has measured the bond energy of the C-H bond in acetylene, branching ratios in the dissociation of HI, the energetics of CH{sub 3}Br, CD{sub 3}Br, C{sub 2}H{sub 5}Br and C{sub 2}H{sub 5}OBr dissociation, and the alignment of the CD{sub 3} fragment from CD{sub 3}I photolysis. In an effort to extend the technique to bimolecular reactions the author has studied the reaction of H with HI and the isotopic exchange reaction between H and D{sub 2}.

  11. Ozone-surface reactions in five homes: surface reaction probabilities, aldehyde yields, and trends.

    Science.gov (United States)

    Wang, H; Morrison, G

    2010-06-01

    Field experiments were conducted in five homes during three seasons (summer 2005, summer 2006 and winter 2007) to quantify ozone-initiated secondary aldehyde yields, surface reaction probabilities, and trends any temporal over a 1.5-year interval. Surfaces examined include living room carpets, bedroom carpets, kitchen floors, kitchen counters, and living room walls. Reaction probabilities for all surfaces for all seasons ranged from 9.4 x 10(-8) to 1.0 x 10(-4). There were no significant temporal trends in reaction probabilities for any surfaces from summer 2005 to summer 2006, nor over the entire 1.5-year period, indicating that it may take significantly longer than this period for surfaces to exhibit any 'ozone aging' or lowering of ozone-surface reactivity. However, all surfaces in three houses exhibited a significant decrease in reaction probabilities from summer 2006 to winter 2007. The total yield of aldehydes for the summer of 2005 were nearly identical to that for summer of 2006, but were significantly higher than for winter 2007. We also observed that older carpets were consistently less reactive than in newer carpets, but that countertops remained consistently reactive, probably because of occupant activities such as cooking and cleaning. Ozone reactions taking place at indoor surfaces significantly influence personal exposure to ozone and volatile reaction products. These field studies show that indoor surfaces only slowly lose their ability to react with ozone over several year time frames, and that this is probably because of a combination of large reservoirs of reactive coatings and periodic additions of reactive coatings in the form of cooking, cleaning, and skin-oil residues. When considering exposure to ozone and its reaction products and in the absence of dramatic changes in occupancy, activities or furnishings, indoor surface reactivity is expected to change very slowly.

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

    Energy Technology Data Exchange (ETDEWEB)

    Flytzani-Stephanopoulos, M; Schmidt, L D

    1979-01-01

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

  13. Surface analytical investigations of the release behaviour of volatile fission products during simulated core meltdown accidents and of the reaction behaviour of iodine with silver surfaces

    International Nuclear Information System (INIS)

    Moers, H.

    1986-07-01

    The report presents the results of the analysis of aerosol particles formed in simulated laboratory scale core meltdown experiments. In addition the interaction of silver surfaces with gaseous molecular iodine and with iodide and molecular iodine in aqueous solution was investigated. The composition of the aerosol samples and the progress of the reactions mentioned were determined by use of surface analytical techniques (X-ray photoelectron spectroscopy, Auger electron spectroscopy, secondary ion mass spectroscopy). The major information can be evaluated from X-ray photoelectron spectra which exhibit chemical shifts of the photoelectron lines which allowing a discrimination between different chemical species of the same element. The analyses showed that iodine is present in the aerosol particles mainly as caesium iodide and, to a smaller fraction, as silver iodide. During the adsorption of gaseous molecular iodine at metallic silver surfaces a closed silver iodide overlayer is formed. In aqueous iodide solutions one observes chemisorption of the iodide anions up to a coverage of the metallic silver surface of about half a monolayer. Molecular iodine in aqueous solution is completely converted to silver iodide which covers the substrate irregularly. (orig./HP) [de

  14. 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

  15. Surface compounds and the routes of formation of the reaction products in the interaction of propylene with zinc oxide

    Energy Technology Data Exchange (ETDEWEB)

    Davydov, A.A.; Yefremov, A.A.; Mikhalchenko, V.G.; Sokolovskii, V.D.

    1979-06-15

    Temperature programed desorption of propylene and allyl bromide from zinc oxide in the absence and presence of oxygen and an IR spectroscopic study of the adsorbed allyl bromide showed that propylene chemisorbed reversibly as a m-allyl species which may undergo dimerization at higher pressures or temperatures but does not form acrolein because the necessary electron transfer does not proceed on the n-type zinc oxide; that propylene also forms carbon dioxide and water via carbonate/carboxylate intermediates; and that the allyl bromide, which forms cations on the zinc oxide surface, is oxidized to acrolein.

  16. 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.

  17. A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product

    International Nuclear Information System (INIS)

    Orr, R.M.; Sims, H.E.; Taylor, R.J.

    2015-01-01

    Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or ‘finishing’ processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO_2 product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles. - Highlights: • Critical review of plutonium oxalate decomposition reactions. • New analysis of relationship between SSA and calcination temperature. • New SEM

  18. A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product

    Energy Technology Data Exchange (ETDEWEB)

    Orr, R.M.; Sims, H.E.; Taylor, R.J., E-mail: robin.j.taylor@nnl.co.uk

    2015-10-15

    Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or ‘finishing’ processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO{sub 2} product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles. - Highlights: • Critical review of plutonium oxalate decomposition reactions. • New analysis of relationship between SSA and calcination temperature.

  19. 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)

  20. Sodium-water reaction product flow system

    Energy Technology Data Exchange (ETDEWEB)

    Shirataki, K; Wada, H

    1978-11-18

    Purpose: To provide the subject equipments wherein thermal insulating layers which neither exfoliate nor react by the impact due to high temperature sodium and hydrogen gas and are used for mitigating the thermal impact are provided on the inner surfaces of the emission system equipments, thereby preventing the destruction of the emission system equipments. Constitution: Thermal insulating layers are formed on the inner surfaces of sodium-water reaction product emission system equipments, that is, the inner surface of the emission system pipeline, that of the accommodation vessel and the surface of the cyclone separator, by film treatment, coating or heat resisting coating, and these surfaces are covered with the layers. Each of the layers is made of a material which does not cause a rapid reaction with high temperature sodium or hydrogen gas nor exfoliates and is withstandable for several seconds in which the thermal impact of at least the emission system comes into question, and its thickness is more than one capable of securing the necessary thermal resistance computed by the thermal impact analysis of the emission system.

  1. Sodium-water reaction product flow system

    International Nuclear Information System (INIS)

    Shirataki, Koji; Wada, Hozumi.

    1978-01-01

    Purpose: To provide the subject equipments wherein thermal insulating layers which neither exfoliate nor react by the impact due to high temperature sodium and hydrogen gas and are used for mitigating the thermal impact are provided on the inner surfaces of the emission system equipments, thereby preventing the destruction of the emission system equipments. Constitution: Thermal insulating layers are formed on the inner surfaces of sodium-water reaction product emission system equipments, that is, the inner surface of the emission system pipeline, that of the accommodation vessel and the surface of the cyclone separator, by film treatment, coating or heat resisting coating, and these surfaces are covered with the layers. Each of the layers is made of a material which does not cause a rapid reaction with high temperature sodium or hydrogen gas nor exfoliates and is withstandable for several seconds in which the thermal impact of at least the emission system comes into question, and its thickness is more than one capable of securing the necessary thermal resistance computed by the thermal impact analysis of the emission system. (Yoshihara, H.)

  2. Bond-selective control of a gas-surface reaction

    Science.gov (United States)

    Killelea, Daniel R.

    rationalizes the observation of vibrational mode-specific and bond-selective behavior and the surface-temperature dependence of direct gas-surface reactions. It also guides predictions for behavior of gas-surface reactions. We also present results that use IR laser excitation of CH4 in the molecular beam to control the isotopic distribution of the reaction products. By exciting one quanta of the 13CH4 v 3 antisymmetric stretch in our methane molecular beam, we enhance the deposition of 13C on the nickel substrate. We also present results indicating the effect surface temperature has on the dissociation probability of vibrationally excited methane molecules.

  3. 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.

  4. 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.)

  5. Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

    2015-10-15

    The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

  6. Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

    International Nuclear Information System (INIS)

    Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

    2015-01-01

    The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

  7. η production in proton-nucleus reactions

    International Nuclear Information System (INIS)

    Cassing, W.; Batko, G.; Vetter, T.; Wolf, G.

    1991-01-01

    The production of η-mesons in proton-nucleus reactions is analysed with respect to primary nucleon-nucleon (NN→NN η ) and secondary pion-nucleon (πN→ηN) production processes on the basis of Hartree-Fock groundstate momentum distributions and free on-shell production processes. The folding model adopted compares well for meson production with more involved simulations based on VUU transport equations. Similar to K + production in proton-nucleus reactions the η-mesons are primarily produced by the πN→ηN channel. However, η-mesons are absorbed in nuclei via excitation of the N * (1535) resonance which leads to strong distortions of the primordial spectra. On the other hand, the experimental mass dependence of the differential cross sections might yield information about the in-medium properties of this resonance. (orig.)

  8. High energy photons production in nuclear reactions

    International Nuclear Information System (INIS)

    Nifenecker, H.; Pinston, J.A.

    1990-01-01

    Hard photon production, in nucleus-nucleus collisions, were studied at beam energies between 10 and 125 MeV. The main characteristics of the photon emission are deduced. They suggest that the neutron-proton collisions in the early stage of the reaction are the main source of high energy gamma-rays. An overview of the theoretical approaches is given and compared with experimental results. Theoretical attempts to include the contribution of charged pion exchange currents to photon production, in calculations of proton-nucleus-gamma and nucleus-nucleus-gamma reactions, showed suitable fitting with experimental data

  9. A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product

    Science.gov (United States)

    Orr, R. M.; Sims, H. E.; Taylor, R. J.

    2015-10-01

    Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or 'finishing' processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO2 product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles.

  10. Effect of reaction products on cathodic reduction of iodic acid

    International Nuclear Information System (INIS)

    Shtejnberg, G.V.; Urisson, N.A.; Revina, A.A.; Volod'ko, V.L.

    1988-01-01

    The effect of reaction products on kinetics of iodic acid reduction is investigated; reaction products are identified by the optical method. It is shown that although being similar from the qualitative viewpoint the effect on HIO 3 reduction of dissolved crystal and ''reduced'' iodine, certain quantitative differences take place, which are explained by the difference in their surface concentration. Explanation of certain sections of complex lgI, E-curve of HIO 3 reduction is given, in particular, advanced wave is related to the reduction from solution of unstable electroactive complex HIO 3 ) x (I 1 ) y or (HIO 3 ) x (I 2 ) y

  11. Fusion reaction product diagnostics in ASDEX

    International Nuclear Information System (INIS)

    Bosch, H.S.

    1987-01-01

    A diagnostic method was developed to look for the charged fusion products from the D(D,p)T-reactions in the divertor tokamak ASDEX. With a semi-conductor detector it was possible to evaluate the ion temperature in thermal plasmas from the proton energy spectra as well as from the triton spectra. In lower-hybrid wave heated plasmas non-thermal (fast) ions were observed. These ions create fusion products with a characteristically different energy spectrum. (orig.)

  12. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1988-01-01

    The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

  13. 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.

  14. 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

  15. 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

  16. Reactions of uranium hexafluoride photolysis products

    Science.gov (United States)

    Lyman, John L.; Laguna, Glenn; Greiner, N. R.

    1985-01-01

    This paper confirms that the ultraviolet photolysis reactions of UF6 in the B band spectral region is simple bond cleavage to UF5 and F. The photolysis products may either recombine to UF6 or the UF5 may dimerize, and ultimately polymerize, to solid UF5 particles. We use four methods to set an upper limit for the rate constant for recombination of krUF6 and UF5 after laser photolysis of the UF6 gas sample.

  17. 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.

  18. 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.

  19. 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)

  20. Influence of transesterification reaction temperature on biodiesel production

    Energy Technology Data Exchange (ETDEWEB)

    Pighinelli, Anna Leticia Montenegro Turtelli; Zorzeto, Thais Queiroz; Park, Kil Jin [Universidade Estadual de Campinas (FEAGRI/UNICAMP), SP (Brazil). Fac. de Engenharia Agricola], E-mail: annalets@agr.unicamp.br; Bevilaqua, Gabriela [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

    2008-07-01

    Brazilian government policy has authorized the introduction of biodiesel into the national energy matrix, law no.11.097 of January 13th, 2005. It is necessary, like any new product, to invest in research which is able to cover its entire production chain (planting of oilseeds, vegetable oils extraction and chemical reactions), providing data and relevant information in order to optimize the process and solve critical issues. The objective of this work was to study the effects of temperature on crude sunflower transesterification reaction with ethanol. A central composite experimental design with five variation levels (25 deg, 32 deg, 47.5 deg, 64 deg and 70 deg C) was used and response surface methodology applied for the data analysis. The statistical analysis of the results showed that the production suffered the influence of temperature (linear and quadratic effects) and reaction time (linear and quadratic). The generated models did not show significant regression. The model generated was not well suited to the experimental data and the value of the coefficient of determination (R{sup 2}=0.52) was low. Consequently it was not possible to build the response surface. (author)

  1. Multifractal scaling analysis of autopoisoning reactions over a rough surface

    International Nuclear Information System (INIS)

    Chaudhari, Ajay; Yan, Ching-Cher Sanders; Lee, S.-L.

    2003-01-01

    Decay type diffusion-limited reactions (DLR) over a rough surface generated by a random deposition model were performed. To study the effect of the decay profile on the reaction probability distribution (RPD), multifractal scaling analysis has been carried out. The dynamics of these autopoisoning reactions are controlled by the two parameters in the decay function, namely, the initial sticking probability (P ini ) of every site and the decay rate (m). The smaller the decay rate, the narrower is the range of α values in the α-f(α) multifractal spectrum. The results are compared with the earlier work of DLR over a surface of diffusion-limited aggregation (DLA). We also considered here the autopoisoning reactions over a smooth surface for comparing our results, which show clearly how the roughness affects the chemical reactions. The q-τ(q) multifractal curves for the smooth surface are linear whereas those for the rough surface are nonlinear. The range of α values in the case of a rough surface is wider than that of the smooth surface

  2. Surface sampling concentration and reaction probe

    Science.gov (United States)

    Van Berkel, Gary J; Elnaggar, Mariam S

    2013-07-16

    A method of analyzing a chemical composition of a specimen is described. The method can include providing a probe comprising an outer capillary tube and an inner capillary tube disposed co-axially within the outer capillary tube, where the inner and outer capillary tubes define a solvent capillary and a sampling capillary in fluid communication with one another at a distal end of the probe; contacting a target site on a surface of a specimen with a solvent in fluid communication with the probe; maintaining a plug volume proximate a solvent-specimen interface, wherein the plug volume is in fluid communication with the probe; draining plug sampling fluid from the plug volume through the sampling capillary; and analyzing a chemical composition of the plug sampling fluid with an analytical instrument. A system for performing the method is also described.

  3. Reaction dynamics of small molecules at metal surfaces

    International Nuclear Information System (INIS)

    Samson, P.A.

    1999-09-01

    The dissociation-desorption dynamics of D 2 upon the Sn/Pt(111) surface alloy are dependent on the surface concentration of Sn. The p(2 x 2) Sn/Pt(111) alloy surface (Θ Sn = 0.25 ML), is initially ∼30 times less reactive towards D 2 adsorption than clean Pt(111). On the (√3 x √3) R30 deg Sn/Pt(111) alloy surface (Θ Sn = 0.33 ML), increased inhibition of D 2 adsorption is reported, with S o ∼ 10 -5 at low energy, coinciding with the loss of stable Pt 3 hollow sites and a significant reduction in the D atom binding energy. Sticking on the √3 alloy is activated with an increased energy threshold of ∼280 meV, with no evidence that vibration enhances dissociation. The barrier to dissociation remains in the entrance channel before the D 2 bond begins to stretch. Vibrational excitation is, however, observed in nitrogen desorption from the catalytic reaction of NO + H 2 over Pd(110). For a surface at 600 K, N 2 vibrational state population ratios of P(v=1/v=0) = 0.50 ± 0.05 and P(v=2/v=0) = 0.60 ± 0.20 are reported. Desorption occurs via the N(ad) + N(ad) recombination channel with little energy released into translation and rotation. The translational energy release observed is dependent on the N 2 vibrational state, with translational temperatures of 425 K, 315 K and 180 K reported for the v=0, 1 and 2 states respectively. Sub-thermal energy releases and normally directed angular distributions suggest the influence of a trapping mechanism, recombining molecules scattering through a molecularly adsorbed state, with a transition state of large d NN responsible for the product vibrational excitation. Although N 2 dissociation on Fe(100) forms a simple overlayer structure, on Fe(110), molecular chemisorption does not occur at or above room temperature and the sticking is extremely small (∼10 -6 to 10 -7 ). Activated nitrogen bombardment can be used to prepare a 'surface nitride' with a structure related to the geometry of bulk Fe 4 N. Scanning tunnelling

  4. 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.

  5. 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

  6. 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.

  7. 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.

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

    International Nuclear Information System (INIS)

    Strickert, R.G.

    1976-01-01

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

  9. 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.

  10. 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...

  11. 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).

  12. 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)

  13. Structure of fungal oxyluciferin, the product of the bioluminescence reaction.

    Science.gov (United States)

    Purtov, K V; Osipova, Z M; Petushkov, V N; Rodionova, N S; Tsarkova, A S; Kotlobay, A A; Chepurnykh, T V; Gorokhovatsky, A Yu; Yampolsky, I V; Gitelson, J I

    2017-11-01

    The structure of fungal oxyluciferin was determined, the enzymatic bioluminescence reaction under substrate saturation conditions with discrete monitoring of formed products was conducted, and the structures of the end products of the reaction were established. On the basis of these studies, the scheme of oxyluciferin degradation to the end products was developed. The structure of fungal oxyluciferin was confirmed by counter synthesis.

  14. 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

  15. Multiparticle production in heavy-ion reactions

    International Nuclear Information System (INIS)

    Pelte, D.

    1980-01-01

    This lecture is concerned with the question how many particles and what kind of them are produced in heavy-ion collisions at energies about 10 MeV/n. We tend to assume that heavy-ion reactions at this energy are binary reactions. The experimental set consisting of two large ionization chambers serving to detection, in coincidence, the reaction fragments is described. With this set-up a number of reactions induced on 27 Al, 28 Si and 40 Ca by the 32 S beam of 135 and 190 MeV energy has been studied. Two-fragments inclusive and exclusive reactions were investigated. The assumption of a sequential statistical decay gives the best agreement with the data for all analyzed cases. (H.M.)

  16. 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

  17. 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)

  18. 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...

  19. Methods for forming complex oxidation reaction products including superconducting articles

    International Nuclear Information System (INIS)

    Rapp, R.A.; Urquhart, A.W.; Nagelberg, A.S.; Newkirk, M.S.

    1992-01-01

    This patent describes a method for producing a superconducting complex oxidation reaction product of two or more metals in an oxidized state. It comprises positioning at least one parent metal source comprising one of the metals adjacent to a permeable mass comprising at least one metal-containing compound capable of reaction to form the complex oxidation reaction product in step below, the metal component of the at least one metal-containing compound comprising at least a second of the two or more metals, and orienting the parent metal source and the permeable mass relative to each other so that formation of the complex oxidation reaction product will occur in a direction towards and into the permeable mass; and heating the parent metal source in the presence of an oxidant to a temperature region above its melting point to form a body of molten parent metal to permit infiltration and reaction of the molten parent metal into the permeable mass and with the oxidant and the at least one metal-containing compound to form the complex oxidation reaction product, and progressively drawing the molten parent metal source through the complex oxidation reaction product towards the oxidant and towards and into the adjacent permeable mass so that fresh complex oxidation reaction product continues to form within the permeable mass; and recovering the resulting complex oxidation reaction product

  20. The Heck reaction in the production of fine chemicals

    NARCIS (Netherlands)

    Vries, Johannes G. de

    2001-01-01

    An overview is given of the use of the Heck reaction for the production of fine chemicals. Five commercial products have been identified that are produced on a scale in excess of 1 ton/year. The herbicide Prosulfuron™ is produced via a Matsuda reaction of 2-sulfonatobenzenediazonium on

  1. 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.

  2. Quantitative surface analysis using deuteron-induced nuclear reactions

    International Nuclear Information System (INIS)

    Afarideh, Hossein

    1991-01-01

    The nuclear reaction analysis (NRA) technique consists of looking at the energies of the reaction products which uniquely define the particular elements present in the sample and it analysis the yield/energy distribution to reveal depth profiles. A summary of the basic features of the nuclear reaction analysis technique is given, in particular emphasis is placed on quantitative light element determination using (d,p) and (d,alpha) reactions. The experimental apparatus is also described. Finally a set of (d,p) spectra for the elements Z=3 to Z=17 using 2 MeV incident deutrons is included together with example of more applications of the (d,alpha) spectra. (author)

  3. 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

  4. Maillard reaction products in pet foods

    NARCIS (Netherlands)

    Rooijen, van C.

    2015-01-01

    Pet dogs and cats around the world are commonly fed processed commercial foods throughout their lives. Often heat treatments are used during the processing of these foods to improve nutrient digestibility, shelf life, and food safety. Processing is known to induce the Maillard reaction, in which

  5. High energy gamma-ray production in nuclear reactions

    International Nuclear Information System (INIS)

    Pinston, J.A.; Nifenecker, H.; Nifenecker, H.

    1989-01-01

    Experimental techniques used to study high energy gamma-ray production in nuclear reactions are reviewed. High energy photon production in nucleus-nucleus collisions is discussed. Semi-classical descriptions of the nucleus-nucleus gamma reactions are introduced. Nucleon-nucleon gamma cross sections are considered, including theoretical aspects and experimental data. High energy gamma ray production in proton-nucleus reactions is explained. Theoretical explanations of photon emission in nucleus-nucleus collisions are treated. The contribution of charged pion currents to photon production is mentioned

  6. Photochemical reaction products in air pollution

    Energy Technology Data Exchange (ETDEWEB)

    Stephens, E R; Darley, E F; Taylor, O C; Scott, W E

    1961-01-01

    Isolation and purification of peroxyacetyl nitrate (PAN) from artificial photochemical reaction of olefins and NO/sub x/ in air are analyzed. Olefin splits at the double bond, one end forming carbonyl compound and the other yielding PAN, among others. At concentrations below 1 ppM, PAN causes plant damage. At a concentration of about 1 ppM, PAN is a strong eye irritant.

  7. Production of radioactive nuclides in inverse reaction kinematics

    International Nuclear Information System (INIS)

    Traykov, E.; Rogachevskiy, A.; Bosswell, M.; Dammalapati, U.; Dendooven, P.; Dermois, O.C.; Jungmann, K.; Onderwater, C.J.G.; Sohani, M.; Willmann, L.; Wilschut, H.W.; Young, A.R.

    2007-01-01

    Efficient production of short-lived radioactive isotopes in inverse reaction kinematics is an important technique for various applications. It is particularly relevant when the isotope of interest is only a few nucleons away from a stable isotope. In this article production via charge exchange and stripping reactions in combination with a magnetic separator is explored. The relation between the separator transmission efficiency, the production yield, and the choice of beam energy is discussed. The results of some exploratory experiments will be presented

  8. 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.

  9. Exclusive hadron production in two photon reactions

    International Nuclear Information System (INIS)

    Poppe, M.

    1986-02-01

    This paper summarises experimental results on exclusive hadron production in two photon collisions at electron positron storage rings and attempts some interpretation. Experimental know how is described and new suggestions are made for future analyses. New model calculations on resonance form factors and pair production amplitudes are presented. The two photon vertex is decomposed such that experiments can be parameterised with the minimal number of free parameters. Selection rules for off shell photon collisions are given in addition to Yang's theorems. (orig.)

  10. Reaction and Aggregation Dynamics of Cell Surface Receptors

    Science.gov (United States)

    Wang, Michelle Dong

    This dissertation is composed of both theoretical and experimental studies of cell surface receptor reaction and aggregation. Project I studies the reaction rate enhancement due to surface diffusion of a bulk dissolved ligand with its membrane embedded target, using numerical calculations. The results show that the reaction rate enhancement is determined by ligand surface adsorption and desorption kinetic rates, surface and bulk diffusion coefficients, and geometry. In particular, we demonstrate that the ligand surface adsorption and desorption kinetic rates, rather than their ratio (the equilibrium constant), are important in rate enhancement. The second and third projects are studies of acetylcholine receptor clusters on cultured rat myotubes using fluorescence techniques after labeling the receptors with tetramethylrhodamine -alpha-bungarotoxin. The second project studies when and where the clusters form by making time-lapse movies. The movies are made from overlay of the pseudocolored total internal reflection fluorescence (TIRF) images of the cluster, and the schlieren images of the cell cultures. These movies are the first movies made using TIRF, and they clearly show the cluster formation from the myoblast fusion, the first appearance of clusters, and the eventual disappearance of clusters. The third project studies the fine structural features of individual clusters observed under TIRF. The features were characterized with six parameters by developing a novel fluorescence technique: spatial fluorescence autocorrelation. These parameters were then used to study the feature variations with age, and with treatments of drugs (oligomycin and carbachol). The results show little variation with age. However, drug treatment induced significant changes in some parameters. These changes were different for oligomycin and carbachol, which indicates that the two drugs may eliminate clusters through different mechanisms.

  11. Reaction kinetics, reaction products and compressive strength of ternary activators activated slag designed by Taguchi method

    NARCIS (Netherlands)

    Yuan, B.; Yu, Q.L.; Brouwers, H.J.H.

    2015-01-01

    This study investigates the reaction kinetics, the reaction products and the compressive strength of slag activated by ternary activators, namely waterglass, sodium hydroxide and sodium carbonate. Nine mixtures are designed by the Taguchi method considering the factors of sodium carbonate content

  12. Tritium production in neutron induced reactions

    International Nuclear Information System (INIS)

    Krasa, A.; Andreotti, E.; Hult, M.; Marissens, G.; Plompen, A.; Angelone, M.; Pillon, M.

    2011-01-01

    We present an overview of the present knowledge of (n,t) reaction excitation functions in the 14-21 MeV energy range for Cd, Cr, Fe, Mg, Mo, Ni, Pb, Pd, Ru, Sn, Ti, Zr. Experimental data are compared with evaluated data libraries, cross-section systematics, and TALYS calculations. The new values for the "5"0Cr(n,t)"4"8V cross-section measured using γ-spectrometry at 15, 16, 17.3 MeV are presented. The trend of the results confirms that while early experimental data at 14.6 MeV are strongly overestimated, the calculations performed with the default version of TALYS strongly underestimate the excitation curve in the measured energy region

  13. Quantitation of Maillard reaction products in commercially available pet foods

    NARCIS (Netherlands)

    Rooijen, van C.; Bosch, G.; Poel, van der A.F.B.; Wierenga, P.A.; Alexander, L.; Hendriks, W.H.

    2014-01-01

    During processing of pet food, the Maillard reaction occurs, which reduces the bioavailability of essential amino acids such as lysine and results in the formation of advanced Maillard reaction products (MRPs). The aim of this study was to quantitate MRPs (fructoselysine (FL), carboxymethyllysine

  14. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    International Nuclear Information System (INIS)

    McCrea, Keith R.

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

  15. 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.

  16. Coherent π0 production in neutrino reactions

    International Nuclear Information System (INIS)

    Rein, D.; Sehgal, L.M.

    1983-01-01

    We have calculated the cross section and angular distribution of the neutral current process ν+K -> ν+K+π 0 involving the coherent interaction of a neutrino with a complex nucleus. A contrast is made to incoherent production ν+n -> ν+n+π 0 on a single nucleon. The results are compared with observations from some recent experiments. (orig.)

  17. EPR and NMR detection of transient radicals and reaction products

    International Nuclear Information System (INIS)

    Trifunac, A.D.

    1981-01-01

    Magnetic resonance methods in radiation chemistry are illustrated. The most recent developments in pulsed EPR and NMR studies in pulse radiolysis are outlined with emphasis on the study of transient radicals and their reaction products. 12 figures

  18. Influence of irradiation on reaction products of nitrite in foodstuffs

    International Nuclear Information System (INIS)

    Mirna, A.; Rau, G.

    1982-01-01

    Nitro alkanes and nitrolic acids are formed in foods by nitrosation reactions with nitrite. Among TEA-responsive compounds nitrolic acid behave to irradiation similar to N-nitrosamines. Some substances, extracted from spices, especially garlic, are also detectable by GC/TEA-chromatogramms of meat products and of reaction products from spices with nitrite show retention times not always clearly differentiated from those of NDMA, NDEA, NPIP and NPYR, respectively. Additional confirmation of such TEA positive compounds, therefore, is necessary. (orig.) [de

  19. Chemistry - Toward efficient hydrogen production at surfaces

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Christensen, Claus H.

    2006-01-01

    Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy.......Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy....

  20. Energy conservation and maximal entropy production in enzyme reactions.

    Science.gov (United States)

    Dobovišek, Andrej; Vitas, Marko; Brumen, Milan; Fajmut, Aleš

    2017-08-01

    A procedure for maximization of the density of entropy production in a single stationary two-step enzyme reaction is developed. Under the constraints of mass conservation, fixed equilibrium constant of a reaction and fixed products of forward and backward enzyme rate constants the existence of maximum in the density of entropy production is demonstrated. In the state with maximal density of entropy production the optimal enzyme rate constants, the stationary concentrations of the substrate and the product, the stationary product yield as well as the stationary reaction flux are calculated. The test, whether these calculated values of the reaction parameters are consistent with their corresponding measured values, is performed for the enzyme Glucose Isomerase. It is found that calculated and measured rate constants agree within an order of magnitude, whereas the calculated reaction flux and the product yield differ from their corresponding measured values for less than 20 % and 5 %, respectively. This indicates that the enzyme Glucose Isomerase, considered in a non-equilibrium stationary state, as found in experiments using the continuous stirred tank reactors, possibly operates close to the state with the maximum in the density of entropy production. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Correlations between reaction product yields as a tool for probing heavy-ion reaction scenarios

    International Nuclear Information System (INIS)

    Gawlikowicz, W.; Agnihotri, D. K.; Baldwin, S. A.; Schroeder, W. U.; Toke, J.; Charity, R. J.; Sarantites, D. G.; Sobotka, L. G.; Souza, R. T. de; Barczyk, T.; Grotowski, K.; Micek, S.; Planeta, R.; Sosin, Z.

    2010-01-01

    Experimental multidimensional joint distributions of neutrons and charged reaction products were analyzed for 136 Xe + 209 Bi reactions at E/A=28, 40, and 62 MeV and were found to exhibit several different types of prominent correlation patterns. Some of these correlations have a simple explanation in terms of the system excitation energy and pose little challenge to most statistical decay theories. However, several other types of correlation patterns are difficult to reconcile with some, but not other, possible reaction scenarios. In this respect, correlations between the average atomic numbers of intermediate-mass fragments, on the one hand, and light particle multiplicities, on the other, are notable. This kind of multiparticle correlation provides a useful tool for probing reaction scenarios, which is different from the traditional approach of interpreting inclusive yields of individual reaction products.

  2. Surface negative ion production in ion sources

    International Nuclear Information System (INIS)

    Belchenko, Y.

    1993-01-01

    Negative ion sources and the mechanisms for negative ion production are reviewed. Several classes of sources with surface origin of negative ions are examined in detail: surface-plasma sources where ion production occurs on the electrode in contact with the plasma, and ''pure surface'' sources where ion production occurs due to conversion or desorption processes. Negative ion production by backscattering, impact desorption, and electron- and photo-stimulated desorption are discussed. The experimental efficiencies of intense surface negative ion production realized on electrodes contacted with hydrogen-cesium or pure hydrogen gas-discharge plasma are compared. Recent modifications of surface-plasma sources developed for accelerator and fusion applications are reviewed in detail

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

    Science.gov (United States)

    Shu, Shi; Morrison, Glenn C

    2011-05-15

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

  4. 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.

  5. THE PRODUCT DESIGN PROCESS USING STYLISTIC SURFACES

    Directory of Open Access Journals (Sweden)

    Arkadiusz Gita

    2017-06-01

    Full Text Available The increasing consumer requirements for the way what everyday use products look like, forces manufacturers to put more emphasis on product design. Constructors, apart from the functional aspects of the parts created, are forced to pay attention to the aesthetic aspects. Software for designing A-class surfaces is very helpful in this case. Extensive quality analysis modules facilitate the work and allow getting models with specific visual features. The authors present a design process of the product using stylistic surfaces based on the front panel of the moped casing. In addition, methods of analysis of the design surface and product technology are presented.

  6. Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

    Science.gov (United States)

    Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

    2017-03-01

    Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

  7. 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.

  8. Microanalysis of solid surfaces by nuclear reactions and elastic scattering

    International Nuclear Information System (INIS)

    Agius, B.

    1975-01-01

    The principles involved in the use of monokinetic light ions beams, of about 1MeV, to the study of surface phenomena are presented. Two complementary techniques are described: the use of elastic scattering, which allows the analysis of impurity elements heavier than the substrate components and the use of nuclear reactions specific of light elements. Typical sensitivities are of the order of 10 11 at/cm 2 in good cases. The depth resolution varies, according to the cases, from about a hundred angstroems to a few thousand angstroems [fr

  9. 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).

  10. 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....

  11. Optimization of the production of ethyl esters by ultrasound assisted reaction of soybean oil and ethanol

    OpenAIRE

    Rodrigues,S.; Mazzone,L. C. A.; Santos,F. F. P.; Cruz,M. G. A.; Fernandes,F. A. N.

    2009-01-01

    Biodiesel is a renewable liquid fuel that can be produced by a transesterification reaction between a vegetable oil and an alcohol. This paper evaluates and optimizes the production of ethyl esters (biodiesel) from soybean oil and ethanol. The reaction was carried out by applying ultrasound under atmospheric pressure and ambient temperature. Response surface methodology was used to evaluate the influence of alcohol to oil molar ratio and catalyst concentration on the yield of conversion of so...

  12. 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.

  13. Duff reaction on phenols: Characterization of non steam volatile products

    Digital Repository Service at National Institute of Oceanography (India)

    Wahidullah, S.; DeSouza, L.; Bhattacharya, J.

    New products having structures 1 and 2 have been characterized in the Duff reaction thymol arid carvacrol. These products have been identified as 2.6'-dithymylmethane 1 and 5.5' -dicarvacryl methane 2 respectively on the basis of spectral data...

  14. Mass formula dependence of calculated spallation reaction product distributions

    International Nuclear Information System (INIS)

    Nishida, Takahiko; Nakahara, Yasuaki

    1990-01-01

    A new version of the spallation reaction simulation code NUCLEUS was developed by incorporating Uno and Yamada's mass formula. This version was used to calculate the distribution of products from the spallation of uranium nuclei by high-energy protons. The dependence of the distributions on the mass formula was examined by comparing the results with those from the original version, which is based on Cameron's mass formula and the mass table compiled by Wapstra et al. As regards the fission component of spallation products, the new version reproduces the reaction product data obtained from thin foil experiments much better, especially on the neutron excess side. (orig.) [de

  15. 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.

  16. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    Science.gov (United States)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  17. GC of catalytic reactions products involved in the promising fuel synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Zheivot, V.; Sazonova, N. [Russian Academy of Sciences, Novosibirsk (Russian Federation). Boreskov Inst. of Catalysis

    2012-09-15

    Catalytic reactions involved in the synthesis of the promising kinds of novel fuel and products formed in these reactions were systematized according to the resulting fuel type. Generalization of the retention of the substances comprising these products is presented. Chromatograms exhibiting their separation on chromatographic materials with the surface of different chemical properties are summarized. We propose procedures for gas-chromatographic analysis of the catalytic reactions products formed in the synthesis of hydrogen, methanol, dimethyl ether and hydrocarbons as a new generation of fuel alternative to petroleum and coal. For partial oxidation of methane into synthesis gas, on-line determination of the components obtained in the reaction was carried out by gas chromatography and gas analyzer based on different physicochemical methods (IR spectroscopy and electrochemical methods). Similarity of the results obtained using these methods is demonstrated. (orig.)

  18. Catalytic activation of molecular hydrogen in alkyne hydrogenation reactions by lanthanide metal vapor reaction products

    International Nuclear Information System (INIS)

    Evans, W.J.; Bloom, I.; Engerer, S.C.

    1983-01-01

    A rotary metal vapor was used in the synthesis of Lu, Er, Nd, Sm, Yb, and La alkyne, diene, and phosphine complexes. A typical catalytic hydrogenation experiment is described. The lanthanide metal vapor product is dissolved in tetrahydrofuran or toluene and placed in a pressure reaction vessel 3-hexyne (or another substrate) is added, the chamber attached to a high vacuum line, cooled to -196 0 C, evacuated, warmed to ambient temperature and hydrogen is added. The solution is stirred magnetically while the pressure in monitored. The reaction products were analyzed by gas chromatography. Rates and products of various systems are listed. This preliminary survey indicates that catalytic reaction chemistry is available to these metals in a wide range of coordination environments. Attempts to characterize these compounds are hampered by their paramagnetic nature and their tendency to polymerize

  19. 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.

  20. 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

  1. Wireless sensing on surface hydrocarbon production systems

    International Nuclear Information System (INIS)

    Kane, D; McStay, D; Mulholland, J; Costello, L

    2009-01-01

    The use of wireless sensor networks for monitoring and optimising the performance of surface hydrocarbon production systems is reported. Wireless sensor networks are shown to be able to produce comprehensively instrumented XTs and other equipment that generate the data required by Intelligent Oilfield systems. The information produced by such systems information can be used for real-time operational control, production optimization and troubleshooting.

  2. Optimization and kinetic studies of sea mango (Cerbera odollam) oil for biodiesel production via supercritical reaction

    International Nuclear Information System (INIS)

    Ang, Gaik Tin; Ooi, San Nee; Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

    2015-01-01

    Highlights: • Sea mango oil as feedstock for biodiesel via non-catalytic supercritical reaction. • Extracted sea mango oil with high FFA could produce high yield of FAME. • Employment of Response Surface Methodology for optimization of FAME. • Kinetic study for reversible transesterification and esterification reactions. - Abstract: Sea mango (Cerbera odollam) oil, which is rich in free fatty acids, was utilized to produce fatty acid methyl esters (FAME) via supercritical transesterification reaction. Sea mango oil was extracted from seeds and was subsequently reacted with methanol in a batch-type supercritical reactor. Response surface methodology (RSM) analysis was used to optimize important parameters, including reaction temperature, reaction time and the molar ratio of methanol to oil. The optimum conditions were found as 380 °C, 40 min and 45:1 mol/mol, respectively, to achieve 78% biodiesel content. The first kinetic modelling of FAME production from sea mango oil incorporating reversible transesterification and reversible esterification was verified simultaneously. The kinetic parameters, including reaction rate constants, k, the pre-exponential constant, A, and the activation energy, Ea, for transesterification and esterification were determined using an ordinary differential equation (ODE45) solver. The highest activation energy of 40 kJ/mol and the lowest reaction rate constant of 2.50 × 10 −5 dm 3 /mol s verified that the first stepwise reaction of TG to produce DG was the rate-limiting step

  3. Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

    Science.gov (United States)

    Hudson, R.; Loeffler, M. J.; Gerakines, P.

    2017-12-01

    The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

  4. 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.

  5. Stochastic aspects of multiparticle production in relativistic nuclear reactions

    International Nuclear Information System (INIS)

    Tachung, M.

    1988-01-01

    Midrapidity multiparticle production process in ordinary hadron and heavy-ion induced reactions at sufficiently high incident energies are analyzed. It is shown that stochastic aspects of multiparticle production process in relativistic range plays a dominating role in understanding the observable phenomena. The basic idea and the main results of the multisource model for hadron-nucleus and nucleus-nucleus collisions are shown. The concept of the NES (number of effective sources) scaling is discussed. 16 refs.; 7 figs

  6. The production of high energy neutrons by secondary reactions

    International Nuclear Information System (INIS)

    Nieschmidt, E.B.; Roney, T.J.; Staples, D.R.; Harmon, J.F.; Burkhart, J.H.

    1994-01-01

    The potential of using binary reactions in targets containing Be is discussed. Data are presented from the use of Be and BeF 2 targets bombarded with 1.5, 1.7, 1.8 and 1.9 MeV protons. Neutron production is enhanced by the presence of the F by factors of ∼4

  7. Two-pion production in photon-induced reactions

    Indian Academy of Sciences (India)

    A deeper understanding of the situation is anticipated from a detailed experimental study of meson photoproduction from nuclei in exclusive reactions. In the energy regime above the (1232) resonance, the dominant double pion production channels are of particular interest. Double pion photoproduction from nuclei is ...

  8. 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

  9. Reaction products of densified silica fume agglomerates in concrete

    International Nuclear Information System (INIS)

    Diamond, Sidney; Sahu, Sadananda; Thaulow, Niels

    2004-01-01

    Most silica fume currently used in concrete is in the dry densified form and consists of agglomerates of sizes between 10 μm and several millimeters. Many of these agglomerates may break down only partially in normal concrete mixing. Examination of various mature silica-fume-bearing concretes using backscatter mode scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis shows that such agglomerates have reacted in situ and given rise to recognizable types of reaction products filling the space within the original outline of the agglomerate. One type is 'quiescent', and usually shows no evidence of volume instability. EDX spectra indicate that the product formed within such grains is C-S-H of very low Ca/Si ratio, with modest alkali contents. Other silica fume agglomerates may undergo a distinct alkali-silica-type reaction (ASR), with the reaction product found within the original outline of the agglomerate having significantly less calcium and usually much higher alkali contents than the quiescent type. Such reacted agglomerates show evidence of local expansion, shrinkage cracking (on drying), and other features common to ASR. Both types may be found within the same concrete, sometimes in close proximity. It further appears that exposure to seawater may convert previously formed reaction products of silica fume agglomerates to magnesium silicate hydrates

  10. Fission-product SiC reaction in HTGR fuel

    International Nuclear Information System (INIS)

    Montgomery, F.

    1981-01-01

    The primary barrier to release of fission product from any of the fuel types into the primary circuit of the HTGR are the coatings on the fuel particles. Both pyrolytic carbon and silicon carbide coatings are very effective in retaining fission gases under normal operating conditions. One of the possible performance limitations which has been observed in irradiation tests of TRISO fuel is chemical interaction of the SiC layer with fission products. This reaction reduces the thickness of the SiC layer in TRISO particles and can lead to release of fission products from the particles if the SiC layer is completely penetrated. The experimental section of this report describes the results of work at General Atomic concerning the reaction of fission products with silicon carbide. The discussion section describes data obtained by various laboratories and includes (1) a description of the fission products which have been found to react with SiC; (2) a description of the kinetics of silicon carbide thinning caused by fission product reaction during out-of-pile thermal gradient heating and the application of these kinetics to in-pile irradiation; and (3) a comparison of silicon carbide thinning in LEU and HEU fuels

  11. Surface chemistry of tribochemical reactions explored in ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Lara-Romero, Javier; Maya-Yescas, Rafael; Rico-Cerda, Jose Luis; Rivera-Rojas, Jose Luis; Castillo, Fernando Chinas; Kaltchev, Matey; Tysoe, Wilfred T.

    2006-01-01

    The thermal decomposition of model extreme-pressure lubricant additives on clean iron was studied in ultrahigh vacuum conditions using molecular beam strategies. Methylene chloride and chloroform react to deposit a solid film consisting of FeCl 2 and carbon, and evolve only hydrogen into the gas phase. No gas-phase products and less carbon on the surface are detected in the case of carbon tetrachloride. Dimethyl and diethyl disulfide react on clean iron to deposit a saturated sulfur plus carbon layer at low temperatures (∼600 K) and an iron sulfide film onto a Fe + C underlayer at higher temperatures (∼950 K). Methane is the only gas-phase product when dimethyl disulfide reacts with iron. Ethylene and hydrogen are detected when diethyl disulfide is used

  12. Cirrus cloud mimic surfaces in the laboratory: organic acids, bases and NOx heterogeneous reactions

    Science.gov (United States)

    Sodeau, J.; Oriordan, B.

    2003-04-01

    CIRRUS CLOUD MIMIC SURFACES IN THE LABORATORY:ORGANIC ACIDS, BASES AND NOX HETEROGENEOUS REACTIONS. B. ORiordan, J. Sodeau Department of Chemistry and Environment Research Institute, University College Cork, Ireland j.sodeau@ucc.ie /Fax: +353-21-4902680 There are a variety of biogenic and anthropogenic sources for the simple carboxylic acids to be found in the troposphere giving rise to levels as high as 45 ppb in certain urban areas. In this regard it is of note that ants of genus Formica produce some 10Tg of formic acid each year; some ten times that produced by industry. The expected sinks are those generally associated with tropospheric chemistry: the major routes studied, to date, being wet and dry deposition. No studies have been carried out hitherto on the role of water-ice surfaces in the atmospheric chemistry of carboxylic acids and the purpose of this paper is to indicate their potential function in the heterogeneous release of atmospheric species such as HONO. The deposition of formic acid on a water-ice surface was studied using FT-RAIR spectroscopy over a range of temperatures between 100 and 165K. In all cases ionization to the formate (and oxonium) ions was observed. The results were confirmed by TPD (Temperature Programmed Desorption) measurements, which indicated that two distinct surface species adsorb to the ice. Potential reactions between the formic acid/formate ion surface and nitrogen dioxide were subsequently investigated by FT-RAIRS. Co-deposition experiments showed that N2O3 and the NO+ ion (associated with water) were formed as products. A mechanism is proposed to explain these results, which involves direct reaction between the organic acid and nitrogen dioxide. Similar experiments involving acetic acid also indicate ionization on a water-ice surface. The results are put into the context of atmospheric chemistry potentially occuring on cirrus cloud surfaces.

  13. 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...

  14. Stochastic thermodynamics and entropy production of chemical reaction systems

    Science.gov (United States)

    Tomé, Tânia; de Oliveira, Mário J.

    2018-06-01

    We investigate the nonequilibrium stationary states of systems consisting of chemical reactions among molecules of several chemical species. To this end, we introduce and develop a stochastic formulation of nonequilibrium thermodynamics of chemical reaction systems based on a master equation defined on the space of microscopic chemical states and on appropriate definitions of entropy and entropy production. The system is in contact with a heat reservoir and is placed out of equilibrium by the contact with particle reservoirs. In our approach, the fluxes of various types, such as the heat and particle fluxes, play a fundamental role in characterizing the nonequilibrium chemical state. We show that the rate of entropy production in the stationary nonequilibrium state is a bilinear form in the affinities and the fluxes of reaction, which are expressed in terms of rate constants and transition rates, respectively. We also show how the description in terms of microscopic states can be reduced to a description in terms of the numbers of particles of each species, from which follows the chemical master equation. As an example, we calculate the rate of entropy production of the first and second Schlögl reaction models.

  15. 1-4 Strangeness Production in Antiproton Induced Nuclear Reactions.

    Institute of Scientific and Technical Information of China (English)

    Feng; Zhaoqing[1

    2014-01-01

    More localized energy deposition is able to be produced in antiproton-nucleus collisions in comparison withheavy-ion collisions due to annihilation reactions. Searching for the cold quark-gluon plasma (QGP) with antiprotonbeamshas been considered as a hot topic both in experiments and in theretical calculations over the past severaldecades. Strangeness production and hypernucleus formation in antiproton-induced nuclear reactions are importancein exploring the hyperon (antihyperon)-nucleon (HN) potential and the antinucleon-nucleon interaction, whichhave been hot topics in the forthcoming experiments at PANDA in Germany.

  16. Studying reaction products in a lithium thionyl chloride cell

    International Nuclear Information System (INIS)

    Vol'fkovich, Yu.M.; Sosenkin, V.E.; Nikol'skaya, N.F.; Blinov, I.A.

    1999-01-01

    Change in the mass, volume and chemical composition of reaction insoluble products (RIP) formed in the course of discharge of thionyl chloride lithium cells under different conditions has been studied by the methods of gravimetry, volumetry and element analysis. It has been ascertained that the measured volume and mass of RIP essentially (by a factor of 1.1-1.8) exceed the calculated values, proceeding from the reaction stoichiometry. Besides lithium chloride and sulfur during discharge additional RIP is formed as LiAlCl 4 · SOCl 2 solvate, its share increasing with temperature decrease, increase in current density and electrolyte concentration [ru

  17. Surface Water Protection by Productive Buffers

    DEFF Research Database (Denmark)

    Christen, Benjamin

    Vegetated riparian buffer zones are a widely recommended best management practice in agriculture for protecting surface and coastal waters from diffuse nutrient pollution. On the background of the EU funded research project NitroEurope (NEU; www.NitroEurope.eu), this study concentrates...... on the mitigation of nitrogen pollution in surface and groundwater, using riparian buffer zones for biomass production. The objectives are to map suitable areas for buffer implementation across the six NEU study landscapes, model tentative N-loss mitigation, calculate biomass production potential and economic...... designed for local conditions could be a way of protecting water quality attractive to many stakeholders....

  18. Converged three-dimensional quantum mechanical reaction probabilities for the F + H2 reaction on a potential energy surface with realistic entrance and exit channels and comparisons to results for three other surfaces

    Science.gov (United States)

    Lynch, Gillian C.; Halvick, Philippe; Zhao, Meishan; Truhlar, Donald G.; Yu, Chin-Hui; Kouri, Donald J.; Schwenke, David W.

    1991-01-01

    Accurate three-dimensional quantum mechanical reaction probabilities are presented for the reaction F + H2 yields HF + H on the new global potential energy surface 5SEC for total angular momentum J = 0 over a range of translational energies from 0.15 to 4.6 kcal/mol. It is found that the v-prime = 3 HF vibrational product state has a threshold as low as for v-prime = 2.

  19. Identification of reaction products from reactions of free chlorine with the lipid-regulator gemfibrozil.

    Science.gov (United States)

    Krkošek, Wendy H; Koziar, Stephen A; White, Robert L; Gagnon, Graham A

    2011-01-01

    High global consumption rates have led to the occurrence of pharmaceutically active compounds (PhACs) in wastewater. The use of chlorine to disinfect wastewater prior to release into the environment may convert PhACs into uncharacterized chlorinated by-products. In this investigation, chlorination of a common pharmaceutical, the antihyperlipidemic agent gemfibrozil, was documented. Gemfibrozil (2,2-dimethyl-5-(2,5-dimethylphenoxy)pentanoic acid) was reacted with sodium hypochlorite and product formation was monitored by gas chromatography-mass spectrometry (GC-MS). The incorporation of one, two or three chlorine atoms into the aromatic region of gemfibrozil was demonstrated using negative-ion electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS). Further analysis using (1)H nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as 4'-ClGem (5-(4-chloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid) 4',6'-diClGem (5-(4,6-dichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), and 3',4',6'-triClGem (5-(3,4,6-trichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), products consistent with electrophilic aromatic substitution reactions. The rapid reaction of gemfibrozil with free chlorine at pH conditions relevant to water treatment indicates that a mixture of chlorinated gemfibrozils is likely to be found in wastewater disinfected with chlorine. Copyright © 2010 Elsevier Ltd. All rights reserved.

  20. Ozone deposition velocities, reaction probabilities and product yields for green building materials

    Science.gov (United States)

    Lamble, S. P.; Corsi, R. L.; Morrison, G. C.

    2011-12-01

    Indoor surfaces can passively remove ozone that enters buildings, reducing occupant exposure without an energy penalty. However, reactions between ozone and building surfaces can generate and release aerosols and irritating and carcinogenic gases. To identify desirable indoor surfaces the deposition velocity, reaction probability and carbonyl product yields of building materials considered green (listed, recycled, sustainable, etc.) were quantified. Nineteen separate floor, wall or ceiling materials were tested in a 10 L, flow-through laboratory reaction chamber. Inlet ozone concentrations were maintained between 150 and 200 ppb (generally much lower in chamber air), relative humidity at 50%, temperature at 25 °C and exposure occurred over 24 h. Deposition velocities ranged from 0.25 m h -1 for a linoleum style flooring up to 8.2 m h -1 for a clay based paint; reaction probabilities ranged from 8.8 × 10 -7 to 6.9 × 10 -5 respectively. For all materials, product yields of C 1 thru C 12 saturated n-aldehydes, plus acetone ranged from undetectable to greater than 0.70 The most promising material was a clay wall plaster which exhibited a high deposition velocity (5.0 m h -1) and a low product yield (

  1. Piecewise Loglinear Estimation of Efficient Production Surfaces

    OpenAIRE

    Rajiv D. Banker; Ajay Maindiratta

    1986-01-01

    Linear programming formulations for piecewise loglinear estimation of efficient production surfaces are derived from a set of basic properties postulated for the underlying production possibility sets. Unlike the piecewise linear model of Banker, Charnes, and Cooper (Banker R. D., A. Charnes, W. W. Cooper. 1984. Models for the estimation of technical and scale inefficiencies in data envelopment analysis. Management Sci. 30 (September) 1078--1092.), this approach permits the identification of ...

  2. 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

  3. Maillard reaction products from chitosan-xylan ionic liquid solution.

    Science.gov (United States)

    Luo, Yuqiong; Ling, Yunzhi; Wang, Xiaoying; Han, Yang; Zeng, Xianjie; Sun, Runcang

    2013-10-15

    A facile method is reported to prepare Maillard reaction products (MRPs) from chitosan and xylan in co-solvent ionic liquid. UV absorbance and fluorescence changes were regarded as indicators of the occurrence of Maillard reaction. FT-IR, NMR, XRD and TG were used to investigate the structure of chitosan-xylan conjugate. The results revealed that when chitosan reacted with xylan in ionic liquid, the hydrogen bonds in chitosan were destroyed, the facts resulted in the formation of chitosan-xylan MRPs. Moreover, when the mass ratio of chitosan to xylan was 1:1, the Maillard reaction proceeded easily. In addition, relatively high antioxidant property was also noted for the chitosan-xylan conjugate with mass ratio 1:1. So the obtained chitosan-xylan MRP is a promising antioxidant agent for food industry. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. [Fission product yields of 60 fissioning reactions]. Final report

    International Nuclear Information System (INIS)

    Rider, B.F.

    1995-01-01

    In keeping with the statement of work, I have examined the fission product yields of 60 fissioning reactions. In co-authorship with the UTR (University Technical Representative) Talmadge R. England ''Evaluation and Compilation of Fission Product Yields 1993,'' LA-UR-94-3106(ENDF-349) October, (1994) was published. This is an evaluated set of fission product Yields for use in calculation of decay heat curves with improved accuracy has been prepared. These evaluated yields are based on all known experimental data through 1992. Unmeasured fission product yields are calculated from charge distribution, pairing effects, and isomeric state models developed at Los Alamos National Laboratory. The current evaluation has been distributed as the ENDF/B-VI fission product yield data set

  5. Nicotiana tabacum as model for ozone - plant surface reactions

    Science.gov (United States)

    Jud, Werner; Fischer, Lukas; Wohlfahrt, Georg; Tissier, Alain; Canaval, Eva; Hansel, Armin

    2015-04-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. The ensuing injuries have been related to the uptake of ozone through the stomatal pores and oxidative effects damaging the internal leaf tissue. A striking question of current research is the environment and plant specific partitioning of ozone loss between gas phase, stomatal or plant surface sink terms. Here we show results from ozone fumigation experiments using various Nicotiana Tabacum varieties, whose surfaces are covered with different amounts of unsaturated diterpenoids exuded by their glandular trichomes. Exposure to elevated ozone levels (50 to 150 ppbv) for 5 to 15 hours in an exceptionally clean cuvette system did neither result in a reduction of photosynthesis nor caused any visible leaf damage. Both these ozone induced stress effects have been observed previously in ozone fumigation experiments with the ozone sensitive tobacco line Bel-W3. In our case ozone fumigation was accompanied by a continuous release of oxygenated volatile organic compounds, which could be clearly associated to their condensed phase precursors for the first time. Gas phase reactions of ozone were avoided by choosing a high enough gas exchange rate of the plant cuvette system. In the case of the Ambalema variety, that is known to exude only the diterpenoid cis-abienol, ozone fumigation experiments yield the volatiles formaldehyde and methyl vinyl ketone (MVK). The latter could be unequivocally separated from isomeric methacrolein (MACR) by the aid of a Selective Reagent Ion Time-of-Flight Mass Spectrometer (SRI-ToF-MS), which was switched every six minutes from H3O+ to NO+ primary ion mode and vice versa. Consistent with the picture of an ozone protection mechanism caused by reactive diterpenoids at the leaf surface are the results from dark-light experiments. The ozone loss obtained from the

  6. What happens when iron becomes wet? Observation of reactions at interfaces between liquid and metal surfaces

    CERN Document Server

    Kimura, M

    2003-01-01

    Synchrotron-radiation has been applied to investigation of interfaces between liquid and metal surfaces, with a special attention to corrosion. Three topics are shown: (1) nano structures of rusts formed on steel after atmospheric corrosion. Evolution of 'Fe(O, OH) sub 6 network' is the key to understand how the durable rusts prevent from formation of more rusts. (2) In situ observation of reactions at the interface has been carried out for localized corrosion of stainless steel. It is shown that change in states of Cr sup 3 sup + and Br sup - ions near the interface is deeply related with a breakout of the passivation film. (3) A structural phase transformation on a Cu sub 3 Au(001) surface was investigated. Ordering remains even at a temperature higher than the bulk-critical temperature, showing surface-induced ordering. These approaches gives us crucial information for a new steel-product. (author)

  7. Modifications of hemoglobin and myoglobin by Maillard reaction products (MRPs.

    Directory of Open Access Journals (Sweden)

    Aristos Ioannou

    Full Text Available High performance liquid chromatography (HPLC coupled with a Fraction Collector was employed to isolate Maillard reaction products (MRPs formed in model systems comprising of asparagine and monosaccharides in the 60-180°C range. The primary MRP which is detected at 60°C is important for Acrylamide content and color/aroma development in foods and also in the field of food biotechnology for controlling the extent of the Maillard reaction with temperature. The discrete fractions of the reaction products were reacted with Hemoglobin (Hb and Myoglobin (Mb at physiological conditions and the reaction adducts were monitored by UV-vis and Attenuated Total Reflection-Fourier transform infrared (FTIR spectrophotometry. The UV-vis kinetic profiles revealed the formation of a Soret transition characteristic of a low-spin six-coordinated species and the ATR-FTIR spectrum of the Hb-MRP and Mb-MRP fractions showed modifications in the protein Amide I and II vibrations. The UV-vis and the FTIR spectra of the Hb-MRPs indicate that the six-coordinated species is a hemichrome in which the distal E7 Histidine is coordinated to the heme Fe and blocks irreversibly the ligand binding site. Although the Mb-MRPs complex is a six-coordinated species, the 1608 cm-1 FTIR band characteristic of a hemichrome was not observed.

  8. Modifications of hemoglobin and myoglobin by Maillard reaction products (MRPs).

    Science.gov (United States)

    Ioannou, Aristos; Varotsis, Constantinos

    2017-01-01

    High performance liquid chromatography (HPLC) coupled with a Fraction Collector was employed to isolate Maillard reaction products (MRPs) formed in model systems comprising of asparagine and monosaccharides in the 60-180°C range. The primary MRP which is detected at 60°C is important for Acrylamide content and color/aroma development in foods and also in the field of food biotechnology for controlling the extent of the Maillard reaction with temperature. The discrete fractions of the reaction products were reacted with Hemoglobin (Hb) and Myoglobin (Mb) at physiological conditions and the reaction adducts were monitored by UV-vis and Attenuated Total Reflection-Fourier transform infrared (FTIR) spectrophotometry. The UV-vis kinetic profiles revealed the formation of a Soret transition characteristic of a low-spin six-coordinated species and the ATR-FTIR spectrum of the Hb-MRP and Mb-MRP fractions showed modifications in the protein Amide I and II vibrations. The UV-vis and the FTIR spectra of the Hb-MRPs indicate that the six-coordinated species is a hemichrome in which the distal E7 Histidine is coordinated to the heme Fe and blocks irreversibly the ligand binding site. Although the Mb-MRPs complex is a six-coordinated species, the 1608 cm-1 FTIR band characteristic of a hemichrome was not observed.

  9. A novel reaction catalysed by active carbons production of dichloromethane from phosgene and formaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, T A; Stacey, M H

    1984-08-01

    A variety of Activated charcoals have been found to catalyse a reaction between phosgene and formaldehyde. In a continuous flow fluidized bed reactor, the reaction rate reaches a broad maximum near 170/sup 0/C where the selectivity is consistent with the stoichiometry. The reaction proceeds via a strongly adsorbed intermediate which has been identified as chloromethyl chloroformate. This ester is an adduct of formaldehyde and phosgen and forms rapidly above 100/sup 0/C in co-adsorption/desorption experiments. It decomposes rapidly 170/sup 0/C without significant desorption of the intact molecule to give the observed products dichloromethane and carbon dioxide. Under steady-state conditions the rate-determining step is the formation of this ester so that it is normally only present on the surface at low coverages; hence it is not observable in the gas phase. The catalysis is probably due to the presence of polar acid or base sites on the surface of the activated charcoals.

  10. SurfKin: an ab initio kinetic code for modeling surface reactions.

    Science.gov (United States)

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-05

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

  11. Products of the reaction between methylene iodide and tertiary arsines

    International Nuclear Information System (INIS)

    Gigauri, R.D.; Arabuli, L.G.; Machaidze, Z.I.; Rusiya, M.Sh.

    2005-01-01

    Iodides of iodomethylenetrialkyl(aryl) arsonium were synthesized with high yields as a result of interaction between methylene iodide and tertiary arsines. Exchange reactions of the iodides prepared with lead(II) nitrate in water-alcohol solutions gave rise to formation of iodomethylenetrialkyl(aryl) arsonium nitrates. All the products prepared were characterized by data of elementary analysis, IR spectroscopy, conductometry and melting points measurements [ru

  12. The hydrogen atom-deuterium molecule reaction: Experimental determination of product quantum state distributions

    International Nuclear Information System (INIS)

    Rinnen, K.

    1989-01-01

    The H + H 2 atom exchange reaction (and its isotopic analogs) is the simplest neutral bimolecular chemical reaction because of the small number of electrons in the system and the lightness of the nuclei. The H 3 potential energy surface (PES) is the most accurately known reactive surface (LSTH surface); there have been both quasiclassical trajectory (QCT) and quantal calculations performed on it. This is one of the few systems for which theory is ahead of experiment, and many theoretical predictions await experimental comparison. The H + D 2 → HD + D reaction is studied using thermal D 2 (∼298 K) and translationally hot hydrogen atoms. Photolysis of HI at 266 nm generates H atoms with center-of-mass collision energies of 1.3 and 0.55 eV, both of which are above the classical reaction barrier of 0.42 eV. The rovibrational population distribution of the molecular product is measured by (2+1) resonance-enhanced multiphoton ionization (REMPI). A major effort has been directed toward calibrating the (2+1) REMPI detection procedure, to determine quantitatively the relationship between ion signals and relative quantum state populations for HD. An effusive, high-temperature nozzle has been constructed to populate thermally the high rovibrational levels observed in the reaction. The results are compared to theoretical calculations of the E,F 1 Σ g + - X 1 Σ g + two-photon transition moments. For the H + D 2 reaction, the populations of all energetically accessible HD product levels are measured. Specifically, the following levels are observed: HD(v = 0, J = 0-15), HD(v = 1, J = 0-12), and HD(v = 2, J = 0-8). Of the available energy, 73% is partitioned into product translation, 18% into HD rotation, and 9% into HD vibration

  13. Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

    Science.gov (United States)

    Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

    2014-07-01

    Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

  14. Enzymatic Transesterification of Ethyl Ferulate with Fish Oil and Reaction Optimization by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Zhiyong Yang

    2012-01-01

    Full Text Available The enzymatic transesterification of ethyl ferulate (EF with fish oil from cod liver was investigated with Novozym® 435 as catalyst under solvent-free conditions. The purpose of the study is to evaluate the synthesis system for the production of feruloyl fish oil in industry. The modified HPLC method was first set up to characterise the reaction products together with liquid chromatography electrospray time-of-flight mass spectrometry (HPLC-ESI-TOF-MS. The influence of the addition of glycerol to the system on the feruloyl acylglycerol profile was investigated in terms of transesterification performance. The bioconversion rate of EF can be significantly increased with the increased formation of feruloyl fish oil products when appropriate amount of glycerol is present in the reaction. Therefore, an equivalent molar amount of glycerol was added to EF for the practical optimization of the system. The mutual effects of temperature (40 to 70 °C, reaction time (1 to 5 days, enzyme load (2 to 20 % and molar ratio of fish oil and EF in the substrate (1 to 5 were thus studied with the assistance of response surface methodology (RSM for the purpose of maximizing the formation of feruloyl fish oil. The models were well fitted and verified. The optimized conditions were found to be: temperature 70 °C, enzyme load 4.3 %, substrate ratio 4.7, and reaction time 5 days. Under these conditions, the maximum conversion of EF reached 92.4 %, and the formation of feruloyl fish oil reached 80.4 %, but the formation of by-product was minimized to 11.4 % only.

  15. Production and decay of baryonic resonances in pion induced reactions

    Directory of Open Access Journals (Sweden)

    Przygoda Witold

    2016-01-01

    Full Text Available Pion induced reactions give unique opportunities for an unambiguous description of baryonic resonances and their coupling channels. A systematic energy scan and high precision data, in conjunction with a partial wave analysis, allow for the study of the excitation function of the various contributions. A review of available world data unravels strong need for modern facilities delivering measurements with a pion beam. Recently, HADES collaboration collected data in pion-induced reactions on light (12C and heavy (74W nuclei at a beam momentum of 1.7 GeV/c dedicated to strangeness production. It was followed by a systematic scan at four different pion beam momenta (0.656, 0.69, 0.748 and 0.8 GeV/c in π− − p reaction in order to tackle the role of N(1520 resonance in conjunction with the intermediate ρ production. First results on exclusive channels with one pion (π− p and two pions (nπ+π−, pπ−π0 in the final state are discussed.

  16. Plasma fluctuations and confinement of fusion reaction products

    International Nuclear Information System (INIS)

    Coppi, B.; Pegoraro, F.

    1981-01-01

    The interaction between the fluctuations that can be excited in a magnetically confined plasma and the high-energy-particle population produced by fusion reactions is analyzed in view of its relevance to the process of thermonuclear ignition. The spectrum of the perturbations that, in the absence of fusion reaction products, would be described by the incompressible ideal magnetohydrodynamic approximation is studied considering finite value of the plasma pressure relative ot the magnetic pressure. The combined effects of the magnetic field curvature and shear are taken into account and the relevant spectrum is shown to consist of a continuous portion, that could be identified as a mixture of shear-Alfven and interchange oscillations, and a discrete unstable part corresponding to the so-called ballooning modes. The rate of diffusion of the fusion reaction products induced by oscillations in the continuous part of the spectrum, as estimated from the appropriate quasi-linear theory, is found to be significantly smaller than could be expected if normal modes (i.e., nonconvective solutions) were excited. However, a relatively wide intermediate region is identified where opalescent fluctuations, capable of achieving significant amplitudes and corresponding to a quasi-discrete spectrum, can be excited

  17. 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

  18. 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.

  19. Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

    International Nuclear Information System (INIS)

    Zamfirescu, C.; Naterer, G.F.; Dincer, I.

    2009-01-01

    The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

  20. Volatilization and reaction of fission products in flowing steam

    International Nuclear Information System (INIS)

    Johnson, I.; Steidl, D.V.; Johnson, C.E.

    1985-01-01

    The principal risk to the public from nuclear power plants derives from the highly radioactive atoms (fission products) generated as energy is produced in the nuclear fuel. The revolatilization of fission products from reactor system surfaces due to self-heating by radioactive decay has become a complicating factor in the source-term redefinition effort. It has had a major impact on calculations of fission product distributions in accident safety analyses. The focus of this research effort was to investigate the volatilization and transport of fission products and control rod materials in a flowing gaseous steam-hydrogen mixture. Fission product and control rod materials in various combinations were studied including CsI, CsOH, TeO 2 , SrO, Ag, In, Cd and Mn. The vaporization behavior of the deposits were characterized with respect to vaporization rates, chemical species and downstream transport behavior

  1. 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.

  2. Energy Accommodation from Surface Catalyzed Reactions in Air Plasmas

    Data.gov (United States)

    National Aeronautics and Space Administration — Understanding energy transport at the gas-surface interface between catalytic/reacting surfaces exposed to highly dissociated plasmas remains a significant research...

  3. 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

  4. 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....

  5. Production of Energetic Light Fragments in Spallation Reactions

    Directory of Open Access Journals (Sweden)

    Mashnik Stepan G.

    2014-03-01

    Full Text Available Different reaction mechanisms contribute to the production of light fragments (LF from nuclear reactions. Available models cannot accurately predict emission of LF from arbitrary reactions. However, the emission of LF is important formany applications, such as cosmic-ray-induced single event upsets, radiation protection, and cancer therapy with proton and heavy-ion beams, to name just a few. The cascade-exciton model (CEM and the Los Alamos version of the quark-gluon string model (LAQGSM, as implemented in the CEM03.03 and LAQGSM03.03 event generators used in the Los Alamos Monte Carlo transport code MCNP6, describe quite well the spectra of fragments with sizes up to 4He across a broad range of target masses and incident energies. However, they do not predict high-energy tails for LF heavier than 4He. The standard versions of CEM and LAQGSM do not account for preequilibrium emission of LF larger than 4He. The aim of our work is to extend the preequilibrium model to include such processes. We do this by including the emission of fragments heavier than 4He at the preequilibrium stage, and using an improved version of the Fermi Break-up model, providing improved agreement with various experimental data.

  6. Two dimensional simulation of hydrogen iodide decomposition reaction using fluent code for hydrogen production using nuclear technology

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Jung Sik [The Institute of Machinery and Electronic Technology, Mokpo National Maritime University, Mokpo (Korea, Republic of); Shin, Young Joon; Lee, Ki Young [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Choi, Jae Hyuk [Division of Marine Engineering System, Korea Maritime and Ocean University, Busan (Korea, Republic of)

    2015-06-15

    The operating characteristics of hydrogen iodide (HI) decomposition for hydrogen production were investigated using the commercial computational fluid dynamics code, and various factors, such as hydrogen production, heat of reaction, and temperature distribution, were studied to compare device performance with that expected for device development. Hydrogen production increased with an increase of the surface-to-volume (STV) ratio. With an increase of hydrogen production, the reaction heat increased. The internal pressure and velocity of the HI decomposer were estimated through pressure drop and reducing velocity from the preheating zone. The mass of H2O was independent of the STV ratio, whereas that of HI decreased with increasing STV ratio.

  7. NUCLEAR MAGNETIC RESONANCE THE GELLED PRODUCT OF CANNIZZARO REACTION

    Directory of Open Access Journals (Sweden)

    Lilia Fernández-Sánchez

    2015-03-01

    Full Text Available The paper presents the nuclear magnetic resonance (NMR of proton 1H, carbon 13C and two dimensional spectrums, product of a green organic synthesis of redox on the Cannizzaro reaction. The product was reported as a tribochemical gel (heterogeneous mixture and confirmed by Infrared Spectroscopy IR, X-ray and scanning electron microscope (SEM. The results in this paper confirm its structure through various techniques of NMR and evaluate the content of sodium benzoate and benzyl alcohol in the spectroscopy sample, examining the values of the integrals on 1H NMR signals. The result of analysis indicates that benzyl alcohol (dispersed phase is in 33.44% mol in comparison with sodium benzoate content (continuous phase. These results confirm that the gel structure over time loses the dispersed phase of the benzyl alcohol producing a xerogel.

  8. Studies of evaporation residue products from krypton and argon reactions

    International Nuclear Information System (INIS)

    Plasil, F.; Ferguson, R.L.; Britt, H.C.; Erkkila, B.H.; Blann, M.; Gutbrod, H.H.; California Univ., Berkeley

    1978-01-01

    Mass distributions of evaporation residue (ER) products from 86 Kr-bombardments of 70 Ge and 74 Ge have been obtained by a time-of-flight method at energies ranging from the interaction barrier to 706 MeV. ER excitation functions have also been obtained for a variety of target and projectile combinations. Results are compared with statistical model calculations and with results obtained from γ-measurements. It is deduced that at the lowest impact parameters, the reaction products belong to the ER group, in contrast with the angular momentum hypothesis of Lefort. Cross sections were found to be consistent with an angular momentum limit arising from the onset of fission. (orig.) [de

  9. 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.

  10. Optimization of the production of ethyl esters by ultrasound assisted reaction of soybean oil and ethanol

    Directory of Open Access Journals (Sweden)

    S. Rodrigues

    2009-06-01

    Full Text Available Biodiesel is a renewable liquid fuel that can be produced by a transesterification reaction between a vegetable oil and an alcohol. This paper evaluates and optimizes the production of ethyl esters (biodiesel from soybean oil and ethanol. The reaction was carried out by applying ultrasound under atmospheric pressure and ambient temperature. Response surface methodology was used to evaluate the influence of alcohol to oil molar ratio and catalyst concentration on the yield of conversion of soybean oil into ethyl esters. The process resulted in a maximum yield of 91.8% after 30 minutes of reaction. The process variables alcohol to oil ratio and catalyst to oil ratio were statistically significant regarding the yield of ethyl esters. The optimal operating condition was obtained applying an alcohol to oil molar ratio of 10.2 and a catalyst to oil weight ratio of 0.0035.

  11. Fluorescent Carbon Dots Derived from Maillard Reaction Products: Their Properties, Biodistribution, Cytotoxicity, and Antioxidant Activity.

    Science.gov (United States)

    Li, Dongmei; Na, Xiaokang; Wang, Haitao; Xie, Yisha; Cong, Shuang; Song, Yukun; Xu, Xianbing; Zhu, Bei-Wei; Tan, Mingqian

    2018-02-14

    Food-borne nanoparticles have received great attention because of their unique physicochemical properties and potential health risk. In this study, carbon dots (CDs) formed during one of the most important chemical reactions in the food processing field, the Maillard reaction from the model system including glucose and lysine, were investigated. The CDs purified from Maillard reaction products emitted a strong blue fluorescence under ultraviolet light with a fluorescent quantum yield of 16.30%. In addition, they were roughly spherical, with sizes of around 4.3 nm, and mainly composed of carbon, oxygen, hydrogen, and nitrogen. Their surface groups such as hydroxyl, amino, and carboxyl groups were found to possibly enable CDs to scavenge DPPH and hydroxyl radicals. Furthermore, the cytotoxicity assessment of CDs showed that they could readily enter HepG2 cells while causing negligible cell death at low concentration. However, high CDs concentrations were highly cytotoxic and led to cell death via interference of the glycolytic pathway.

  12. An investigation of oxidation products and SOA yields from OH + pesticide reactions

    Science.gov (United States)

    Murschell, T.; Friedman, B.; Link, M.; Farmer, D.

    2016-12-01

    Pesticides are used globally in agricultural and residential areas. After application and/or volatilization from a surface, these compounds can be transported over long distances in the atmosphere. However, their chemical fate, including oxidation and gas-particle partitioning in the atmosphere, is not well understood. We present gas and particle measurements of oxidation products from pesticide + OH reactions using a dynamic solution injection system coupled to an Oxidative Flow Reactor. Products were detected with a High Resolution Time of Flight Iodide Chemical Mass Spectrometer (HR-ToF-CIMS) and a Size Mobility Particle Scanner (SMPS). The OFR allows pesticides to react with variable OH radical exposures, ranging from the equivalent of one day to a full week of atmospheric oxidative aging. In this work, we explore pesticide oxidation products from reaction with OH and ozone, and compare those products to photolysis reactions. Pesticides of similar chemical structures were explored, including acetochlor / metolachlor and permethrin / cypermethrin, to explore mechanistic differences. We present chemical parameters including average product oxidation state, average oxygen to carbon ratio, and potential secondary organic aerosol formation for each of these compounds.

  13. Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time.

    Science.gov (United States)

    Thompson, Katherine C; Rennie, Adrian R; King, Martin D; Hardman, Samantha J O; Lucas, Claire O M; Pfrang, Christian; Hughes, Brian R; Hughes, Arwel V

    2010-11-16

    The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known about the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface, suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of (1)H-POPC on D(2)O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air-water interface leading to the formation of OH radicals. The highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation of oxidized lipids with shorter alkyl tails.

  14. Potential surfaces in symmetric heavy-ion reactions

    International Nuclear Information System (INIS)

    Royer, G.; Piller, C.; Mignen, J.; Raffray, Y.

    1989-01-01

    The entrance channel in symmetric heavy-ion reactions is studied in the liquid-drop model approach including the nuclear proximity energy and allowing ellipsoidal deformations of the colliding nuclei. In the whole mass range a sudden transition occurs from oblate to prolate shapes when the proximity forces become important. This strongly affects the effective moment of inertia. The ellipsoidal deformations reduce the fusion barrier width for light systems and lower the potential barrier height for medium and heavy nuclei. The results are in agreement with the empirical effective barrier shift determined by Aguiar et al for the 58 Ni + 58 Ni, 74 Ge + 74 Ge and 80 Se + 80 Se systems. The sub-barrier fusion enhancement in heavy-ion reactions might be explained by the slowness of the process. Below the static fusion barrier, the reaction time is long; allowing some adiabaticity and deformations of the colliding ions. Above the barrier, the reaction is more sudden and the deformation degree of freedom is frozen

  15. Performing chemical reactions in virtual capillary of surface tension ...

    Indian Academy of Sciences (India)

    The flow paths were fabricated by making parallel lines using permanent marker pen ink or other polymer on glass surfaces. Two mirror image patterned glass plates were then sandwiched one on top of the other, separated by a thin gap - created using a spacer. The aqueous liquid moves between the surfaces by capillary ...

  16. 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.

  17. Flavin-catalyzed redox tailoring reactions in natural product biosynthesis.

    Science.gov (United States)

    Teufel, Robin

    2017-10-15

    Natural products are distinct and often highly complex organic molecules that constitute not only an important drug source, but have also pushed the field of organic chemistry by providing intricate targets for total synthesis. How the astonishing structural diversity of natural products is enzymatically generated in biosynthetic pathways remains a challenging research area, which requires detailed and sophisticated approaches to elucidate the underlying catalytic mechanisms. Commonly, the diversification of precursor molecules into distinct natural products relies on the action of pathway-specific tailoring enzymes that catalyze, e.g., acylations, glycosylations, or redox reactions. This review highlights a selection of tailoring enzymes that employ riboflavin (vitamin B2)-derived cofactors (FAD and FMN) to facilitate unusual redox catalysis and steer the formation of complex natural product pharmacophores. Remarkably, several such recently reported flavin-dependent tailoring enzymes expand the classical paradigms of flavin biochemistry leading, e.g., to the discovery of the flavin-N5-oxide - a novel flavin redox state and oxygenating species. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. 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)

  19. Reaction of Br2 with adsorbed CO on Pt, studied by the surface interrogation mode of scanning electrochemical microscopy.

    Science.gov (United States)

    Wang, Qian; Rodríguez-López, Joaquín; Bard, Allen J

    2009-12-02

    Scanning electrochemical microscopy surface interrogation (SI-SECM) in the cyclic voltammetry mode was successfully used to detect and quantify adsorbed CO on a Pt electrode by reaction with electrogenerated Br(2). The two-electrode setup used in this new technique allowed the production of Br(2) on an interrogator tip, which reported a transient positive feedback above a Pt substrate at open circuit as an indication of the reactivity of this halogen with CO((ads)). Br(-) and CO(2) are shown to be the main products of the reaction (in the absence of O(2)), which may involve the formation of bromophosgene as a hydrolyzable intermediate. Under saturation conditions, CO((ads)) was reproducibly quantified at the polycrystalline Pt surface with theta(CO) approximately = 0.5. The reaction is shown to be blocked by the action of pre-adsorbed cyanide, which demonstrates the surface character of the process. The formation of CO(2) as an end product was further tested in a bulk experiment: addition of Pt black to a mixture of Br(2) in 0.5 M H(2)SO(4) through which CO was bubbled gave a precipitate of BaCO(3) in a saturated solution of Ba(OH)(2). The use of SI-SECM allowed access to a reaction that would otherwise be difficult to prove through conventional electrochemistry on a single electrode.

  20. Fluctuation-Induced Pattern Formation in a Surface Reaction

    DEFF Research Database (Denmark)

    Starke, Jens; Reichert, Christian; Eiswirth, Markus

    2006-01-01

    Spontaneous nucleation, pulse formation, and propagation failure have been observed experimentally in CO oxidation on Pt(110) at intermediate pressures ($\\approx 10^{-2}$mbar). This phenomenon can be reproduced with a stochastic model which includes temperature effects. Nucleation occurs randomly...... due to fluctuations in the reaction processes, whereas the subsequent damping out essentially follows the deterministic path. Conditions for the occurence of stochastic effects in the pattern formation during CO oxidation on Pt are discussed....

  1. Evaluation of Neutron Induced Reactions for 32 Fission Products

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyeong Il

    2007-02-15

    Neutron cross sections for 32 fission products were evaluated in the neutron-incident energy range from 10{sup -5} eV to 20 MeV. The list of fission products consists of the priority materials for several applications, extended to cover complete isotopic chains for three elements. The full list includes 8 individual isotopes, {sup 95}Mo, {sup 101}Ru, {sup 103}Rh, {sup 105}Pd, {sup 109}Ag, {sup 131}Xe, {sup 133}Cs, {sup 141}Pr, and 24 isotopes in complete isotopic chains for Nd (8), Sm (9) and Dy (7). Our evaluation methodology covers both the low energy region and the fast neutron region.In the low energy region, our evaluations are based on the latest data published in the Atlas of Neutron Resonances. This resource was used to infer both the thermal values and the resolved resonance parameters that were validated against the capture resonance integrals. In the unresolved resonance region we performed the additional evaluation by using the averages of the resolved resonances and adjusting them to the experimental data.In the fast neutron region our evaluations are based on the nuclear reaction model code EMPIRE-2.19 validated against the experimental data. EMPIRE is the modular system of codes consisting of many nuclear reaction models, including the spherical and deformed Optical Model, Hauser-Feshbach theory with the width fluctuation correction and complete gamma-ray emission cascade, DWBA, Multi-step Direct and Multi-step Compound models, and several versions of the phenomenological preequilibrium models. The code is equipped with a power full GUI, allowing an easy access to support libraries such as RIPL and CSISRS, the graphical package, as well the utility codes for formatting and checking. In general, in our calculations we used the Reference Input Parameter Library, RIPL, for the initial set model parameters. These parameters were properly adjusted to reproduce the available experimental data taken from the CSISRS library. Our evaluations cover cross

  2. Evaluation of Neutron Induced Reactions for 32 Fission Products

    International Nuclear Information System (INIS)

    Kim, Hyeong Il

    2007-02-01

    Neutron cross sections for 32 fission products were evaluated in the neutron-incident energy range from 10 -5 eV to 20 MeV. The list of fission products consists of the priority materials for several applications, extended to cover complete isotopic chains for three elements. The full list includes 8 individual isotopes, 95 Mo, 101 Ru, 103 Rh, 105 Pd, 109 Ag, 131 Xe, 133 Cs, 141 Pr, and 24 isotopes in complete isotopic chains for Nd (8), Sm (9) and Dy (7). Our evaluation methodology covers both the low energy region and the fast neutron region.In the low energy region, our evaluations are based on the latest data published in the Atlas of Neutron Resonances. This resource was used to infer both the thermal values and the resolved resonance parameters that were validated against the capture resonance integrals. In the unresolved resonance region we performed the additional evaluation by using the averages of the resolved resonances and adjusting them to the experimental data.In the fast neutron region our evaluations are based on the nuclear reaction model code EMPIRE-2.19 validated against the experimental data. EMPIRE is the modular system of codes consisting of many nuclear reaction models, including the spherical and deformed Optical Model, Hauser-Feshbach theory with the width fluctuation correction and complete gamma-ray emission cascade, DWBA, Multi-step Direct and Multi-step Compound models, and several versions of the phenomenological preequilibrium models. The code is equipped with a power full GUI, allowing an easy access to support libraries such as RIPL and CSISRS, the graphical package, as well the utility codes for formatting and checking. In general, in our calculations we used the Reference Input Parameter Library, RIPL, for the initial set model parameters. These parameters were properly adjusted to reproduce the available experimental data taken from the CSISRS library. Our evaluations cover cross sections for almost all reaction channels

  3. 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.

  4. Evidence for the Active Phase of Heterogeneous Catalysts through In Situ Reaction Product Imaging and Multiscale Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Matera, S.; Blomberg, S.; Hoffmann, M. J.; Zetterberg, J.; Gustafson, J.; Lundgren, E.; Reuter, K.

    2015-06-17

    We use multiscale modeling to analyze laser-induced fluorescence (LIF) measurements of the CO oxidation reaction over Pd(100) at near-ambient reaction conditions. Integrating density functional theory-based kinetic Monte Carlo simulations of the active catalyst into fluid-dynamical simulations of the mass transport inside the reactor chamber, we calculate the reaction product concentration directly above the catalyst surface. Comparing corresponding data calculated for different surface models against the measured LIF signals, we can discriminate the one that predominantly actuates the experimentally measured catalytic activity. For the probed CO oxidation reaction conditions, the experimental activity is due to pristine Pd(100) possibly coexisting with other (oxidic) domains on the surface.

  5. Flavor production in bar pp reactions at low energies

    International Nuclear Information System (INIS)

    Eisenstein, R.A.

    1994-01-01

    Associated production processes have been known since the 1050's. The solution to the puzzle they presented was to introduce the 'strangeness' quantum number, along with the notion of its conservation in strong interactions. For example, the reaction π + n → K + Λ is described both as the t-channel exchange of a K 0 meson, ans as an s-channel process involving the annihilation of a d bar d quark pair and the subsequent production of an s bar s pair. This basic 'flavor-production' process and ones like it are the focus of widespread interest and the subject of this talk. The physics to be addressed is the nature of the quark annihilation and the creation process, which is expected to proceed according to the rules of quantum chromodynamics (QCD). According to these ideas, it will be dominated by perturbative QCD (essentially single-gluon exchange) at high momentum; at low momentum the process is expected to involve a very complicated multiple gluon exchange since it is in the nonperturbative regime

  6. 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.

  7. Maillard reaction products as antimicrobial components for packaging films.

    Science.gov (United States)

    Hauser, Carolin; Müller, Ulla; Sauer, Tanja; Augner, Kerstin; Pischetsrieder, Monika

    2014-02-15

    Active packaging foils with incorporated antimicrobial agents release the active ingredient during food storage. Maillard reaction products (MRPs) show antimicrobial activity that is at least partially mediated by H2O2. De novo generation of H2O2 by an MRP fraction, extracted from a ribose/lysine Maillard reaction mixture by 85% ethanol, was monitored at three concentrations (1.6, 16.1, and 32.3g/L) and three temperatures (4, 25, and 37 °C) between 0 and 96 h, reaching a maximum of 335 μM H2O2 (32.3g/L, 37 °C, 96 h). The active MRP fraction (16.1g/L) completely inhibited the growth of Escherichia coli for 24h and was therefore incorporated in a polyvinyl acetate-based lacquer and dispersed onto a low-density polyethylene film. The coated film generated about 100 μM H2O2 and resulted in a log-reduction of >5 log-cycles against E. coli. Thus, MRPs can be considered as active ingredients for antimicrobial packaging materials. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Production cross sections of proton-induced reactions on yttrium

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Sung-Chul; Song, Tae-Yung; Lee, Young-Ouk [Nuclear Data Center, Korea Atomic Energy Research Institute, Daejeon 34057 (Korea, Republic of); Kim, Guinyun, E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 41566 (Korea, Republic of)

    2017-05-01

    The production cross sections of residual radionuclides such as {sup 86,88,89g}Zr, {sup 86g,87m,87g,88}Y, {sup 83g,85g}Sr, and {sup 83,84g}Rb in the {sup 89}Y(p,x) reaction were measured using a stacked-foil activation and offline γ-ray spectrometric technique with proton energies of 57 MeV and 69 MeV at the 100 MeV proton linac in the Korea Multi-purpose Accelerator Complex (KOMAC), Gyeongju, Korea. The induced activities of the activated samples were measured using a high purity germanium (HPGe) detector, and the proton flux was determined using the {sup nat}Cu(p,x){sup 62}Zn reaction. The measured data was compared with other experimental data and the data from the TENLD-2015 library based on the TALYS code. The present results are generally lower than those in literature, but are found to be in agreement with the shape of the excitation functions. The integral yields for the thick target using the measured cross sections are given.

  9. Reactions and reaction intermediates on iron surfaces--1. Methanol, ethanol, and isopropanol on Fe(100). 2. Hydrocarbons and carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Benziger, J.B.; Madix, R.J.

    1980-09-01

    Temperature-programed desorption and ESCA showed that the alcohols formed alkoxy intermediates on Fe(100) surfaces at room temperature, but that the methoxy and ethoxy species were much more stable than the isopropoxy intermediate. The alkoxy species reacted above 400/sup 0/K by decomposing into carbon monoxide and hydrogen, hydrogenation to alcohol, and scission of C-C and C-O bonds with hydrogenation of the hydrocarbon fragments. Ethylene, acetylene, and cis-2-butene formed stable, unidentified surface species. Methyl chloride formed stable surface methyl groups which decomposed into hydrogen and surface carbide at 475/sup 0/K. Formic and acetic acids yielded stable carboxylate intermediates which decomposed above 490/sup 0/K to hydrogen, carbon monoxide, and carbon dioxide. The studies suggested that the alkoxy surface species may be important intermediates in the Fischer-Tropsch reaction on iron.

  10. Near threshold two meson production in hardonic fusion reactions

    International Nuclear Information System (INIS)

    Jahn, R.

    1991-01-01

    An approved and funded exclusive COSY experiment is presented, which focuses on near threshold two meson production via the reactions p+d→ 3 He + π + π - and p+d→ 3 He+K + K-. It takes advantage of the high quality of the cooled external COSY beam and the existing spectrometer BIG KARL. The setup consists of a vertex wall and a scintillator cylinder and endcap covering a 4π solid angle. The large efficiency and high resolution of this detection method will yield precision data on the low energy (T 0 (975). Existing inclusive data as well as first results of a very recent 'semi-exclusive' experiment performed at SATURNE will be also be presented

  11. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    International Nuclear Information System (INIS)

    Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang

    2016-01-01

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H_2O_2 concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K_C_A_T and K_C_A_T/K_M values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H_2O_2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H_2O_2 concentration, while the optimal pH and H_2O_2 concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL"−"1 SBP in 30 min reaction time, while an HRP dose of 0.3 U mL"−"1 was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K_C_A_T) and catalytic efficiency (K_C_A_T/K_M) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment.

  12. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jianhua; Peng, Jianbiao [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Zhang, Ya [Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection of the People’s Republic of China, Nanjing 210042 (China); Ji, Yuefei [College of Resources and Environmental Science, Nanjing Agricultural University, Nanjing 210095 (China); Shi, Huanhuan; Mao, Liang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Gao, Shixiang, E-mail: ecsxg@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-06-05

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H{sub 2}O{sub 2} concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K{sub CAT} and K{sub CAT}/K{sub M} values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H{sub 2}O{sub 2} concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H{sub 2}O{sub 2} concentration, while the optimal pH and H{sub 2}O{sub 2} concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL{sup −1} SBP in 30 min reaction time, while an HRP dose of 0.3 U mL{sup −1} was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K{sub CAT}) and catalytic efficiency (K{sub CAT}/K{sub M}) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water

  13. Sorption enhanced reaction process (SERP) for the production of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Hufton, J.; Mayorga, S.; Gaffney, T.; Nataraj, S.; Rao, M.; Sircar, S. [Air Products and Chemicals, Inc., Allentown, PA (United States)

    1998-08-01

    The novel Sorption Enhanced Reaction Process has the potential to decrease the cost of hydrogen production by steam methane reforming. Current effort for development of this technology has focused on adsorbent development, experimental process concept testing, and process development and design. A preferred CO{sub 2} adsorbent, K{sub 2}CO{sub 3} promoted hydrotalcite, satisfies all of the performance targets and it has been scaled up for process testing. A separate class of adsorbents has been identified which could potentially improve the performance of the H{sub 2}-SER process. Although this material exhibits improved CO{sub 2} adsorption capacity compared to the HTC adsorbent, its hydrothermal stability must be improved. Single-step process experiments (not cyclic) indicate that the H{sub 2}-SER reactor performance during the reaction step improves with decreasing pressure and increasing temperature and steam to methane ratio in the feed. Methane conversion in the H{sub 2}-SER reactor is higher than for a conventional catalyst-only reactor operated at similar temperature and pressure. The reactor effluent gas consists of 90+% H{sub 2}, balance CH{sub 4}, with only trace levels (< 50 ppm) of carbon oxides. A best-case process design (2.5 MMSCFD of 99.9+% H{sub 2}) based on the HTC adsorbent properties and a revised SER process cycle has been generated. Economic analysis of this design indicates the process has the potential to reduce the H{sub 2} product cost by 25--31% compared to conventional steam methane reforming.

  14. Experimental measurements of negative hydrogen ion production from surfaces

    International Nuclear Information System (INIS)

    Graham, W.G.

    1977-09-01

    Experimental measurements of the production of H - from surfaces bombarded with hydrogen are reviewed. Some measurements of H + and H 0 production from surfaces are also discussed with particular emphasis on work which might be relevant to ion source applications

  15. Sorption Enhanced Reaction Process (SERP) for production of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Anand, M.; Hufton, J.; Mayorga, S. [Air Products and Chemicals, Inc., Allentown, PA (United States)] [and others

    1996-10-01

    Sorption Enhanced Reaction Process (SERP) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The key consequences of SERP are: (i) reformation reaction is carried out at a significantly lower temperature (300-500{degrees}C) than that in a conventional SMR reactor (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (ii) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 98+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (iii) downstream hydrogen purification step is either eliminated or significantly reduced in size. The first phase of the program has focused on the development of a sorbent for CO{sub 2} which has (a) reversible CO{sub 2} capacity >0.3 mmol/g at low partial pressures of CO{sub 2} (0.1 - 1.0 atm) in the presence of excess steam (pH{sub 2}O/pCO{sub 2}>20) at 400-500{degrees}C and (b) fast sorption-desorption kinetics for CO{sub 2}, at 400-500{degrees}C. Several families of supported sorbents have been identified that meet the target CO{sub 2} capacity. A few of these sorbents have been tested under repeated sorption/desorption cycles and extended exposure to high pressure steam at 400-500{degrees}C. One sorbent has been scaled up to larger quantities (2-3 kg) and tested in the laboratory process equipment for sorption and desorption kinetics of CO{sub 2}. The CO{sub 2}, sorption and desorption kinetics are desirably fast. This was a critical path item for the first phase of the program and now has been successfully demonstrated. A reactor has been designed that will allow nearly isothermal operation for SERP-SMR. This reactor was integrated into an overall process flow diagram for the SERP-SMR process.

  16. 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.

  17. Transfusion reactions in pediatric compared with adult patients: a look at rate, reaction type, and associated products.

    Science.gov (United States)

    Oakley, Fredrick D; Woods, Marcella; Arnold, Shanna; Young, Pampee P

    2015-03-01

    The majority of reports on transfusion reactions address adult patients. Less is known about the types, incidence, and other clinical details of transfusion reactions in pediatric populations. Furthermore, to our knowledge, there have been no previous reports directly comparing these aspects between adults and pediatric patient populations to assess if there are differences. Between the period of January 1, 2011, and February 1, 2013, all reported adult and pediatric transfusion reactions at Vanderbilt University Medical Center (VUMC) were evaluated by transfusion medicine clinical service. The information was subsequently shared with the hemovigilance database. Data provided to hemovigilance included age, sex, blood product associated with the reaction, severity of the reaction, and the type of transfusion reactions. These were collated with hospital and blood bank information system-acquired data on overall admission and product transfusion. A total of 133,671 transfusions were performed at VUMC during the study period including 20,179 platelet (PLT) transfusions, 31,605 plasma transfusions, 79,933 red blood cell (RBC) transfusions, and 2154 cryoprecipitate transfusions. Over the same period, 108 pediatric and 277 adult transfusion reactions were recorded. This corresponds to an incidence of 6.2 reactions per 1000 transfusions within the pediatric (age reactions per 1000 transfusions within the adult population. In both adult and pediatric populations, transfusion reactions were most commonly associated with PLT, followed by RBC, and then plasma transfusions. Within the pediatric population, subset analysis identified multiple differences when compared to the adult population, including an increased incidence of allergic transfusion reactions (2.7/1000 vs. 1.1/1000, p reactions (1.9/1000 vs. 0.47/1000, p reactions (0.29/1000 vs. 0.078/1000, p reaction incidence was the same between sexes in adults, in pediatric patients, reactions were more common in male

  18. 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

  19. 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

  20. 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.

  1. Surface Properties of Titanium dioxide and its Structural Modifications by Reactions with Transition Metals

    Science.gov (United States)

    Halpegamage, Sandamali

    Surfaces of metal oxides play a vital role in many technologically important applications. The surfaces of titanium dioxide, in particular, show quite promising properties that can be utilized in solid-state gas sensing and photocatalysis applications. In the first part of this dissertation we investigate these properties of TiO2 surfaces through a vigorous surface scientific approach. In the second part, we investigate the possibilities of modifying the TiO2 surfaces by depositing multi-component transition metal oxide monolayers so that the properties of bare TiO2 surface can be influenced in a beneficial way. For instance, via formation of new surface sites or cations that have different valance states, the chemisorption and catalytic properties can be modified. We use sophisticated experimental surface science techniques that are compatible with ultra-high vacuum technology for surface characterization. All the experimental results, except for the photocatalysis experiments, were compared to and verified by supporting DFT-based theoretical results produced by our theory collaborators. TiO2 based solid-state gas sensors have been used before for detecting trace amounts of explosives such as 2,4-dinitrololuene (DNT), a toxic decomposition product of the explosive 2,4,6-trinitrotoluene (TNT) that have very low vapor pressure. However, the adsorption, desorption and reaction mechanism were not well- understood. Here, we investigate 2,4-DNT adsorption on rutile-TiO2(110) surface in order to gain insight about these mechanisms in an atomistic level and we propose an efficient way of desorbing DNT from the surface through UV-light induced photoreactions. TiO2 exists in different polymorphs and the photocatalytic activity differs from one polymorph to another. Rutile and anatase are the most famous forms of TiO2 in photocatalysis and anatase is known to show higher activity than rutile. The photoactivity also varies depending on the surface orientation for the same

  2. Reaction dynamics of molecular hydrogen on silicon surfaces

    DEFF Research Database (Denmark)

    Bratu, P.; Brenig, W.; Gross, A.

    1996-01-01

    of the preexponential factor by about one order of magnitude per lateral degree of freedom. Molecular vibrations have practically no effect on the adsorption/desorption dynamics itself, but lead to vibrational heating in desorption with a strong isotope effect. Ab initio calculations for the H-2 interaction...... between the two surfaces. These results indicate that tunneling, molecular vibrations, and the structural details of the surface play only a minor role for the adsorption dynamics. Instead, they appear to be governed by the localized H-Si bonding and Si-Si lattice vibrations. Theoretically, an effective......Experimental and theoretical results on the dynamics of dissociative adsorption and recombinative desorption of hydrogen on silicon are presented. Using optical second-harmonic generation, extremely small sticking probabilities in the range 10(-9)-10(-5) could be measured for H-2 and D-2 on Si(111...

  3. Near-surface analysis with nuclear reactions and scattering

    International Nuclear Information System (INIS)

    Dunning, K.L.; Hirvonen, J.K.

    1974-01-01

    Very useful information about the elemental composition of solids in the surface and near-surface regions can be obtained with small accelerators and suitable auxiliary apparatus. Two methods which produce data from which quantitative concentration depth profiles can be constructed and which have been used extensively at this laboratory are: nuclear resonance profiling and Rutherford backscattering. The first method is described in detail. Data are given on profiles of Al and Al + Na films implanted on silicon substrates. Rutherford backscattering spectra for chromium implanted into silicon dioxide are used to illustrate the improved depth sensitivity that can be obtained with a magnetic spectrometer in depth concentration profiles of heavy impurities relative to that obtainable with a conventional semiconductor detector

  4. Electrochemical Characterization of Surface Reactions on Biomedical Titanium alloys

    OpenAIRE

    Alkhateeb, Emad Hashim

    2008-01-01

    Titanium and its alloys are successfully used as implant materials for dental, orthopedic and osteosynthesis applications. The processes that take place at the implant tissue interface are important for the acceptance and integration of the implant. This thesis is divided into two parts: the first part deals with surface modification of titanium to improve the osseointegration, and the second part studies metastable pitting of titanium and its alloys. The weakly attached layer of a bone-like ...

  5. Evidence concerning oxidation as a surface reaction in Baltic amber

    DEFF Research Database (Denmark)

    Shashoua, Yvonne

    2012-01-01

    , obtained from pressed amber powder, were subjected to accelerated thermal ageing. Cross-sections of the pellets were analyzed by infrared micro-spectroscopy, in order to identify and quantify changes in chemical properties. The experimental results showed strong oxidation exclusively at the exterior part...... of cross-sections from samples subjected to long-term thermal ageing, confirming that oxidation of Baltic amber starts from the surface....

  6. Calculations of long-lived isomer production in neutron reactions

    International Nuclear Information System (INIS)

    Chadwick, M.B.; Young, P.G.

    1992-01-01

    We present theoretical calculations for the production of the long-lived isomers 93m Nb (1/2-, 16 yr), 121m Sn (11/2-, 55 yr), 166m Ho (7-, 1200 yr), 184m Re (8+, 165 d), 186m Re (8+, 2x10 5 yr), 178 Hf (16+, 31 yr), 179m Hf (25/2-, 25 d), and 192m Ir (9+, 241 yr), all of which pose potential radiation activation problems in nuclear fusion reactors if produced in 14-MeV neutron-induced reactions. We consider (n,2n), (n,n'), and (n,γ) production modes and compare our results both with experimental data (where available) and systematics. We also investigate the dependence of the isomeric cross section ratio on incident neutron energy for the isomers under consideration. The statistical Hauser-Feshbach plus preequilibrium code GNASH was used for the calculations. Where discrete state experimental information was lacking, rotational band members above the isomeric state, which can be justified theoretically but have not been experimentally resolved, were reconstructed. (author). 16 refs, 10 figs, 4 tabs

  7. Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

    Directory of Open Access Journals (Sweden)

    Rahul Bhosale

    2016-01-01

    Full Text Available The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2 into Tb and O2, whereas the 2nd step corresponds to the production of H2 through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2 and effect of water splitting temperature (TL on Gibbs free energy related to the H2 production step were examined in detail. The cycle (ηcycle and solar-to-fuel energy conversion (ηsolar-to-fuel efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate that ηcycle and ηsolar-to-fuel increase with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH. It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. At TH=2280 K, by applying 60% heat recuperation, maximum ηcycle of 39.0% and ηsolar-to-fuel of 47.1% for the Tb-WS cycle can be attained.

  8. A Review of Microwave-Assisted Reactions for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Saifuddin Nomanbhay

    2017-06-01

    Full Text Available The conversion of biomass into chemicals and biofuels is an active research area as trends move to replace fossil fuels with renewable resources due to society’s increased concern towards sustainability. In this context, microwave processing has emerged as a tool in organic synthesis and plays an important role in developing a more sustainable world. Integration of processing methods with microwave irradiation has resulted in a great reduction in the time required for many processes, while the reaction efficiencies have been increased markedly. Microwave processing produces a higher yield with a cleaner profile in comparison to other methods. The microwave processing is reported to be a better heating method than the conventional methods due to its unique thermal and non-thermal effects. This paper provides an insight into the theoretical aspects of microwave irradiation practices and highlights the importance of microwave processing. The potential of the microwave technology to accomplish superior outcomes over the conventional methods in biodiesel production is presented. A green process for biodiesel production using a non-catalytic method is still new and very costly because of the supercritical condition requirement. Hence, non-catalytic biodiesel conversion under ambient pressure using microwave technology must be developed, as the energy utilization for microwave-based biodiesel synthesis is reported to be lower and cost-effective.

  9. Measurement of charmed particle production in hadronic reactions

    CERN Multimedia

    2002-01-01

    The aim of the experiment is to measure the production cross-section for charmed particles in hadronic reactions, study their production mechanism, and search for excited charmed hadrons.\\\\ \\\\ Charmed Mesons and Baryons will be measured in $\\pi$ and $p$ interactions on Beryllium between 100 and 200 GeV/c. The trigger will be on an electron from the leptonic decay of one charmed particle by signals from the Cerenkov counter (Ce), the electron trigger calorimeter (eCal), scintillation counters, and proportional wire chambers. The accompanying charmed particle will be measured via its hadronic decay in a two-stage magnetic spectrometer with drift chambers (arms 2, 3a, 3b, 3c), two large-area multicell Cerenkov counters (C2, C3) and a large-area shower counter ($\\gamma$-CAL). The particles which can be measured and identified include $\\gamma, e, \\pi^{\\pm}, \\pi^{0}, K^{\\pm}, p, \\bar{p}$ so that a large number of hadronic decay modes of charmed particles can be studied. \\\\ \\\\ A silicon counter telescope with 5 $\\m...

  10. 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.

  11. Final Report Theoretical Studies of Surface Reactions on Metals and Electronic Materials

    Energy Technology Data Exchange (ETDEWEB)

    Jerry L. Whitten

    2012-04-23

    This proposal describes the proposed renewal of a theoretical research program on the structure and reactivity of molecules adsorbed on transition metal surfaces. A new direction of the work extends investigations to interfaces between solid surfaces, adsorbates and aqueous solutions and includes fundamental work on photoinduced electron transport into chemisorbed species and into solution. The goal is to discover practical ways to reduce water to hydrogen and oxygen using radiation comparable to that available in the solar spectrum. The work relates to two broad subject areas: photocatalytic processes and production of hydrogen from water. The objective is to obtain high quality solutions of the electronic structure of adsorbate-metal-surface-solution systems so as to allow activation barriers to be calculated and reaction mechanisms to be determined. An ab initio embedding formalism provides a route to the required accuracy. New theoretical methods developed during the previous grant period will be implemented in order to solve the large systems involved in this work. Included is the formulation of a correlation operator that is used to treat localized electron distributions such as ionic or regionally localized distributions. The correlation operator which is expressed as a two-particle projector is used in conjunction with configuration interaction.

  12. Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

    Science.gov (United States)

    Scott, Carl D.; Farhat, Samir; Greendyke, Robert B.

    2004-01-01

    The development of processes to produce fullerenes and carbon nanotubes has largely been empirical. Fullerenes were first discovered in the soot produced by laser ablation of graphite [1]and then in the soot of electric arc evaporated carbon. Techniques and conditions for producing larger and larger quantities of fullerenes depended mainly on trial and error empirical variations of these processes, with attempts to scale them up by using larger electrodes and targets and higher power. Various concepts of how fullerenes and carbon nanotubes were formed were put forth, but very little was done based on chemical kinetics of the reactions. This was mainly due to the complex mixture of species and complex nature of conditions in the reactors. Temperatures in the reactors varied from several thousand degrees Kelvin down to near room temperature. There are hundreds of species possible, ranging from atomic carbon to large clusters of carbonaceous soot, and metallic catalyst atoms to metal clusters, to complexes of metals and carbon. Most of the chemical kinetics of the reactions and the thermodynamic properties of clusters and complexes have only been approximated. In addition, flow conditions in the reactors are transient or unsteady, and three dimensional, with steep spatial gradients of temperature and species concentrations. All these factors make computational simulations of reactors very complex and challenging. This article addresses the development of the chemical reaction involved in fullerene production and extends this to production of carbon nanotubes by the laser ablation/oven process and by the electric arc evaporation process. In addition, the high-pressure carbon monoxide (HiPco) process is discussed. The article is in several parts. The first one addresses the thermochemical aspects of modeling; and considers the development of chemical rate equations, estimates of reaction rates, and thermodynamic properties where they are available. The second part

  13. 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.

  14. Large fragment production calculations in relativistic heavy-ion reactions

    International Nuclear Information System (INIS)

    Seixas de Oliveira, L.F.

    1978-12-01

    The abrasion-ablation model is briefly described and then used to calculate cross sections for production of large fragments resulting from target or projectile fragmentation in high-energy heavy-ion collisions. The number of nucleons removed from the colliding nuclei in the abrasion stage and the excitation energy of the remaining fragments (primary products) are calculated with the geometrical picture of two different models: the fireball and the firestreak models. The charge-to-mass dispersion of the primary products is calculated using either a model which assumes no correlations between proton and neutron positions inside the nucleus (hypergeometric distribution) or a model based upon the zero-point oscillations of the giant dipole resonance (NUC-GDR). Standard Weisskopf--Ewing statistical evaporation calculations are used to calculate final product distributions. Results of the pure abrasion-ablation model are compared with a variety of experimental data. The comparisons show the insufficiency of the extra-surface energy term used in the abrasion calculations. A frictional spectator interaction (FSI) is introduced which increases the average excitation energy of the primary products, and improves the results considerably in most cases. Agreements and discrepancies of the results calculated with the different theoretical assumptions and the experimental data are studied. Of particular relevance is the possibility of observing nuclear ground-state correlations.Results of the recently completed experiment of fragmentation of 213 Mev/A 40 Ar projectiles are studied and shown not to be capable of answering that question unambiguously. But predictions for the upcoming 48 Ca fragmentation experiment clearly show the possibility of observing correlation effects. 78 references

  15. 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.

  16. 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.

  17. 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.

  18. Light-induced nitrous acid (HONO) production from NO2 heterogeneous reactions on household chemicals

    Science.gov (United States)

    Gómez Alvarez, Elena; Sörgel, Matthias; Gligorovski, Sasho; Bassil, Sabina; Bartolomei, Vincent; Coulomb, Bruno; Zetzsch, Cornelius; Wortham, Henri

    2014-10-01

    Nitrous acid (HONO) can be generated in various indoor environments directly during combustion processes or indirectly via heterogeneous NO2 reactions with water adsorbed layers on diverse surfaces. Indoors not only the concentrations of NO2 are higher but the surface to volume (S/V) ratios are larger and therefore the potential of HONO production is significantly elevated compared to outdoors. It has been claimed that the UV solar light is largely attenuated indoors. Here, we show that solar light (λ > 340 nm) penetrates indoors and can influence the heterogeneous reactions of gas-phase NO2 with various household surfaces. The NO2 to HONO conversion mediated by light on surfaces covered with domestic chemicals has been determined at atmospherically relevant conditions i.e. 50 ppb NO2 and 50% RH. The formation rates of HONO were enhanced in presence of light for all the studied surfaces and are determined in the following order: 1.3·109 molecules cm-2 s-1 for borosilicate glass, 1.7·109 molecules cm-2 s-1 for bathroom cleaner, 1.0·1010 molecules cm-2 s-1 on alkaline detergent (floor cleaner), 1.3·1010 molecules cm-2 s-1 for white wall paint and 2.7·1010 molecules cm-2 s-1 for lacquer. These results highlight the potential of household chemicals, used for cleaning purposes to generate HONO indoors through light-enhanced NO2 heterogeneous reactions. The results obtained have been applied to predict the timely evolution of HONO in a real indoor environment using a dynamic mass balance model. A steady state mixing ratio of HONO has been estimated at 1.6 ppb assuming a contribution from glass, paint and lacquer and considering the photolysis of HONO as the most important loss process.

  19. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    Science.gov (United States)

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-03-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

  20. Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy

    Science.gov (United States)

    Xu, Meng-Lei; Gao, Yu; Li, Yali; Li, Xueliang; Zhang, Huanjie; Han, Xiao Xia; Zhao, Bing; Su, Liang

    2018-05-01

    Glyphosate is one of the most commonly-used and non-selective herbicides in agriculture, which may directly pollute the environment and threaten human health. A simple and effective approach to assessment of its damage to the natural environment is thus quite necessary. However, traditional chromatography-based detection methods usually suffer from complex pretreatment procedures. Herein, we propose a simple and sensitive method for the determination of glyphosate by combining ninhydrin reaction and surface-enhanced Raman scattering (SERS) spectroscopy. The product (purple color dye, PD) of the ninhydrin reaction is found to SERS-active and directly correlate with the glyphosate concentration. The limit of detection of the proposed method for glyphosate is as low as 1.43 × 10- 8 mol·L- 1 with a relatively wider linear concentration range (1.0 × 10- 7-1.0 × 10- 4 mol·L- 1), which demonstrates its great potential in rapid, highly sensitive concentration determination of glyphosate in practical applications for safety assessment of food and environment.

  1. 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

  2. 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

  3. 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

  4. Oxidation of β-lactam antibiotics by peracetic acid: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Zhang, Kejia; Zhou, Xinyan; Du, Penghui; Zhang, Tuqiao; Cai, Meiquan; Sun, Peizhe; Huang, Ching-Hua

    2017-10-15

    Peracetic acid (PAA) is a disinfection oxidant used in many industries including wastewater treatment. β-Lactams, a group of widely prescribed antibiotics, are frequently detected in wastewater effluents and surface waters. The reaction kinetics and transformation of seven β-lactams (cefalexin (CFX), cefadroxil (CFR), cefapirin (CFP), cephalothin (CFT), ampicillin (AMP), amoxicillin (AMX) and penicillin G (PG)) toward PAA were investigated to elucidate the behavior of β-lactams during PAA oxidation processes. The reaction follows second-order kinetics and is much faster at pH 5 and 7 than at pH 9 due to speciation of PAA. Reactivity to PAA follows the order of CFR ∼ CFX > AMP ∼ AMX > CFT ∼ CFP ∼ PG and is related to β-lactam's nucleophilicity. The thioether sulfur of β-lactams is attacked by PAA to generate sulfoxide products. Presence of the phenylglycinyl amino group on β-lactams can significantly influence electron distribution and the highest occupied molecular orbital (HOMO) location and energy in ways that enhance the reactivity to PAA. Reaction rate constants obtained in clean water matrix can be used to accurately model the decay of β-lactams by PAA in surface water matrix and only slightly overestimate the decay in wastewater matrix. Results of this study indicate that the oxidative transformation of β-lactams by PAA can be expected under appropriate wastewater treatment conditions. Copyright © 2017. Published by Elsevier Ltd.

  5. Monitorizing nitinol alloy surface reactions for biofouling studies

    International Nuclear Information System (INIS)

    Dinu, C.Z.; Dinca, V.C.; Soare, S.; Moldovan, A.; Smarandache, D.; Scarisoareanu, N.; Barbalat, A.; Birjega, R.; Dinescu, M.; DiStefano, V. Ferrari

    2007-01-01

    Growth and deposition of unwanted bacteria on implant metal alloys affect their use as biomedical samples. Monitoring any bacterial biofilm accumulation will provide early countermeasures. For a reliable antifouling strategy we prepared nitinol (NiTi) thin films on Ti-derived substrates by using a pulsed laser deposition (PLD) method. As the microstructure of Ti-alloy is dictated by the tensile strength, fatigue and the fracture toughness we tested the use of hydrogen as an alloying element. X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM) investigated the crystalline structure, chemical composition and respectively the surface morphology of the nitinol hydrogen and hydrogen-free samples. Moreover, the alloys were integrated and tested using a cellular metric and their responses were systematic evaluated and quantified. Our attractive approach is meant to select the suitable components for an effective and trustworthy anti-fouling strategy. A greater understanding of such processes should lead to novel and effective control methods that would improve in the future implant stability and capabilities

  6. 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.

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

    Science.gov (United States)

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

    2018-03-01

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

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

    KAUST Repository

    Hong, Jongsup

    2015-08-01

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

  9. The production rate of cosmogenic deuterium at the Moon's surface

    Science.gov (United States)

    Füri, Evelyn; Deloule, Etienne; Trappitsch, Reto

    2017-09-01

    The hydrogen (D/H) isotope ratio is a key tracer for the source of planetary water. However, secondary processes such as solar wind implantation and cosmic ray induced spallation reactions have modified the primordial D/H signature of 'water' in all rocks and soils recovered on the Moon. Here, we re-evaluate the production rate of cosmogenic deuterium (D) at the Moon's surface through ion microprobe analyses of hydrogen isotopes in olivines from eight Apollo 12 and 15 mare basalts. These in situ measurements are complemented by CO2 laser extraction-static mass spectrometry analyses of cosmogenic noble gas nuclides (3He, 21Ne, 38Ar). Cosmic ray exposure (CRE) ages of the mare basalts, derived from their cosmogenic 21Ne content, range from 60 to 422 Ma. These CRE ages are 35% higher, on average, than the published values for the same samples. The amount of D detected in the olivines increases linearly with increasing CRE ages, consistent with a production rate of (2.17 ± 0.11) ×10-12 mol(g rock)-1 Ma-1. This value is more than twice as high as previous estimates for the production of D by galactic cosmic rays, indicating that for water-poor lunar samples, i.e., samples with water concentrations ≤50 ppm, corrected D/H ratios have been severely overestimated.

  10. A COMBINED REACTION/PRODUCT RECOVERY PROCESS FOR THE CONTINUOUS PRODUCTION OF BIODIESEL

    Energy Technology Data Exchange (ETDEWEB)

    Birdwell, J.F., Jr.; McFarlane, J.; Schuh, D.L.; Tsouris, C; Day, J.N. (Nu-Energie, LLC); Hullette, J.N. (Nu-Energie, LLC)

    2009-09-01

    Oak Ridge National Laboratory (ORNL) and Nu-Energie, LLC entered into a Cooperative Research And Development Agreement (CRADA) for the purpose of demonstrating and deploying a novel technology for the continuous synthesis and recovery of biodiesel from the transesterification of triglycerides. The focus of the work was the demonstration of a combination Couette reactor and centrifugal separator - an invention of ORNL researchers - that facilitates both product synthesis and recovery from reaction byproducts in the same apparatus. At present, transesterification of triglycerides to produce biodiesel is performed in batch-type reactors with an excess of a chemical catalyst, which is required to achieve high reactant conversions in reasonable reaction times (e.g., 1 hour). The need for long reactor residence times requires use of large reactors and ancillary equipment (e.g., feed and product tankage), and correspondingly large facilities, in order to obtain the economy of scale required to make the process economically viable. Hence, the goal of this CRADA was to demonstrate successful, extended operation of a laboratory-scale reactor/separator prototype to process typical industrial reactant materials, and to design, fabricate, and test a production-scale unit for deployment at the biodiesel production site. Because of its ease of operation, rapid attainment of steady state, high mass transfer and phase separation efficiencies, and compact size, a centrifugal contactor was chosen for intensification of the biodiesel production process. The unit was modified to increase the residence time from a few seconds to minutes*. For this application, liquid phases were introduced into the reactor as separate streams. One was composed of the methanol and base catalyst and the other was the soy oil used in the experiments. Following reaction in the mixing zone, the immiscible glycerine and methyl ester products were separated in the high speed rotor and collected from separate

  11. A COMBINED REACTION/PRODUCT RECOVERY PROCESS FOR THE CONTINUOUS PRODUCTION OF BIODIESEL

    International Nuclear Information System (INIS)

    Birdwell, J.F. Jr.; McFarlane, J.; Schuh, D.L.; Tsouris, C.; Day, J.N.; Hullette, J.N.

    2009-01-01

    Oak Ridge National Laboratory (ORNL) and Nu-Energie, LLC entered into a Cooperative Research And Development Agreement (CRADA) for the purpose of demonstrating and deploying a novel technology for the continuous synthesis and recovery of biodiesel from the transesterification of triglycerides. The focus of the work was the demonstration of a combination Couette reactor and centrifugal separator - an invention of ORNL researchers - that facilitates both product synthesis and recovery from reaction byproducts in the same apparatus. At present, transesterification of triglycerides to produce biodiesel is performed in batch-type reactors with an excess of a chemical catalyst, which is required to achieve high reactant conversions in reasonable reaction times (e.g., 1 hour). The need for long reactor residence times requires use of large reactors and ancillary equipment (e.g., feed and product tankage), and correspondingly large facilities, in order to obtain the economy of scale required to make the process economically viable. Hence, the goal of this CRADA was to demonstrate successful, extended operation of a laboratory-scale reactor/separator prototype to process typical industrial reactant materials, and to design, fabricate, and test a production-scale unit for deployment at the biodiesel production site. Because of its ease of operation, rapid attainment of steady state, high mass transfer and phase separation efficiencies, and compact size, a centrifugal contactor was chosen for intensification of the biodiesel production process. The unit was modified to increase the residence time from a few seconds to minutes*. For this application, liquid phases were introduced into the reactor as separate streams. One was composed of the methanol and base catalyst and the other was the soy oil used in the experiments. Following reaction in the mixing zone, the immiscible glycerine and methyl ester products were separated in the high speed rotor and collected from separate

  12. Determination of 68Ga production parameters by different reactions ...

    Indian Academy of Sciences (India)

    function of 68Zn(p, n)68Ga reaction was compared with the reported ... 2.1.1 Brief description of nuclear models applied for cross-section calculations ... tion of isotope impurities is not possible by chemical methods, so this reaction is.

  13. 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.

  14. 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)

  15. 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).

  16. AES study of the reaction between a thin Fe-film and β-SiC (100) surface

    International Nuclear Information System (INIS)

    Mizokawa, Yusuke; Nakanishi, Shigemitsu; Miyase, Sunao

    1989-01-01

    The solid state reaction between thin Fe-films and β-SiC(100) in UHV has been studied using AES. Even at room temperature, the reaction between the thin Fe-film and SiC occurred and formed Fe-silicide and graphite with a minor product of Fe-carbide (Fe 3 C). The reaction proceeded with an increase of Fe-coverage to some extent. With annealing of 15 A-Fe-film/SiC below 540degC, the Fe-silicide formation was accelerated, but because the amount of available Fe was small, the dissolved carbon atoms were forced to form not the Fe-carbide but the graphite phase. Above 640degC, the Fe-silicide started to decompose and the carbon atoms diffused to the surface and formed surface graphite layers. With annealing at 1080degC, the free-Si segregats at the surface and formed Si-Si bonds, as well as the Si-C bonds consuming the surface graphite phase. (author)

  17. 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.

  18. 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.

  19. 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

  20. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    Science.gov (United States)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  1. State-to-state quantum dynamics of the F + HCl (vi = 0, ji = 0) → HF(vf, jf) + Cl reaction on the ground state potential energy surface.

    Science.gov (United States)

    Li, Anyang; Guo, Hua; Sun, Zhigang; Kłos, Jacek; Alexander, Millard H

    2013-10-07

    The state-to-state reaction dynamics of the title reaction is investigated on the ground electronic state potential energy surface using two quantum dynamical methods. The results obtained using the Chebyshev real wave packet method are in excellent agreement with those obtained using the time-independent method, except at low translational energies. It is shown that this exothermic hydrogen abstraction reaction is direct, resulting in a strong back-scattered bias in the product angular distribution. The HF product is highly excited internally. Agreement with available experimental data is only qualitative. We discuss several possible causes of disagreement with experiment.

  2. XPS study on the surface reaction of uranium metal with carbon monoxide at 200 degree C

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-12-01

    The surface reaction of uranium metal with carbon monoxide at 200 degree C has been studied by X-ray photoelectron spectroscopy (XPS). The carbon monoxide adsorption on the surface oxide layer resulted in U4f peak shifting to the lower binding energy and the content of oxygen in the oxide is decreased. O/U radio decreases with increasing the exposure of carbon monoxide to the surface layer. The investigation indicated the surface layer of uranium metal was further reduced in the atmosphere of carbon monoxide at high temperature. (3 refs., 5 figs.)

  3. HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

    International Nuclear Information System (INIS)

    Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

    2004-01-01

    We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

  4. Surface/subsurface observation and removal mechanisms of ground reaction bonded silicon carbide

    Science.gov (United States)

    Yao, Wang; Zhang, Yu-Min; Han, Jie-cai; Zhang, Yun-long; Zhang, Jian-han; Zhou, Yu-feng; Han, Yuan-yuan

    2006-01-01

    Reaction Bonded Silicon Carbide (RBSiC) has long been recognized as a promising material for optical applications because of its unique combination of favorable properties and low-cost fabrication. Grinding of silicon carbide is difficult because of its high hardness and brittleness. Grinding often induces surface and subsurface damage, residual stress and other types of damage, which have great influence on the ceramic components for optical application. In this paper, surface integrity, subsurface damage and material removal mechanisms of RBSiC ground using diamond grinding wheel on creep-feed surface grinding machine are investigated. The surface and subsurface are studied with scanning electron microscopy (SEM) and optical microscopy. The effects of grinding conditions on surface and subsurface damage are discussed. This research links the surface roughness, surface and subsurface cracks to grinding parameters and provides valuable insights into the material removal mechanism and the dependence of grind induced damage on grinding conditions.

  5. Process and device for energy production from thermonuclear fusion reactions

    International Nuclear Information System (INIS)

    Bussard, R.W.; Coppi, Bruno.

    1977-01-01

    An energy generating system is described using a fusion reaction. It includes several contrivances for confining a plasma in an area, a protective device around a significant part of each of these confinement contrivances, an appliance for introducing a fusion reaction fuel in each of the confinements so that the plasma may be formed. Each confinement can be separated from the protective device so that it may be replaced by another. The system is connected to the confinements, to the protective devices or to both. It enables the thermal energy to be extracted and transformed into another form, electric, mechanical or both [fr

  6. Production of nanocrystalline metal powders via combustion reaction synthesis

    Science.gov (United States)

    Frye, John G.; Weil, Kenneth Scott; Lavender, Curt A.; Kim, Jin Yong

    2017-10-31

    Nanocrystalline metal powders comprising tungsten, molybdenum, rhenium and/or niobium can be synthesized using a combustion reaction. Methods for synthesizing the nanocrystalline metal powders are characterized by forming a combustion synthesis solution by dissolving in water an oxidizer, a fuel, and a base-soluble, ammonium precursor of tungsten, molybdenum, rhenium, or niobium in amounts that yield a stoichiometric burn when combusted. The combustion synthesis solution is then heated to a temperature sufficient to substantially remove water and to initiate a self-sustaining combustion reaction. The resulting powder can be subsequently reduced to metal form by heating in a reducing gas environment.

  7. 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.

  8. Nuclear reactions and application to production rates of krypton in extraterrestrial materials

    International Nuclear Information System (INIS)

    Lavielle, B.

    1982-01-01

    Noble gases have been largely outgassed from most solar system materials through several heating processes. Consequently, their cosmogenic component, produced by cosmic-ray-induced nuclear reactions near the surface of atmosphere-free planetary objects, is detectable in meteorites and lunar samples. This work deals with the production of cosmogenic Krypton in the four main targets Zr, Y, Sr and Rb. Excitation functions of Krypton isotopes with A = 78, 80, 81, 82, 83, 84, 85 and 86 were mass-spectrometrically measured in Y and Zr targets bombarded with 0.059, 0.075, 0.168, 0.200, 1.0, 2.5 and 24 GeV protons. Also the Krypton relative cross sections were measured in Sr at 0.168 GeV. The results, combined with a general survey of nuclear reactions in Ga to Nb targets, permitted the development of new systematics in order to estimate unknown cross-sections in Rb and Sr. Measured and estimated excitation functions allowed to calculate the concentrations and isotopic ratios of cosmogenic Krypton in same well-documented lunar samples. Compared to observed values in 9 rocks, 83 Kr is predicted with a precision better than 33% and the production ratios sup(i)Kr/ 83 Kr are predicted to better than 25%. Also it is concluded that the cosmogenic ratios 86 Kr/ 83 Kr and 81 Kr/ 83 Kr are dependent on the main target elements concentrations [fr

  9. Contamination of Optical Surfaces Under Irradiation by Outgassed Volatile Products

    International Nuclear Information System (INIS)

    Khasanshin, R. H.; Grigorevskiy, A. V.; Galygin, A. N.; Alexandrov, N. G.

    2009-01-01

    Deposition of outgassed products of a polymeric composite on model material surfaces being irradiated by electrons and protons with initial energies of E e = 40 keV and E p = 30 keV respectively was studied. It was shown that deposition of volatile products on model material surfaces being under ionizing radiations results in increase of organic film growth rate.

  10. Two-pion production in photon-induced reactions

    Indian Academy of Sciences (India)

    photoproduction from nuclei is also used to investigate the in-medium modification of meson–meson interactions. ... the observation of an in-medium modification of the vector meson masses can pro- vide a unique .... similar behavior is found in (γ,π+π0) reactions, shown in the right panel of figure 3. Additionally, the peak in ...

  11. Determination of 68Ga production parameters by different reactions ...

    Indian Academy of Sciences (India)

    Gallium-68 (1/2 = 68 min, + = 89%) is an important positron-emitting radionuclide for positron emission tomography and used in nuclear medicine for diagnosing tumours. This study gives a suitable reaction to produce 68Ga. Gallium-68 excitation function via 68Zn(, ) 68Ga, 68Zn(, 2) 68Ga, 70Zn(, 3) 68Ga and ...

  12. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

  13. Research project AUS-10370/CF: electron impact ionization and surface induced reactions of edge plasma constituents

    International Nuclear Information System (INIS)

    Maerk, T.D.

    1999-01-01

    In order to better understand elementary reactions which are taking place at the plasma edge of thermonuclear fusion devices, three areas of research were persuaded: I) Experimental studies about electron ionization of neutrals and ions and electron attachment to molecules, II) Theoretical studies about electron ionisation of neutrals and ions and III) Reactive interaction of molecular ions with surfaces

  14. Oxidation kinetics of reaction products formed in uranium metal corrosion

    International Nuclear Information System (INIS)

    Totemeier, T. C.

    1998-01-01

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O 2 and Ar-20%O 2 were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates

  15. Oxidation kinetics of reaction products formed in uranium metal corrosion.

    Energy Technology Data Exchange (ETDEWEB)

    Totemeier, T. C.

    1998-04-22

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O{sub 2} and Ar-20%O{sub 2} were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates.

  16. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    Science.gov (United States)

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

    2015-02-17

    CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on

  17. Adsorption and reaction of propanal, 2-propenol and 1-propanol on Ni/Pt(111) bimetallic surfaces

    Science.gov (United States)

    Murillo, Luis E.; Chen, Jingguang G.

    2008-07-01

    The hydrogenation of acrolein (CH 2dbnd CH sbnd CH dbnd O) can lead to the formation of three hydrogenation products, 2-propenol (CH 2dbnd CH sbnd CH 2sbnd OH), propanal (CH 3sbnd CH 2sbnd CH dbnd O), and 1-propanol (CH 3sbnd CH 2sbnd CH 2sbnd OH). In the current study the adsorption and reaction of these three molecules were investigated on Ni/Pt(111) surfaces to understand the different hydrogenation pathways of acrolein, using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). TPD experiments showed that 2-propenol underwent isomerization toward propanal on Pt(111) and the Pt sbnd Ni sbnd Pt(111) bimetallic surface, with a dominant decarbonylation pathway on the Pt(111) surface. A self-hydrogenation (disproportionation) pathway toward 1-propanol was observed on the Ni(111) film, however, the decarbonylation pathway was found to be the most dominant on this surface. Unlike 2-propenol, propanal did not undergo isomerization or self-hydrogenation pathways on any of the surfaces, with the dominant pathway being primarily the decarbonylation on Pt(111) and Ni(111). In contrast, 1-propanol underwent mainly molecular desorption from all three surfaces. These results provided additional understanding of previous studies of hydrogenation pathways of acrolein on the Ni/Pt(111) surfaces.

  18. Hydrogen production via thermochemical water-splitting by lithium redox reaction

    International Nuclear Information System (INIS)

    Nakamura, Naoya; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

    2013-01-01

    Highlights: •Hydrogen production via water-splitting by lithium redox reactions possibly proceeds below 800 °C. •Entropy control by using nonequilibrium technique successfully reduces the reaction temperature. •The operating temperature should be further reduced by optimizing the nonequilibrium condition to control the cycle. -- Abstracts: Hydrogen production via thermochemical water-splitting by lithium redox reactions was investigated as energy conversion technique. The reaction system consists of three reactions, which are hydrogen generation by the reaction of lithium and lithium hydroxide, metal separation by thermolysis of lithium oxide, and oxygen generation by hydrolysis of lithium peroxide. The hydrogen generation reaction completed at 500 °C. The metal separation reaction is thermodynamically difficult because it requires about 3400 °C in equilibrium condition. However, it was indicated from experimental results that the reaction temperature was drastically reduced to 800 °C by using nonequilibrium technique. The hydrolysis reaction was exothermic reaction, and completed by heating up to 300 °C. Therefore, it was expected that the water-splitting by lithium redox reactions was possibly operated below 800 °C under nonequilibrium condition

  19. Selective Production of Renewable para-Xylene by Tungsten Carbide Catalyzed Atom-Economic Cascade Reactions.

    Science.gov (United States)

    Dai, Tao; Li, Changzhi; Li, Lin; Zhao, Zongbao Kent; Zhang, Bo; Cong, Yu; Wang, Aiqin

    2018-02-12

    Tungsten carbide was employed as the catalyst in an atom-economic and renewable synthesis of para-xylene with excellent selectivity and yield from 4-methyl-3-cyclohexene-1-carbonylaldehyde (4-MCHCA). This intermediate is the product of the Diels-Alder reaction between the two readily available bio-based building blocks acrolein and isoprene. Our results suggest that 4-MCHCA undergoes a novel dehydroaromatization-hydrodeoxygenation cascade process by intramolecular hydrogen transfer that does not involve an external hydrogen source, and that the hydrodeoxygenation occurs through the direct dissociation of the C=O bond on the W 2 C surface. Notably, this process is readily applicable to the synthesis of various (multi)methylated arenes from bio-based building blocks, thus potentially providing a petroleum-independent solution to valuable aromatic compounds. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Magnetophoretic potential at the movement of cluster products of electrochemical reactions in an inhomogeneous magnetic field

    International Nuclear Information System (INIS)

    Gorobets, O. Yu.; Gorobets, Yu. I.; Rospotniuk, V. P.

    2015-01-01

    An electric field arises from the influence of a nonuniform static magnetic field on charged colloid particles with magnetic susceptibility different from that of the surrounding liquid. It arises, for example, under the influence of a nonuniform static magnetic field in clusters of electrochemical reaction products created during metal etching, deposition, and corrosion processes without an external electric current passing through an electrolyte near a magnetized electrode surface. The corresponding potential consists of a Nernst potential of inhomogeneous distribution of concentration of colloid particles and a magnetophoretic potential (MPP). This potential has been calculated using a thermodynamic approach based on the equations of thermodynamics of nonequilibrium systems and the Onsager relations for a mass flow of correlated magnetic clusters under a gradient magnetic force in the electrolyte. The conditions under which the MPP contribution to the total electric potential may be significant are discussed with a reference to the example of a corroding spherical ferromagnetic steel electrode

  1. Magnetophoretic potential at the movement of cluster products of electrochemical reactions in an inhomogeneous magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Gorobets, O. Yu., E-mail: pitbm@ukr.net; Gorobets, Yu. I., E-mail: Gorobets@imag.kiev.ua [National Technical University of Ukraine “KPI”, Peremogy Avenue 37, Kyiv 03056 (Ukraine); Institute of Magnetism NAS of Ukraine and National Academy of Sciences of Ukraine, Vernadsky Avenue, 36-b, Kyiv 03142 (Ukraine); Rospotniuk, V. P. [National Technical University of Ukraine “KPI”, Peremogy Avenue 37, Kyiv 03056 (Ukraine)

    2015-08-21

    An electric field arises from the influence of a nonuniform static magnetic field on charged colloid particles with magnetic susceptibility different from that of the surrounding liquid. It arises, for example, under the influence of a nonuniform static magnetic field in clusters of electrochemical reaction products created during metal etching, deposition, and corrosion processes without an external electric current passing through an electrolyte near a magnetized electrode surface. The corresponding potential consists of a Nernst potential of inhomogeneous distribution of concentration of colloid particles and a magnetophoretic potential (MPP). This potential has been calculated using a thermodynamic approach based on the equations of thermodynamics of nonequilibrium systems and the Onsager relations for a mass flow of correlated magnetic clusters under a gradient magnetic force in the electrolyte. The conditions under which the MPP contribution to the total electric potential may be significant are discussed with a reference to the example of a corroding spherical ferromagnetic steel electrode.

  2. Utility of spectral measurements of secondary reaction products

    International Nuclear Information System (INIS)

    Heidbrink, W.E.

    1986-02-01

    The spectra of 15 MeV protons and 14 MeV neutrons produced in the burnup of 0.8 MeV 3 He ions and 1 MeV tritons through the d( 3 He,p)α and d(t,n)α fusion reactions contain information on the velocity distributions of the energetic 3 He ions and tritons. 11 refs., 2 figs

  3. 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.

  4. 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.

  5. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  6. Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction

    Science.gov (United States)

    Aogaki, Ryoichi; Sugiyama, Atsushi; Miura, Makoto; Oshikiri, Yoshinobu; Miura, Miki; Morimoto, Ryoichi; Takagi, Satoshi; Mogi, Iwao; Yamauchi, Yusuke

    2016-07-01

    As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton’s second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field.

  7. Analysis of a Buchwald-Hartwig amination: reaction for pharmaceutical production

    DEFF Research Database (Denmark)

    Christensen, Henrik

    The Buchwald-Hartwig amination reaction is widely used in the production of N-arylated amines in the pharmaceutical industry. The reaction is betweenan aryl halogen and a primary or secondary amine in the presence of a base and a homogeneous catalyst giving the desired N-arylated amine. Due to mild...... is to increase the understanding of the chem­ical reaction mechanisms and kinetics for the Buchwald-Hartwig amination reaction. Also, to develop methods for application of these mechanisms and kinetics to optimize and scale up an organic synthesis to an industrial phar­maceutical production. The Buchwald...

  8. Analysis of a Buckwald-Hartwig amination: reaction for pharmaceutical production

    DEFF Research Database (Denmark)

    Christensen, Henrik; Kiil, Søren; Dam-Johansen, Kim

    The Buchwald-Hartwig amination reaction is widely used in the production of N-arylated amines in the pharmaceutical industry. The reaction is betweenan aryl halogen and a primary or secondary amine in the presence of a base and a homogeneous catalyst giving the desired N-arylated amine. Due to mild...... is to increase the understanding of the chem­ical reaction mechanisms and kinetics for the Buchwald-Hartwig amination reaction. Also, to develop methods for application of these mechanisms and kinetics to optimize and scale up an organic synthesis to an industrial phar­maceutical production. The Buchwald...

  9. 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)

  10. 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.

  11. 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.)

  12. Application of the aza-Diels-Alder reaction in the synthesis of natural products.

    Science.gov (United States)

    Cao, Min-Hui; Green, Nicholas J; Xu, Sheng-Zhen

    2017-04-11

    The Diels-Alder reaction that involves a nitrogen atom in the diene or dienophile is termed the aza-Diels-Alder reaction. As well as the powerful all-carbon Diels-Alder reaction, the aza-Diels-Alder reaction has also played an important role in the total synthesis of natural products. Herein, we review various natural products using an aza-Diels-Alder reaction as a key step to their total synthesis, and divide the syntheses into inter- and intra-molecular aza-Diels-Alder reactions and a retro-aza-Diels-Alder reaction. Inter- and intra-molecular aza-Diels-Alder reactions involve an imine as an electron deficient dienophile and an imine as an electron deficient azadiene. The significance of the aza-Diels-Alder reaction for the construction of a six-membered ring containing nitrogen is tremendous, but the development of asymmetric, in particular catalytic enantioselective intramolecular aza-Diels-Alder reaction in the total synthesis of natural products remains highly challenging, and will no doubt see enormous advances in the future.

  13. Electro-deposition of Pd on carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions usingthe electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substratesfor the electrodeposition of the metal...

  14. Origin of Power Laws for Reactions at Metal Surfaces Mediated by Hot Electrons

    DEFF Research Database (Denmark)

    Olsen, Thomas; Schiøtz, Jakob

    2009-01-01

    A wide range of experiments have established that certain chemical reactions at metal surfaces can be driven by multiple hot-electron-mediated excitations of adsorbates. A high transient density of hot electrons is obtained by means of femtosecond laser pulses and a characteristic feature of such...... density functional theory and the delta self-consistent field method. With a simplifying assumption, the power law becomes exact and we obtain a simple physical interpretation of the exponent n, which represents the number of adsorbate vibrational states participating in the reaction....

  15. Modeling heat dissipation at the nanoscale: an embedding approach for chemical reaction dynamics on metal surfaces.

    Science.gov (United States)

    Meyer, Jörg; Reuter, Karsten

    2014-04-25

    We present an embedding technique for metallic systems that makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. The separation of chemical and elastic contributions to the interaction potential provides a quantitative description of both electronic and phononic band structure. Application to the dissociation of O2 at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This finding questions the instant thermalization of reaction enthalpies generally assumed in models of heterogeneous catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Molecular resonances, fusion reactions and surface transparency of interaction between heavy ions

    International Nuclear Information System (INIS)

    Abe, Yasuhisa.

    1980-01-01

    A review of the Band Crossing Model is given, including recent results on the 16 O + 16 O system. Surface Transparency is discussed in the light of the recent development in our understanding of the fusion reaction mechanisms and by calculating the number of open channels available to direct reactions. The existence of the Molecular Resonance Region is suggested in several systems by the fact that Band Crossing Region overlaps with the Transparent Region. A systematic study predicts molecular resonances in the 14 C + 14 C and 12 C + 14 C systems as prominent as those observed in the 16 O + 16 O and 12 C + 16 O systems

  17. Surface Modification Reaction of Photocatalytic Titanium Dioxide with Triethoxysilane for Improving Dispersibility

    International Nuclear Information System (INIS)

    Lee, Myung Jin; Kim, Ji Ho; Park, Young Tae

    2010-01-01

    We have carried out the surface modification of photocatalytic TiO 2 with triethoxysilane through dehydrogenation reaction and characterized the modified photocatalyst by spectroscopic methods, such as FT-IR, solid-state 29 Si MAS NMR, XPS, and XRF, etc. We also examined photocatalytic activity of the immobilized photocatalytic titanium dioxide with triethoxysilane by decolorization reaction of dyes such as cong red and methylene blue under visible light. Dispersion test showed that the photocatalytic titanium dioxide immobilized with triethoxysilane group has kept higher dispersibility than titanium dioxide itself. No appreciable precipitation takes place even after standing for 24 h in the 4:6 mixture ratio of ethanol and water

  18. Surface reactions during atomic layer deposition of Pt derived from gas phase infrared spectroscopy

    NARCIS (Netherlands)

    Kessels, W.M.M.; Knoops, H.C.M.; Dielissen, S.A.F.; Mackus, A.J.M.; Sanden, van de M.C.M.

    2009-01-01

    Infrared spectroscopy was used to obtain absolute number information on the reaction products during atomic layer deposition of Pt from (methylcyclopentadienyl)trimethylplatinum [(MeCp)PtMe3] and O2. From the detection of CO2 and H2O it was established that the precursor ligands are oxidatively

  19. Chemical surface reactions by click chemistry: coumarin dye modification of 11-bromoundecyltrichlorosilane monolayers

    International Nuclear Information System (INIS)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S

    2008-01-01

    The functionalization of surfaces and the ability to tailor their properties with desired physico-chemical functions is an important field of research with a broad spectrum of applications. These applications range from the modification of wetting properties, over the alteration of optical properties, to the fabrication of molecular electronic devices. In each of these fields, it is of specific importance to be able to control the quality of the layers with high precision. The present study demonstrates an approach that utilizes the 1,3-dipolar cycloaddition of terminal acetylenes to prepare triazole-terminated monolayers on different substrates. The characterization of the precursor monolayers, the optimization of the chemical surface reactions as well as the clicking of a fluorescent dye molecule on such azide-terminated monolayers was carried out. A coumarin 343 derivative was utilized to discuss the aspects of the functionalization approach. Based on this approach, a number of potential surface reactions, facilitated via the acetylene-substituted functional molecules, for a broad range of applications is at hand, thus leading to numerous possibilities where surface modifications are concerned. These modifications can be applied on non-structured surfaces of silicon or glass or can be used on structured surfaces. Various possibilities are discussed

  20. Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

    Science.gov (United States)

    Obermeyer, Genevieve; Aschmann, Sara M.; Atkinson, Roger; Arey, Janet

    To convert gaseous carbonyls to oximes during sampling, an XAD-4 resin denuder system pre-coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and followed by analysis with methane positive chemical ionization gas chromatography/mass spectrometry was used to measure carbonyls in ambient air samples in Riverside, CA. In conjunction with similar analyses of environmental chamber OH radical-initiated reactions of o- and p-xylene, 1,2,4-trimethylbenzene, ethylbenzene, 4-hydroxy-2-butanone and 1,4-butanediol, we identified benzaldehyde, o-, m- and p-tolualdehyde and acetophenone and the dicarbonyls glyoxal, methylglyoxal, biacetyl, ethylglyoxal, 1,4-butenedial, 3-hexene-2,5-dione, 3-oxo-butanal, 1,4-butanedial and malonaldehyde in the ambient air samples. As discussed, these carbonyls and dicarbonyls can be formed from the OH radical-initiated reactions of aromatic hydrocarbons and other volatile organic compounds emitted into the atmosphere, and we conclude that in situ atmospheric formation is a major source of these carbonyls in our Riverside, CA, ambient air samples.

  1. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-04-20

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  2. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    International Nuclear Information System (INIS)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-01-01

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  3. 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.

  4. 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.

  5. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  6. Propulsion of a Molecular Machine by Asymmetric Distribution of Reaction Products

    Science.gov (United States)

    Golestanian, Ramin; Liverpool, Tanniemola B.; Ajdari, Armand

    2005-06-01

    A simple model for the reaction-driven propulsion of a small device is proposed as a model for (part of) a molecular machine in aqueous media. The motion of the device is driven by an asymmetric distribution of reaction products. The propulsive velocity of the device is calculated as well as the scale of the velocity fluctuations. The effects of hydrodynamic flow as well as a number of different scenarios for the kinetics of the reaction are addressed.

  7. A nanojet: propulsion of a molecular machine by an asymmetric distribution of reaction--products

    Science.gov (United States)

    Liverpool, Tanniemola; Golestanian, Ramin; Ajdari, Armand

    2006-03-01

    A simple model for the reaction-driven propulsion of a small device is proposed as a model for (part of) a molecular machine in aqueous media. Motion of the device is driven by an asymmetric distribution of reaction products. We calculate the propulsive velocity of the device as well as the scale of the velocity fluctuations. We also consider the effects of hydrodynamic flow as well as a number of different scenarios for the kinetics of the reaction.

  8. Reactions of 3-Formylchromone with Active Methylene and Methyl Compounds and Some Subsequent Reactions of the Resulting Condensation Products

    Directory of Open Access Journals (Sweden)

    M. Lácova

    2005-08-01

    Full Text Available This review presents a survey of the condensations of 3-formylchromone with various active methylene and methyl compounds, e.g. malonic or barbituric acid derivatives, five-membered heterocycles, etc. The utilisation of the condensation products for the synthesis of different heterocyclic systems, which is based on the ability of the γ-pyrone ring to be opened by the nucleophilic attack is also reviewed. Finally, the applications of microwave irradiation as an unconventional method of reaction activation in the synthesis of condensation products is described and the biological activity of some chromone derivatives is noted.

  9. The effects of reactants ratios, reaction temperatures and times on Maillard reaction products of the L-ascorbic acid/L-glutamic acid system

    Directory of Open Access Journals (Sweden)

    Yong-Yan ZHOU

    2016-01-01

    Full Text Available Abstract The transformation law of the Maillard reaction products with three different reactants ratios - equimolar reactants, excess L-glutamic acid and excess L-ascorbic acid reaction respectively, five different temperatures, and different time conditions for the L-ascorbic acid / L-glutamic acid system were investigated. Results showed that, the increase of the reaction time and temperature led to the increase of the browning products, uncoloured intermediate products, as well as aroma compounds. Compared with the equimolar reaction system, the excess L-ascorbic acid reaction system produced more browning products and uncoloured intermediate products, while the aroma compounds production remained the same. In the excess L-glutamic acid system, the uncoloured intermediate products increased slightly, the browning products remained the same, while the aroma compounds increased.

  10. CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

    Science.gov (United States)

    Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

    2002-01-01

    Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

  11. Advances of zeolite based membrane for hydrogen production via water gas shift reaction

    Science.gov (United States)

    Makertihartha, I. G. B. N.; Zunita, M.; Rizki, Z.; Dharmawijaya, P. T.

    2017-07-01

    Hydrogen is considered as a promising energy vector which can be obtained from various renewable sources. However, an efficient hydrogen production technology is still challenging. One technology to produce hydrogen with very high capacity with low cost is through water gas shift (WGS) reaction. Water gas shift reaction is an equilibrium reaction that produces hydrogen from syngas mixture by the introduction of steam. Conventional WGS reaction employs two or more reactors in series with inter-cooling to maximize conversion for a given volume of catalyst. Membrane reactor as new technology can cope several drawbacks of conventional reactor by removing reaction product and the reaction will favour towards product formation. Zeolite has properties namely high temperature, chemical resistant, and low price makes it suitable for membrane reactor applications. Moreover, it has been employed for years as hydrogen selective layer. This review paper is focusing on the development of membrane reactor for efficient water gas shift reaction to produce high purity hydrogen and carbon dioxide. Development of membrane reactor is discussed further related to its modification towards efficient reaction and separation from WGS reaction mixture. Moreover, zeolite framework suitable for WGS membrane reactor will be discussed more deeply.

  12. C-13 isotopic studies of the surface catalysed reactions of methane

    International Nuclear Information System (INIS)

    Long, M.A.; He, S.J.X.; Adebajo, M.

    1997-01-01

    The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

  13. 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.)

  14. Recent applications of intramolecular Diels-Alder reactions to natural product synthesis

    DEFF Research Database (Denmark)

    Juhl, M.; Tanner, David Ackland

    2009-01-01

    This tutorial review presents some recent examples of intramolecular Diels-Alder (IMDA) reactions as key complexity-generating steps in the total synthesis of structurally intricate natural products. The opportunities afforded by transannular (TADA) versions of the IMDA reaction in complex molecu...... comprehensive, reviews....

  15. Mapping Students' Conceptual Modes When Thinking about Chemical Reactions Used to Make a Desired Product

    Science.gov (United States)

    Weinrich, M. L.; Talanquer, V.

    2015-01-01

    The central goal of this qualitative research study was to uncover major implicit assumptions that students with different levels of training in the discipline apply when thinking and making decisions about chemical reactions used to make a desired product. In particular, we elicited different ways of conceptualizing why chemical reactions happen…

  16. Chemical methods and techniques to monitor early Maillard reaction in milk products; A review.

    Science.gov (United States)

    Aalaei, Kataneh; Rayner, Marilyn; Sjöholm, Ingegerd

    2018-01-23

    Maillard reaction is an extensively studied, yet unresolved chemical reaction that occurs as a result of application of the heat and during the storage of foods. The formation of advanced glycation end products (AGEs) has been the focus of several investigations recently. These molecules which are formed at the advanced stage of the Maillard reaction, are suspected to be involved in autoimmune diseases in humans. Therefore, understanding to which extent this reaction occurs in foods, is of vital significance. Because of their composition, milk products are ideal media for this reaction, especially when application of heat and prolonged storage are considered. Thus, in this work several chemical approaches to monitor this reaction in an early stage are reviewed. This is mostly done regarding available lysine blockage which takes place in the very beginning of the reaction. The most popular methods and their applications to various products are reviewed. The methods including their modifications are described in detail and their findings are discussed. The present paper provides an insight into the history of the most frequently-used methods and provides an overview on the indicators of the Maillard reaction in the early stage with its focus on milk products and especially milk powders.

  17. Geostationary Surface and Insolation Products (GSIP), Version 3

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The Geostationary Surface and Insolation Products (GSIP) Version 3 contains upwelling and downwelling shortwave (0.2-4.0 um) and visible (0.4-0.7 um) radiative...

  18. NOAA High-Resolution Sea Surface Temperature (SST) Analysis Products

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This archive covers two high resolution sea surface temperature (SST) analysis products developed using an optimum interpolation (OI) technique. The analyses have a...

  19. 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...

  20. Radioactive nuclide production and isomeric state branching ratios in P + W reactions to 200 mev

    International Nuclear Information System (INIS)

    Young, P.G.; Chadwick, M.B.

    1995-01-01

    Calculations of nuclide yields from spallation reactions usually assume that the products are formed in their ground states. We are performing calculations of product yields from proton reactions on tungsten isotopes that explicitly account for formation of the residual nuclei in excited states. The Hauser-Feshbach statistical/preequilibrium code GNASH, with full accounting for angular momentum conservation and electromagnetic transitions, is utilized in the calculations. We present preliminary results for isomer branching ratios for proton reactions to 200 MeV for several products including the 31-y, 16+ state in l78 Hf and the 25-d, 25/2- state in 179 Hf. Knowledge of such branching ratios, might be important for concepts such as accelerator production of tritium that utilize intermediate-energy proton reactions on tungsten

  1. A new branch of advertising: reviewing factors that influence reactions to product placement

    NARCIS (Netherlands)

    van Reijmersdal, E.; Neijens, P.; Smit, E.G.

    2009-01-01

    This iiterature review presents a quantitative synthesis of 57 studies on product placement and shows which factors are most effective, it shows that placement characteristics, such as placement commerciality, modality, and prominence, have a strong impact on audience reactions. Audience

  2. Liquid composition having ammonia borane and decomposing to form hydrogen and liquid reaction product

    Science.gov (United States)

    Davis, Benjamin L; Rekken, Brian D

    2014-04-01

    Liquid compositions of ammonia borane and a suitably chosen amine borane material were prepared and subjected to conditions suitable for their thermal decomposition in a closed system that resulted in hydrogen and a liquid reaction product.

  3. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L S; Kenny, M J; Wieczorek, L [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1994-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  4. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S.; Kenny, M.J.; Wieczorek, L. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1993-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  5. Analysis of Anomaly in Land Surface Temperature Using MODIS Products

    Science.gov (United States)

    Yorozu, K.; Kodama, T.; Kim, S.; Tachikawa, Y.; Shiiba, M.

    2011-12-01

    Atmosphere-land surface interaction plays a dominant role on the hydrologic cycle. Atmospheric phenomena cause variation of land surface state and land surface state can affect on atmosphereic conditions. Widely-known article related in atmospheric-land interaction was published by Koster et al. in 2004. The context of this article is that seasonal anomaly in soil moisture or soil surface temperature can affect summer precipitation generation and other atmospheric processes especially in middle North America, Sahel and south Asia. From not only above example but other previous research works, it is assumed that anomaly of surface state has a key factor. To investigate atmospheric-land surface interaction, it is necessary to analyze anomaly field in land surface state. In this study, soil surface temperature should be focused because it can be globally and continuously observed by satellite launched sensor. To land surface temperature product, MOD11C1 and MYD11C1 products which are kinds of MODIS products are applied. Both of them have 0.05 degree spatial resolution and daily temporal resolution. The difference of them is launched satellite, MOD11C1 is Terra and MYD11C1 is Aqua. MOD11C1 covers the latter of 2000 to present and MYD11C1 covers the early 2002 to present. There are unrealistic values on provided products even if daily product was already calibrated or corrected. For pre-analyzing, daily data is aggregated into 8-days data to remove irregular values for stable analysis. It was found that there are spatial and temporal distribution of 10-years average and standard deviation for each 8-days term. In order to point out extreme anomaly in land surface temperature, standard score for each 8-days term is applied. From the analysis of standard score, it is found there are large anomaly in land surface temperature around north China plain in early April 2005 and around Bangladesh in early May 2009.

  6. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

    Science.gov (United States)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-28

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

  7. Biodiesel Production from Vegetable Oil over Plasma Reactor: Optimization of Biodiesel Yield using Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Bambang Tri Nugroho

    2009-06-01

    Full Text Available Biodiesel production has received considerable attention in the recent past as a renewable fuel. The production of biodiesel by conventional transesterification process employs alkali or acid catalyst and has been industrially accepted for its high conversion and reaction rates. However for alkali catalyst, there may be risk of free acid or water contamination and soap formation is likely to take place which makes the separation process difficult. Although yield is high, the acids, being corrosive, may cause damage to the equipment and the reaction rate was also observed to be low. This research focuses on empirical modeling and optimization for the biodiesel production over plasma reactor. The plasma reactor technology is more promising than the conventional catalytic processes due to the reducing reaction time and easy in product separation. Copyright (c 2009 by BCREC. All Rights reserved.[Received: 10 August 2009, Revised: 5 September 2009, Accepted: 12 October 2009][How to Cite: I. Istadi, D.D. Anggoro, P. Marwoto, S. Suherman, B.T. Nugroho (2009. Biodiesel Production from Vegetable Oil over Plasma Reactor: Optimization of Biodiesel Yield using Response Surface Methodology. Bulletin of Chemical Reaction Engineering and Catalysis, 4(1: 23-31. doi:10.9767/bcrec.4.1.23.23-31][How to Link/ DOI: http://dx.doi.org/10.9767/bcrec.4.1.23.23-31

  8. Biodiesel Production from Vegetable Oil over Plasma Reactor: Optimization of Biodiesel Yield using Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2009-06-01

    Full Text Available Biodiesel production has received considerable attention in the recent past as a renewable fuel. The production of biodiesel by conventional transesterification process employs alkali or acid catalyst and has been industrially accepted for its high conversion and reaction rates. However for alkali catalyst, there may be risk of free acid or water contamination and soap formation is likely to take place which makes the separation process difficult. Although yield is high, the acids, being corrosive, may cause damage to the equipment and the reaction rate was also observed to be low. This research focuses on empirical modeling and optimization for the biodiesel production over plasma reactor. The plasma reactor technology is more promising than the conventional catalytic processes due to the reducing reaction time and easy in product separation. Copyright (c 2009 by BCREC. All Rights reserved.[Received: 10 August 2009, Revised: 5 September 2009, Accepted: 12 October 2009][How to Cite: I. Istadi, D.D. Anggoro, P. Marwoto, S. Suherman, B.T. Nugroho (2009. Biodiesel Production from Vegetable Oil over Plasma Reactor: Optimization of Biodiesel Yield using Response Surface Methodology. Bulletin of Chemical Reaction Engineering and Catalysis, 4(1: 23-31.  doi:10.9767/bcrec.4.1.7115.23-31][How to Link/ DOI: http://dx.doi.org/10.9767/bcrec.4.1.7115.23-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/7115

  9. The unexpected product of Diels-Alder reaction between "indanocyclon" and maleimide

    Science.gov (United States)

    Dobrowolski, Michał A.; Roszkowski, Piotr; Struga, Marta; Szulczyk, Daniel

    2017-02-01

    A heterocyclic compound commonly known as "indanocyclon" undergoes an unexpected Diels-Alder addition with maleimide. The resulting product has been isolated and characterized in order to get an information about its structure and possible mechanism of the reaction. Extensive comparison of single crystal properties of 3-(2,8-dioxo-1,3-diphenyl-2,8-dihydrocyclopenta[a]inden-8a(1H)-yl)pyrrolidine-2,5-dione and favorable product of the reaction has been also performed.

  10. Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model.

    Science.gov (United States)

    Kroonblawd, Matthew P; Pietrucci, Fabio; Saitta, Antonino Marco; Goldman, Nir

    2018-04-10

    We demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTB model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol -1 .

  11. Light-induced heterogeneous reactions of NO2 on indoor surfaces: How they affect the balance of nitrous acid

    Science.gov (United States)

    Gomez Alvarez, E.; Soergel, M.; Bassil, S.; Zetzsch, C.; Gligorovski, S.; Wortham, H.

    2011-12-01

    Nitrous acid (HONO) is an important indoor pollutant. The adverse health effects due to the formation of nitrosamines are well known. HONO acts as a nitrosating agent after wall reactions of HONO with nicotine [Sleiman et al., 2010]. Indoor air can be surprisingly rich in HONO (homes with fireplaces, stoves, gas heating and cooking) and also surfaces are abundant. High HONO concentrations have been measured in indoor environments, from the direct emissions and heterogeneous reactions of NO2 in darkness. However, the measured HONO concentrations do not correspond to the HONO levels determined by the models [Carslaw, 2007]. We have tested in a flow tube reactor on-line coupled to a NOx analyzer and a sensitive Long Path Absorption Photometry instrument, the behaviour of various indoor surfaces towards NO2 under simulated solar light irradiation (λ= 300-700 nm). Our study has allowed us to obtain a deeper knowledge on the mechanisms of heterogeneous formation of HONO, quantifying the dependence of HONO formation on behalf of NO2 concentration and relative humidity and the enhancement of HONO formation in the presence of light. Pyrex, acidic detergent, alkaline detergent, paint and lacquer were tested on behalf of their heterogeneous reactivity towards NO2 in the absence and in presence of light. The results obtained demonstrated that indoor surfaces are photo-chemically active under atmospherically relevant conditions. The strongly alkaline surfaces (such as certain types of detergent) show a strong long-term uptake capacity. However, other surfaces such as detergents with a more acidic character released HONO. In some cases such as paint and varnish, a strong HONO release with light was detected, which was significantly higher than that obtained over clean glass surfaces. Certain organics present on their composition could exert a photo-sensitizing effect that may explain their increased reactivity. Unfortunately, the final balance points towards an important net

  12. 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.

  13. Lambda-HYPERNUCLEAR PRODUCTION IN (K(stop)(-), pi) REACTIONS

    Czech Academy of Sciences Publication Activity Database

    Krejčiřík, Vojtěch; Cieplý, Aleš

    2011-01-01

    Roč. 26, 3-4 (2011), s. 663-664 ISSN 0217-751X. [11th International Workshop on Meson Production, Properties and Interaction. Krakow, 10.06.2010-15.06.2010] R&D Projects: GA ČR GA202/09/1441 Institutional research plan: CEZ:AV0Z10480505 Keywords : Hypernuclei * DWIA * chiral model Subject RIV: BE - Theoretical Physics Impact factor: 1.053, year: 2011

  14. Laser application for nuclear reaction product detecting system alignment

    International Nuclear Information System (INIS)

    Grantsev, V.I.; Dryapachenko, I.P.; Kornilov, V.A.; Nemets, O.F.; Rudenko, B.A.; Sokolov, M.V.; Struzhko, B.G.; Gnatovskij, A.V.; Bojchuk, V.N.

    1982-01-01

    A method for optical alignment of nuclear particle detector system using a laser beam and hologram is described. The method permits to arrange detectors very precisely in accordance with any chosen space coordinate values. The results of modelling the geometry of an experiment based on using the suggested method on cyclotron beams are described. A gas helium-neon laser with wavelength of 0.63 μm radiation power of an order of 2 MW and angular beam divergence less than 10 angular minutes is used for modelling. It is concluded that the laser and hologram application provides large possibilities for the modelling the geometry of experiments on nuclear reaction investigation. When necessary it is possible to obtain small nonius scale of reference beams by means of multiplicating properties of the wave front modulator-hologram system. It is also possible to record holograms shaping the reference beams in two or several planes crossing along the central beam direction. Such holograms can be used for modelling the noncoplanar geometry of correlation experiments [ru

  15. Aromatic products from reaction of lignin model compounds with UV-alkaline peroxide

    International Nuclear Information System (INIS)

    Sun, Y.P.; Wallis, A.F.A.; Nguyen, K.L.

    1997-01-01

    A series of guaiacyl and syringyl lignin model compounds and their methylated analogues were reacted with alkaline hydrogen peroxide while irradiating with UV light at 254 nm. The aromatic products obtained were investigated by gas chromatography-mass spectrometry (GC-MS). Guaiacol, syringol and veratrol gave no detectable aromatic products. However, syringol methyl ether gave small amounts of aromatic products, resulting from ring substitution and methoxyl displacement by hydroxyl radicals. Reaction of vanillin and syringaldehyde gave the Dakin reaction products, methoxy-1,4-hydroquinones, while reaction of their methyl ethers yielded benzoic acids. Acetoguaiacone, acetosyringone and their methyl ethers afforded several hydroxylated aromatic products, but no aromatic products were identified in the reaction mixtures from guaiacylpropane and syringylpropane. In contrast, veratrylpropane gave a mixture from which 17 aromatic hydroxylated compounds were identified. It is concluded that for phenolic lignin model compounds, particularly those possessing electrondonating aromatic ring substituents, ring-cleavage reactions involving superoxide radical anions are dominant, whereas for non-phenolic lignin models, hydroxylation reactions through attack of hydroxyl radicals prevail

  16. Transformation reactions in TOXSWA : transformation reactions of plant protection products in surface water

    NARCIS (Netherlands)

    Deneer, J.W.; Beltman, W.H.J.; Adriaanse, P.I.

    2010-01-01

    This report aims to give a general description of transformation processes for future use in the TOXSWA model. Hydrolysis, photolysis and biotic transformation are described as distinct processes, employing separate rate constants. Additionally, a way to introduce into TOXSWA the daily variation of

  17. Application of radioanalytical techniques in the study of the products of heavy-ion reactions

    International Nuclear Information System (INIS)

    Hoffman, D.C.

    1989-01-01

    The use of heavy ions to induce nuclear reactions was reported as early as 1950. Since then it has been one of the most active areas of nuclear research. Intense beams of ions as heavy as uranium with energies high enough to overcome the Coulomb barriers of even the heaviest elements are available. The large variety of possible reactions gives rise to a multitude of products, which have been studied by many chemical and physical techniques. Chemical techniques have been of special value for the separation and unequivocal identification of low-yield species from the plethora of other nuclides present. Heavy-ion reactions have been essential for the production of the transmendelevium elements and a host of new isotopes. The systematics of compound nucleus reactions, transfer reactions and deeply inelastic reactions have been elucidated using chemical techniques. The variety of chemical procedures and techniques which have been developed for the study of heavy-ion reactions and their products has been examined. The determination of the chemical properties of the transmendelevium elements, which are very short-lived and can only be produced an ''atom at a time'' via heavy-ion reactions, is discussed. (author)

  18. Optimization and Modeling of Process Variables of Biodiesel Production from Marula Oil using Response Surface Methodology

    International Nuclear Information System (INIS)

    Enweremadu, C. C.; Rutto, H. L.

    2015-01-01

    This paper presents an optimization study in the production of biodiesel production from Marula oil. The study was carried out using a central composite design of experiments under response surface methodology. A mathematical model was developed to correlate the transesterification process variables to biodiesel yield. The transesterification reaction variables were methanol to oil ratio, x /sub 1/ (10-50 wt percentage), reaction time, x /sub 2/ (30-90 min), reaction temperature, x /sub 3/ (30-90 Degree C) stirring speed, x /sub 4/ (100-400 rpm) and amount of catalyst, x /sub 5/ (0.5-1.5 g). The optimum conditions for the production of the biodiesel were found to be methanol to oil ratio (29.43 wt percentage), reaction time (59.17 minutes), reaction temperature (58.80 Degree C), stirring speed (325 rpm) and amount of catalyst (1.02 g). The optimum yield of biodiesel that can be produced was 95 percentage. The results revealed that the crucial fuel properties of the biodiesel produced at the optimum conditions met the ASTM biodiesel specifications. (author)

  19. GOES Surface and Insolation Products (GSIP), Version 2

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Version 2 of the GOES Surface and Insolation Products (GSIP) is a high spatial resolution (1/8 x 1/8 degrees) solar radiation product estimated from the GOES-East...

  20. Dilepton and vector meson production in heavy-ion reactions

    International Nuclear Information System (INIS)

    Wolf, Gy.

    1997-01-01

    A nonperturbative dynamical study of dilepton an vector meson production in heavy-ion collisions from 1 to 2 GeV/A bombarding energies is presented incorporating all known sources relevant in this energy range. The dynamical evolution of the nucleus-nucleus collision is described by a transport equation of the Boltzmann-Uehling-Uhlenbeck type evolving phase-space distribution functions for nucleons, baryon resonances, pions, η's, ρ's and σ's with their isospin degrees of freedom. In particular, the sensitivity of the calculated yields to predicted changes of the ρ and ω mesons in dense matter is investigated. (author)

  1. 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

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

    Science.gov (United States)

    Csernica, Stephen N.

    transitions from two phases to a single phase, or pseudo-single phase. The transition to a single phase or pseudo-single phase is a function of the methanol content. Regardless, the maximum observed reaction rate occurs at the point of the phase transition, when the concentration of triglycerides in the methanol phase is largest. The phase transition occurs due to the accumulation of the primary product, biodiesel methyl esters. Through various experiments, it was determined that the rate of the triglyceride mass transfer into the methanol phase, as well as the solubility of triglycerides in methanol, increases with increasing methyl ester concentration. Thus, there exists some critical methyl ester concentration which favors the formation of a single or pseudo-single phase system. The effect of the by-product glycerol on the reaction kinetics was also investigated. It was determined that at low methanol to triglyceride molar ratios, glycerol acts to inhibit the reaction rate and limit the overall triglyceride conversion. This occurs because glycerol accumulates in the methanol phase, i.e. the primary reaction volume. When glycerol is at relatively high concentrations within the methanol phase, triglycerides become excluded from the reaction volume. This greatly reduces the reaction rate and limits the overall conversion. As the concentration of methanol is increased, glycerol becomes diluted and the inhibitory effects become dampened. Assuming pseudo-homogeneous phase behavior, a simple kinetic model incorporating the inhibitory effects of glycerol was proposed based on batch reactor data. The kinetic model was primarily used to theoretically compare the performance of different types of continuous flow reactors for continuous biodiesel production. It was determined that the inhibitory effects of glycerol result in the requirement of very large reactor volumes when using continuous stirred tank reactors (CSTR). The reactor volume can be greatly reduced using tubular style

  3. Determination of gamma production from (n, gamma) reactions

    International Nuclear Information System (INIS)

    Kostal, M.

    2007-06-01

    Calculation of gamma production by interaction of neutrons with materials requires a reasonable accuracy of the nuclear libraries, i. e. effective cross sections, nuclear levels and probabilities of transitions between them. Accurate data enable accurate calculations to be performed, e.g. for PGNAA. First, gamma production in a thick 56 Fe target was examined. Appreciable discrepancies were found among the nuclear libraries available. Additional calculations were performed and compared with the observed data. The fluence of photons observed behind a thick iron target was investigated, the target being irradiated with neutrons from the front side. The results were evaluated for the various nuclear libraries. It is concluded that the libraries ENDF/B VI.2., i.e. data embedded in the MCNPX code, are sufficient for a number of applications. However, their accuracy is insufficient for prompt gamma neutron activation analysis. This is also true of data from the libraries JEFF 3.1. a JENDL 3.3, so that other libraries will have to be used for PGNAA. Specifically for 56 Fe, the data from the libraries ENDF/B VII.0 seem to be usable. (P.A.)

  4. 40 CFR 721.6181 - Fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acid, reaction product with... Specific Chemical Substances § 721.6181 Fatty acid, reaction product with substituted oxirane, formaldehyde... as fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

  5. Projectile like fragment production in Ar induced reactions around the Fermi energy

    International Nuclear Information System (INIS)

    Borrel, V.; Gatty, B.; Jacquet, D.; Galin, J.

    1986-01-01

    The production of projectile like fragments (PLF) has been studied in Ar induced reactions on various targets. It shows very clearly, that besides the predominance of fragmentation for most of the products, the transfer process is still a very strong component for products nearby the projectile. The influence of the target neutron excess on the PLF production is investigated as well as the evolution with incident energy of the characteristics of the different competing processes

  6. Effect of Reaction Conditions on the Surface Modification of Cellulose Nanofibrils with Aminopropyl Triethoxysilane

    Directory of Open Access Journals (Sweden)

    Eduardo Robles

    2018-04-01

    Full Text Available Nine different surface modifications of cellulose nanofibrils (CNF with 3-aminopropyl triethoxysilane (ATS by using three different solvent systems (water, ethanol, and a mixture of both were investigated. The effect of reaction conditions, such as silane to cellulose ratio and solvent type were evaluated to determine their contribution to the extent of the silane modification. Nanofibril properties were evaluated by infrared spectroscopy, powder X-ray diffraction, surface free energy, thermogravimetry, 13C and 29Si nuclear magnetic resonance, and electronic microscopy. The influence of the solvent in the solvolysis of the silane was reflected in the presence or absence of ethoxy groups in the silane. On the other hand, whereas the surface modification was increased directly proportionally to silane ratio on the reaction, the aggregation of nanofibrils was also increased, which can play a negative role in certain applications. The increment of silane modification also had substantial repercussions on the crystallinity of the nanofibrils by the addition of amorphous components to the crystalline unit; moreover, silane surface modifications enhanced the hydrophobic character of the nanofibrils.

  7. 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

  8. Study on interfacial reaction between lead-free solders and alternative surface finishes

    International Nuclear Information System (INIS)

    Siti Rabiatul Aisha; Ourdjini, A.; Saliza Osman

    2007-01-01

    This study investigates the interfacial reactions occurring during reflow soldering between Sn-Ag-Cu lead-free solder and two surface finishes: electroless nickel/ immersion gold (ENIG) and immersion silver (IAg). The study focuses on interfacial reactions evolution and growth kinetics of intermetallic compounds (IMC) formed during soldering and isothermal ageing at 150 degree Celsius for up to 2000 hours. Optical and scanning electron microscopy were used to measure IMC thickness and examine the morphology of IMC respectively, whereas the IMC phases were identified by energy dispersive X-ray analysis (EDX). The results showed that the IMC formed on ENIG finish is thinner compared to that formed on IAg finish. For IAg surface finish, Cu 6 Sn 5 IMCs with scallop morphology are formed at the solder/ surface finish interface after reflow while a second IMC, Cu 3 Sn was formed between the copper and Cu 6 Sn 5 IMC after the isothermal ageing treatment. For ENIG surface finish both (Cu,Ni) 6 Sn 5 and (Ni,Cu) 3 Sn 4 are formed after soldering. Isothermal aging of the solder joints formed on ENIG finish was found to have a significant effect on the morphology of the intermetallics by transforming to more spherical and denser morphology in addition to increase i their thickness with increased ageing time. (author)

  9. Novel ion-molecular surface reaction to result in CH3 adsorbates on (111) surface of chemical vapor deposition diamond from ethane and surface anionic sites

    International Nuclear Information System (INIS)

    Komatsu, Shojiro; Okada, Katsuyuki; Shimizu, Yoshiki; Moriyoshi, Yusuke

    2001-01-01

    The existence of CH 3 adsorbates on (111) surface of chemical vapor deposited diamond, which was observed by scanning tunneling microscopy, was explained by the following S N 2 (bimolecular, substitutional, and nucleophilic) type surface reaction; C(s) - +C 2 H 6 ->C(s)-CH 3 +CH 3 - , where C(s) denotes a surface carbon atom. The activation energy was estimated to be 36.78 kcal/mol and the reaction proved to be exothermic with the enthalpy change of -9.250 kcal/mol, according to ab initio molecular orbital calculations at MP2/3-21+G * //RHF/3-21G * level; this result is consistent with typical substrate temperatures, namely about 900 degree C, for chemical vapor deposition of diamond. Charge transfer from the highest occupied molecular orbital of the surface anionic site to the lowest unoccupied molecular orbital of ethane, that is antibonding at the CH 3 - CH 3 bond, has been clearly visualized. A characteristic configuration of an ethane molecule which is associated with an anionic vacant site C(s) - on hydrogenated (111) surface of diamond was also found. [copyright] 2001 American Institute of Physics

  10. Characterisation and surface reactions of iron oxides and fluorapatite in aqueous suspensions

    OpenAIRE

    Jarlbring, Mathias

    2004-01-01

    The final objective of this study is to produce chemical models of flotation- like systems, including oxidation products of magnetite (maghemite and hematite) together with apatite. This is started by investigating the acid base properties, surface complexation and surface characteristics of the systems hematite-H+ and maghemite-H+ (paper I), fluorapatite-OH- (paper II) and a mixed system of maghemite-fluorapatite-OH- (paper III). Synthetic minerals were prepared and characterised with BET, S...

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

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

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

  12. Computational study of ethanol adsorption and reaction over rutile TiO2 (110) surfaces

    KAUST Repository

    Muir, J. N.

    2012-01-01

    Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO 2 rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti 4+ 5c) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E ads was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti 4+ 5c closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti 3+ cations. In this case the dissociative adsorption becomes strongly favoured (E ads = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode. This journal is © 2012 the Owner Societies.

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

    Science.gov (United States)

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

    2018-03-13

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

  14. Optimization of Maillard reaction with ribose for enhancing anti-allergy effect of fish protein hydrolysates using response surface methodology.

    Science.gov (United States)

    Yang, Sung-Yong; Kim, Se-Wook; Kim, Yoonsook; Lee, Sang-Hoon; Jeon, Hyeonjin; Lee, Kwang-Won

    2015-06-01

    Halibut is served on sushi and as sliced raw fish fillets. We investigated the optimal conditions of the Maillard reaction (MR) with ribose using response surface methodology to reduce the allergenicity of its protein. A 3-factored and 5-leveled central composite design was used, where the independent variables were substrate (ribose) concentration (X1, %), reaction time (X2, min), and pH (X3), while the dependent variables were browning index (Y1, absorbance at 420nm), DPPH scavenging (Y2, EC50 mg/mL), FRAP (Y3, mM FeSO4/mg extract) and β-hexosaminidase release (Y4, %). The optimal conditions were obtained as follows: X1, 28.36%; X2, 38.09min; X3, 8.26. Maillard reaction products of fish protein hydrolysate (MFPH) reduced the amount of nitric oxide synthesis compared to the untreated FPH, and had a significant anti-allergy effect on β-hexosaminidase and histamine release, compared with that of the FPH control. We concluded that MFPH, which had better antioxidant and anti-allergy activities than untreated FPH, can be used as an improved dietary source. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Effectiveness and reaction networks of H2O2 vapor with NH3 gas for decontamination of the toxic warfare nerve agent, VX on a solid surface.

    Science.gov (United States)

    Gon Ryu, Sam; Wan Lee, Hae

    2015-01-01

    The nerve agent, O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) must be promptly eliminated following its release into the environment because it is extremely toxic, can cause death within a few minutes after exposure, acts through direct skin contact as well as inhalation, and persists in the environment for several weeks after release. A mixture of hydrogen peroxide vapor and ammonia gas was examined as a decontaminant for the removal of VX on solid surfaces at ambient temperature, and the reaction products were analyzed by gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectrometry (NMR). All the VX on glass wool filter disks was found to be eliminated after 2 h of exposure to the decontaminant mixtures, and the primary decomposition product was determined to be non-toxic ethyl methylphosphonic acid (EMPA); no toxic S-[2-(diisopropylamino)ethyl] methylphosphonothioic acid (EA-2192), which is usually produced in traditional basic hydrolysis systems, was found to be formed. However, other by-products, such as toxic O-ethyl S-vinyl methylphosphonothioate and (2-diisopropylaminoethyl) vinyl disulfide, were detected up to 150 min of exposure to the decontaminant mixture; these by-products disappeared after 3 h. The two detected vinyl byproducts were identified first in this study with the decontamination system of liquid VX on solid surfaces using a mixture of hydrogen peroxide vapor and ammonia gas. The detailed decontamination reaction networks of VX on solid surfaces produced by the mixture of hydrogen peroxide vapor and ammonia gas were suggested based on the reaction products. These findings suggest that the mixture of hydrogen peroxide vapor and ammonia gas investigated in this study is an efficient decontaminant mixture for the removal of VX on solid surfaces at ambient temperature despite the formation of a toxic by-product in the reaction process.

  16. 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.

  17. Limonene ozonolysis in the presence of nitric oxide: Gas-phase reaction products and yields

    Science.gov (United States)

    Ham, Jason E.; Harrison, Joel C.; Jackson, Stephen R.; Wells, J. R.

    2016-05-01

    The reaction products from limonene ozonolysis were investigated using the new carbonyl derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX). With ozone (O3) as the limiting reagent, five carbonyl compounds were detected. The yields of the carbonyl compounds are discussed with and without the presence of a hydroxyl radical (OHrad) scavenger, giving insight into the influence secondary OH radicals have on limonene ozonolysis products. The observed reaction product yields for limonaketone (LimaKet), 7-hydroxyl-6-oxo-3-(prop-1-en-2-yl)heptanal (7H6O), and 2-acetyl-5-oxohexanal (2A5O) were unchanged suggesting OHrad generated by the limonene + O3 reaction does not contribute to their formation. The molar yields of 3-isopropenyl-6-oxo-heptanal (IPOH) and 3-acetyl-6-oxoheptanal (3A6O) decreased by 68% and >95%; respectively, when OHrad was removed. This suggests that OHrad radicals significantly impact the formation of these products. Nitric oxide (NO) did not significantly affect the molar yields of limonaketone or IPOH. However, NO (20 ppb) considerably decreased the molar reaction product yields of 7H6O (62%), 2A5O (63%), and 3A6O (47%), suggesting NO reacted with peroxyl intermediates, generated during limonene ozonolysis, to form other carbonyls (not detected) or organic nitrates. These studies give insight into the transformation of limonene and its reaction products that can lead to indoor exposures.

  18. 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)

  19. Animal DNA identification in food products and animal feed by real time polymerase chain reaction method

    Directory of Open Access Journals (Sweden)

    Людмила Мар’янівна Іщенко

    2016-11-01

    Full Text Available Approbation of diagnostic tests for species identification of beef, pork and chicken by real time polymerase chain reaction method was done. Meat food, including heat treated and animal feed, was used for research. The fact of inconsistencies was revealed for product composition of some meat products that is marked by manufacturer 

  20. Maillard reaction products of rice protein hydrolysates with mono-, oligo- and polysaccharides

    Science.gov (United States)

    Rice protein, a byproduct of rice syrup production, is abundant but, its lack of functionality prevents its wide use as a food ingredient. Maillard reaction products of (MRPs) hydrolysates from the limited hydrolysis of rice protein (LHRP) and various mono-, oligo- and polysaccharides were evaluat...

  1. Surface reaction modification: The effect of structured overlayers of sulfur on the kinetics and mechanism of the decomposition of formic acid on Pt(111)

    Science.gov (United States)

    Abbas, N.; Madix, R. J.

    The reaction of formic acid (DCOOH) on Pt(111), Pt(111)-(2×2)S and Pt(111)-(√3×√3)R30°S surfaces was examined by temperature programmed reaction spectroscopy. On the clean surface formic acid decomposed to yield primarily carbon dioxide and the hydrogenic species (H 2, HD and D 2) at low coverages. Although the formation of water and carbon monoxide via a dehydration reaction was observed at these coverages, the yield of these products was small when compared to the other products of reaction. The evolution of CO 2 at low temperature was ascribed to the decomposition of the formate intermediate. In the presence of sulfur the amount of molecularly adsorbed formic acid decreased up to a factor of three on the (√3×√3)R30°S surface, and a decline in the reactivity of over an order of magnitude was also observed. The only products formed were the hydrogenic species and carbon dioxide. The absence of carbon monoxide indicated that the dehydration pathway was blocked by sulfur. In addition to the low temperature CO 2 peak a high temperature CO 2-producing path was also evident. It was inferred from both the stoichiometry and the coincident evolution of D 2 and CO 2 in the high temperature states that these products also evolved due to the decomposition of the formate intermediate. On increasing the sulfur coverage to one-third monolayer this intermediate was further stabilized, and a predominance of the decomposition via the high temperature path was observed. Stability of the formate intermediate was attributed to inhibition of the decomposition reaction by sulfur atoms. The activation energy for formate decomposition increased from 15 kcal/gmole on the clean surface to 24.3 kcal/gmol on the (√3×√3)R30°S overlayer.

  2. Reactions

    DEFF Research Database (Denmark)

    Søndergaard, Morten

    2011-01-01

      My concern is to understand augmentation as an emergent modality - among many others in ‘the expanding digital field' (Søndergaard M. , Transformative Creativity in the Expanded Digital Field, 2009)' - attributed to the production of contemporary art and the ‘archive of knowledge' in the (art) ...

  3. On the angular distributions of the heavy products of (HI, xn) reactions

    International Nuclear Information System (INIS)

    Sagajdak, R.N.

    1989-01-01

    The effects of neutron evaporation and scattering in the target on the angular distribution of the heavy products of (HI, xn) reactions is considered. Based on the analysis of the experimental angular distributions and their calculated parameters a simple phenomenological approach to the description of these distributions is proposed. The calculated distributions are compared with the experimental ones cited in the literature. The possibilities of using the proposed approach to calculate the integrated angular distributions of heavy products and to determine the efficiency of collecting (HI, xn) reaction products under the conditions of the kinematic separation of recoil nuclei are outlined. 28 refs.; 9 figs

  4. "Cleaning" the Surface of Hydroxyapatite Nanorods by a Reaction-Dissolution Approach.

    Science.gov (United States)

    Cao, Binrui; Yang, Mingying; Wang, Lin; Xu, Hong; Zhu, Ye; Mao, Chuanbin

    2015-10-21

    Synthetic nanoparticles are always terminated with coating molecules, which are often cytotoxic and not desired in biomedicine. Here we propose a novel reaction-dissolution approach to remove the cytotoxic coating molecules. A two-component solution is added to the nanoparticle solution; one component reacts with the coating molecules to form a salt whereas another is a solvent for dissolving and thus removing the salt. As a proof of concept, this work uses a NaOH-ethanol solution to remove the cytotoxic linoleic acid molecules coated on the hydroxyapatite nanorods (HAP-NRs). The removal of the coating molecules not only significantly improves the biocompatibility of HAP-NRs but also enables their oriented attachment into tightly-bound superstructures, which mimic the organized HAP crystals in bone and enamel and can promote the osteogenic differentiation of mesenchymal stem cells. Our reaction-dissolution approach can be extended to the surface "cleaning" of other nanomaterials.

  5. Self-cleaning and surface chemical reactions during hafnium dioxide atomic layer deposition on indium arsenide.

    Science.gov (United States)

    Timm, Rainer; Head, Ashley R; Yngman, Sofie; Knutsson, Johan V; Hjort, Martin; McKibbin, Sarah R; Troian, Andrea; Persson, Olof; Urpelainen, Samuli; Knudsen, Jan; Schnadt, Joachim; Mikkelsen, Anders

    2018-04-12

    Atomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy. We find that the widely used ligand exchange model of the ALD process for the removal of native oxide on the semiconductor and the simultaneous formation of the first hafnium dioxide layer must be significantly revised. Our study provides substantial evidence that the efficiency of the self-cleaning process and the quality of the resulting semiconductor-oxide interface can be controlled by the molecular adsorption process of the ALD precursors, rather than the subsequent oxide formation.

  6. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jaramillo, Thomas F. [Stanford Univ., CA (United States). Dept. of Chemical Engineering. Shriram Center

    2016-04-20

    In this project, we have employed a systematic approach to develop active, selective, and stable catalyst materials for important electrochemical reactions involving energy conversion. In particular, we have focused our attention on developing active catalyst materials for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). HER: We have synthesized and investigated several highly active and acid stable non-precious metal HER catalysts, including: [Mo3S13]2- nanoclusters (Nature Chemistry, 2014) and molybdenum phosphosulfide (MoP|S) (Angewandte Chemie, 2014). We have also aimed to engineer these catalyst formulations in a membrane electrode assembly (MEA) for fundamental studies of water electrolysis at high current densities, approximately 1 A/cm2 (ChemSusChem, 2015). We furthermore investigated transition metal phosphide (TMP) catalysts for HER by a combined experimental–theoretical approach (Energy & Environmental Science, 2015). By synthesizing different TMPs and comparing experimentally determined HER activities with the hydrogen adsorption free energies, ΔGH, calculated by density functional theory, we showed that the TMPs follow a volcano relationship for the HER. Using our combined experimental–theoretical model, we predicted that the mixed metal TMP, Fe0.5Co0.5P, should have a near-optimal ΔGH. We synthesized several mixtures of Co and Fe phosphides alloys and confirmed that Fe0.5Co0.5P exhibits the highest HER activity of the investigated TMPs (Energy & Environmental Science, 2015). The understanding gained as to how to improve catalytic activity for the HER, particularly for non-precious metal materials, is important to DOE targets for sustainable H2 production. OER: We have developed a SrIrO3/IrOx catalyst for acidic conditions (submitted, 2016). The Sr

  7. 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.

  8. 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.

  9. The Surface Reactions of Ethanol over UO2(100) Thin Film

    KAUST Repository

    Senanayake, Sanjaya D.; Mudiyanselage, Kumudu; Burrell, Anthony K; Sadowski, Jerzy T.; Idriss, Hicham

    2015-01-01

    The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C1s, O1s and U4f to investigate the bonding mode, surface composition, electronic structure and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion sputtering of this UO2(100) did not result in noticeable reduction of U cations. The ethanol molecule has C-C, C-H, C-O and O-H bonds, and readily donates the hydroxyl H while interacting strongly with the UO2 surfaces. Upon ethanol adsorption (saturation occurred at 0.5 ML), only ethoxy (CH3CH2O-) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO-) on the Ar+-sputtered UO2(100) surface. All ethoxy and acetate species are removed from the surface between 600 and 700 K.

  10. The Surface Reactions of Ethanol over UO2(100) Thin Film

    KAUST Repository

    Senanayake, Sanjaya D.

    2015-10-08

    The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C1s, O1s and U4f to investigate the bonding mode, surface composition, electronic structure and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion sputtering of this UO2(100) did not result in noticeable reduction of U cations. The ethanol molecule has C-C, C-H, C-O and O-H bonds, and readily donates the hydroxyl H while interacting strongly with the UO2 surfaces. Upon ethanol adsorption (saturation occurred at 0.5 ML), only ethoxy (CH3CH2O-) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO-) on the Ar+-sputtered UO2(100) surface. All ethoxy and acetate species are removed from the surface between 600 and 700 K.

  11. Competing reactions of selected atmospheric gases on Fe3O4 nanoparticles surfaces.

    Science.gov (United States)

    Eltouny, N; Ariya, Parisa A

    2014-11-14

    Heterogeneous reactions on atmospheric aerosol surfaces are increasingly considered important in understanding aerosol-cloud nucleation and climate change. To understand potential reactions in polluted atmospheres, the co-adsorption of NO2 and toluene to magnetite (Fe3O4i.e. FeO·Fe2O3) nanoparticles at ambient conditions was investigated for the first time. The surface area, size distribution, and morphology of Fe3O4 nanoparticles were characterized by BET method and high-resolution transmission electron microscopy. Adsorption isotherms, collected by gas chromatography with flame ionization detection, showed that the presence of NO2 decreased the adsorption of toluene. The analyses of the surface chemical composition of Fe3O4 by X-ray photoelectron spectroscopy (XPS) reveal that, upon the addition of NO2, the surface is oxidized and a contribution at 532.5 ± 0.4 eV in the O1s spectrum appears, showing that NO2 likely competes with toluene by dissociating on Fe(2+) sites and forming NO3(-). Different competing effects were observed for oxidized Fe3O4; oxidation occurred when exposed solely to NO2, whereas, the mixture of toluene and NO2 resulted in a reduction of the surface i.e. increased Fe(2+)/Fe(3+). Analyses by time of flight secondary ion mass spectrometry further suggest toluene reacts with Fe(3+) sites forming oxygenated organics. Our results indicate that on reduced magnetite, NO2 is more reactive and competes with toluene; in contrast, on oxidized Fe3O4, toluene is more reactive. Because magnetite can assume a range of oxidation ratios in the environment, different competing interactions between pollutants like NO2 and toluene could influence atmospheric processes, namely, the formation of Fe(2+) and the formation of atmospheric oxidants.

  12. Adiabatic surface thermometer for improved production braze quality

    International Nuclear Information System (INIS)

    Dittbenner, G.R.

    1975-01-01

    An adiabatic surface thermometer was developed to control automatically the critical temperature-time cycle of a production vacuum-brazing process. Investigations revealed that optimum braze-joint strength required precise control of the brazing temperature. Spot-welded thermocouples could not be used because the spot welds cause surface damage. This thermometer touches the surface and uses a differential thermocouple and heater to measure surface temperature without heat flow, thereby eliminating large errors caused by conduction losses common to conventional spring-loaded thermocouples. Temperatures in air or vacuum are measured to 800 0 C with errors less than 5 0 C. This thermometer has minimized the rejection of production parts, resulting in a cost saving to the U. S. Energy Research and Development Administration

  13. Analysis of reaction cross-section production in neutron induced fission reactions on uranium isotope using computer code COMPLET.

    Science.gov (United States)

    Asres, Yihunie Hibstie; Mathuthu, Manny; Birhane, Marelgn Derso

    2018-04-22

    This study provides current evidence about cross-section production processes in the theoretical and experimental results of neutron induced reaction of uranium isotope on projectile energy range of 1-100 MeV in order to improve the reliability of nuclear stimulation. In such fission reactions of 235 U within nuclear reactors, much amount of energy would be released as a product that able to satisfy the needs of energy to the world wide without polluting processes as compared to other sources. The main objective of this work is to transform a related knowledge in the neutron-induced fission reactions on 235 U through describing, analyzing and interpreting the theoretical results of the cross sections obtained from computer code COMPLET by comparing with the experimental data obtained from EXFOR. The cross section value of 235 U(n,2n) 234 U, 235 U(n,3n) 233 U, 235 U(n,γ) 236 U, 235 U(n,f) are obtained using computer code COMPLET and the corresponding experimental values were browsed by EXFOR, IAEA. The theoretical results are compared with the experimental data taken from EXFOR Data Bank. Computer code COMPLET has been used for the analysis with the same set of input parameters and the graphs were plotted by the help of spreadsheet & Origin-8 software. The quantification of uncertainties stemming from both experimental data and computer code calculation plays a significant role in the final evaluated results. The calculated results for total cross sections were compared with the experimental data taken from EXFOR in the literature, and good agreement was found between the experimental and theoretical data. This comparison of the calculated data was analyzed and interpreted with tabulation and graphical descriptions, and the results were briefly discussed within the text of this research work. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  14. 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.

  15. Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

    International Nuclear Information System (INIS)

    Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

    2017-01-01

    Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

  16. Light-Baryon Production in Binary $pd$ Annihilation Reactions at Rest

    CERN Document Server

    Denisov, O Yu; Balestra, F; Botta, E; Bressani, Tullio; Bussa, M P; Busso, L; Calvo, D; Cerello, P G; Costa, S; D'Isep, D; Fava, L; Feliciello, A; Ferrero, L; Filippi, A; Garfagnini, R; Grasso, A; Iazzi, F; Maggiora, A; Marcello, S; Minetti, B; Mirfakhraee, N; Panzarasa, A; Panzieri, D; Piragino, G; Tosello, F; Zosi, G; Alberico, V; Bertin, A; Bruschi, M; Capponi, M; D'Antone, I; De Castro, S; Ferretti, A; Galli, D; Giacobbe, B; Marconi, U; Piccinini, M; Poli, M; Semprini-Cesari, N; Spighi, R; Vecchi, S; Vagnoni, V M; Vigotti, F; Villa, M; Vitale, A; Zoccoli, A; Bianconi, A; Corradini, M; Lodi-Rizzini, E; Venturelli, L; Zenoni, A; Cicalò, C; Masoni, A; Mauro, S; Puddu, G; Serci, S; Temnikov, P P; Usai, G L; Gortchakov, O E; Prakhov, S N; Rozhdestvensky, A M; Sapozhnikov, M G; Tretyak, V I; Gianotti, P; Guaraldo, C; Lanaro, A; Lucherini, V; Nichitiu, F; Petrascu, C; Ableev, V G; Cavion, C; Gastaldi, Ugo; Lombardi, M; Maron, G; Vannucci, Luigi; Vedovato, G; Bendiscioli, G; Filippini, V; Fontana, A; Montagna, P; Rotondi, A; Salvini, P; Pauli, G; Tessaro, S; Santi, L

    1999-01-01

    We report the study of light baryon production in two-prong annihilation reactions due to antiprotons stopping in gaseous deuterium and detected by the OBELIX spectrometer (LEAR, CERN). A clear signal of the Delta (1232) production in binary reactions was found in both annihilation channels: pd to pi /sup -/ Delta /sup +/( Delta /sup +/ to pi /sup 0/p) and pd to pi /sup 0/ Delta /sup 0/( Delta /sup 0/ to pi /sup -/p). The annihilation probabilities for these reactions turned out to be Y=(1.01+or-0.08)*10/sup -5/ and Y= (1.12+or-0.20)*10/sup -5/, respectively. In addition, the annihilation probability for the prototype Pontecorvo reaction pd to pi /sup -/p was measured with the best world statistics: Y= (1.46+or-0.08)*10/sup -5/. (16 refs).

  17. Reaction Acceleration in Thin Films with Continuous Product Deposition for Organic Synthesis.

    Science.gov (United States)

    Wei, Zhenwei; Wleklinski, Michael; Ferreira, Christina; Cooks, R Graham

    2017-08-01

    Thin film formats are used to study the Claisen-Schmidt base-catalyzed condensation of 6-hydroxy-1-indanone with substituted benzaldehydes and to compare the reaction acceleration relative to the bulk. Relative acceleration factors initially exceeded 10 3 and were on the order of 10 2 at steady state, although the confined volume reaction was not electrostatically driven. Substituent effects were muted compared to those in the corresponding bulk and microdroplet reactions and it is concluded that the rate-limiting step at steady state is reagent transport to the interface. Conditions were found that allowed product deposition from the thin film to occur continuously as the reaction mixture was added and as the solvent evaporated. Yields of 74 % and production rates of 98 mg h -1 were reached in a very simple experimental system that could be multiplexed to greater scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Bioactive Properties of Maillard Reaction Products Generated From Food Protein-derived Peptides.

    Science.gov (United States)

    Arihara, K; Zhou, L; Ohata, M

    Food protein-derived peptides are promising food ingredients for developing functional foods, since various bioactive peptides are released from food proteins. The Maillard reaction, which plays an important role in most processed foods, generates various chemical components during processing. Although changes of amino acids or proteins and reduced sugars by the Maillard reaction have been studied extensively, such changes of peptides by the Maillard reaction are still not resolved enough. Since food protein-derived peptides are widely utilized in many processed foods, it deserves concern and research on the changes of peptides by the Maillard reaction in foods during processing or storage. This chapter initially overviewed food protein-derived bioactive peptides. Then, Maillard reaction products generated from peptides are discussed. We focused particularly on their bioactivities. © 2017 Elsevier Inc. All rights reserved.

  19. Integrated system of production information processing for surface mines

    Energy Technology Data Exchange (ETDEWEB)

    Li, K.; Wang, S.; Zeng, Z.; Wei, J.; Ren, Z. [China University of Mining and Technology, Xuzhou (China). Dept of Mining Engineering

    2000-09-01

    Based on the concept of geological statistic, mathematical program, condition simulation, system engineering, and the features and duties of each main department in surface mine production, an integrated system for surface mine production information was studied systematically and developed by using the technology of data warehousing, CAD, object-oriented and system integration, which leads to the systematizing and automating of the information management, data processing, optimization computing and plotting. In this paper, its overall object, system design, structure and functions and some key techniques were described. 2 refs., 3 figs.

  20. SCALP: Scintillating ionization chamber for ALPha particle production in neutron induced reactions

    Science.gov (United States)

    Galhaut, B.; Durand, D.; Lecolley, F. R.; Ledoux, X.; Lehaut, G.; Manduci, L.; Mary, P.

    2017-09-01

    The SCALP collaboration has the ambition to build a scintillating ionization chamber in order to study and measure the cross section of the α-particle production in neutron induced reactions. More specifically on 16O and 19F targets. Using the deposited energy (ionization) and the time of flight measurement (scintillation) with a great accuracy, all the nuclear reaction taking part on this project will be identify.

  1. Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

    2009-12-23

    Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

  2. Ozone production in the reaction of T2 and O2 gas: A comparison of experimental results and model predictions

    International Nuclear Information System (INIS)

    Failor, R.A.; Souers, P.C.; Magnotta, F.

    1992-01-01

    Ozone, predicted to be an important intermediate species in T 2 oxidation, was monitored in situ by UV absorption spectroscopy for 0.01-1.0 mol % T 2 in O 2 (1 atm, 298 K). These are the first measurements of a tritium oxidation reaction intermediate. The experimental results were compared with the predictions of the author's comprehensive model of tritium oxidation. The experimentally determined temporal variation in ozone concentration is qualitatively reproduced by the model. As predicted, the measured initial rate of ozone production varied linearly with the initial T 2 concentration ([T 2 ] o ), but with a value one-third of that predicted. The steady-state ozone concentration ([O 3 ] ss ) a factor of 4 larger than predicted for a 1.0% T 2 -O 2 mixture. Addition of H 2 to the T 2 O 2 mixture, to differentiate between the radiolytic and chemical behavior of the tritium, produced a decrease in [O 3 ] ss which was larger than predicted. Changing the reaction cell surface-to-volume ratio showed indications of minor surface removal of ozone. No reasonable variation in model input parameters brought both the predicted initial ozone production rates and steady-state concentrations of ozone into agreement with the experimental results. Though qualitative agreement was achieved, further studies, with emphasis on surface effects, are necessary to explain quantitative differences and gain a greater understanding of the oxidation mechanism. 27 refs., 11 figs., 4 tabs

  3. Age influences the skin reaction pattern to mechanical stress and its repair level through skin care products.

    Science.gov (United States)

    Zouboulis, Christos C; Elewa, Rana; Ottaviani, Monica; Fluhr, Joachim; Picardo, Mauro; Bernois, Armand; Heusèle, Catherine; Camera, Emanuela

    2018-03-01

    Skin aging is associated with alterations of surface texture, sebum composition and immune response. Mechanical stress induces repair mechanisms, which may be dependent on the age and quality of the skin. The response to mechanical stress in young and aged individuals, their subjective opinion and the objective effectiveness of skin care products were evaluated by biophysical skin quality parameters (stratum corneum hydration, transepidermal water loss, skin pH, pigmentation and erythema) at baseline, 1, 6, 24h and 7days at the forearms of 2 groups of healthy volunteers, younger than 35 years (n=11) and older than 60 years (n=13). In addition, casual surface lipid composition was studied under the same conditions at the baseline and day 7 after mechanical stress induction. Evaluations were also performed in stressed skin areas treated daily with skin care products and the subjective opinion of the volunteers was additionally documented. The tested groups exhibited age-associated baseline skin functions as well as casual surface lipid composition and different reaction patterns to mechanical stress. Skin care was more effective in normalizing skin reaction to stress in the young than in the aged group. The subjective volunteer opinion correlated with the objective measurements. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Study of reactions for the production of uranium titrafluoride and uranium hexafluoride

    International Nuclear Information System (INIS)

    Guzella, M.F.R.

    1985-01-01

    The main production processes of uranium hexafluoride in pilot plants and industrial facilities are described. The known reactions confirmed in laboratory experiments that lead to Uf 6 or other intermediate fluorides are discussed. For the purpose of determining a thermodinamically feasible reaction involving the sulfur hexafluoride as fluorinating agent, a mock-up facility was designed and constructed as a part of the R and D work planned at the CDTN (Nuclebras Center for Nuclear Technology Development). IN the uranium tatrafluoride synthesis employing U 3 O 8 and SF 6 several experimental parameters are studied. The reaction time, gasflow, temperature and stoechiometic relations among reagents are described in detail. (Author) [pt

  5. Complex nuclear-structure phenomena revealed from the nuclide production in fragmentation reactions

    International Nuclear Information System (INIS)

    Ricciardi, M.V.; Kelic, A.; Napolitani, P.; Schmidt, K.H.; Yordanov, O.; Ignatyuk, A.V.; Rejmund, F.

    2003-12-01

    Complex structural effects in the nuclide production from the projectile fragmentation of 1 A GeV 238 U nuclei in a titanium target are reported. The structure seems to be insensitive to the excitation energy induced in the reaction. This is in contrast to the prominent structural features found in nuclear fission and in transfer reactions, which gradually disappear with increasing excitation energy. Using the statistical model of nuclear reactions, relations to structural effects in nuclear binding and in the nuclear level density are demonstrated. (orig.)

  6. High-intensity ultrasound production of Maillard reaction flavor compounds in a cysteine-xylose model system.

    Science.gov (United States)

    Ong, Olivia X H; Seow, Yi-Xin; Ong, Peter K C; Zhou, Weibiao

    2015-09-01

    Application of high intensity ultrasound has shown potential in the production of Maillard reaction odor-active flavor compounds in model systems. The impact of initial pH, sonication duration, and ultrasound intensity on the production of Maillard reaction products (MRPs) by ultrasound processing in a cysteine-xylose model system were evaluated using Response Surface Methodology (RSM) with a modified mathematical model. Generation of selected MRPs, 2-methylthiophene and tetramethyl pyrazine, was optimal at an initial pH of 6.00, accompanied with 78.1 min of processing at an ultrasound intensity of 19.8 W cm(-2). However, identification of volatiles using gas chromatography-mass spectrometry (GC/MS) revealed that ultrasound-assisted Maillard reactions generated fewer sulfur-containing volatile flavor compounds as compared to conventional heat treatment of the model system. Likely reasons for this difference in flavor profile include the expulsion of H2S due to ultrasonic degassing and inefficient transmission of ultrasonic energy. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Photocatalysis of irradiated semiconductor surfaces: Its application to water splitting and some organic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sakata, T

    1985-05-01

    Hydrogen production from organic compounds and water was investigated using powdered semiconductor photocatalysts. The complete decomposition observed for several organic compounds demonstrated that water is involved in the reactions as an oxidizing agent. Photocatalyses of dyes and semiconductors were found to be applicable to amino acid synthesis. The quantum yields of photocatalytic amino acid synthesis using visible light are about 20%-40% in the absence of a metal catalyst such as platinum. Moreover the reactions are highly selective and depend strongly on the type of semiconductor. This method was applied to the asymmetric synthesis of amino acids using asymmetric catalysts. Rather high optical yields of 50% were achieved for the synthesis of L-phenylalanine.

  8. 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.

  9. A field ion microscope study of the surface reaction of tungsten with n-octanol under an applied positive voltage: reaction conditions for the 'splitting' of (110) plane

    International Nuclear Information System (INIS)

    Terao, T.; Iwatsu, F.; Morikawa, H.

    1993-01-01

    Field ion microscopy is a powerful tool for the study of surface phenomena on an atomic scale, especially when they are crystal plane dependent, because the microscope shows many crystal planes of the sample tip simultaneously. Although a large number of FIM studies on vapor deposition, surface diffusion and surface reactions at a metal-gas interface have been reported, those on reactions at a metal-liquid interface are few. The authors have studied the corrosion or tungsten with aqueous solutions and found that water corroded the tungsten tips very severely to reduce the radius of curvature of the tip cap drastically. The reaction was so severe that it was not possible to trace it back to the very initial stages. They adopted, as a weaker reagent, one of the higher alcohols, n-octanol(C 8 H 17 OH), and found that it reacted with tungsten tips when an electrical pulse with a positive voltage between 5 and 10V was applied to the tip, giving very interesting field ion images in which the central (110) plane was divided into two parts located side by side across the [001] zone line. This means that some anisotropic surface reaction occurred which made a groove along the [001] zone line going through the (110) plane, usually the most stable plane chemically for bcc metals. They named this phenomenon 'splitting'. This reaction was less severe than that with water and some results on the morphology of the groove and on the reaction sequence have been reported. In the present paper more detailed reaction conditions which give rise to the splitting are described

  10. An ab initio potential energy surface for the reaction N+ + H2→ NH+ + H

    International Nuclear Information System (INIS)

    Gittins, M.A.; Hirst, D.M.

    1975-01-01

    Preliminary results of ab initio unrestricted Hartree-Fock calculations for the potential energy surface for the reaction N + + H 2 →NH + + H are reported. For the collinear approach of N + to H 2 , the 3 Σ - surface has no activation barrier and has a shallow well (ca.1eV). For perpendicular approach (Csub(2V)symmetry) the 3 B 2 states is of high energy, the 3 A 2 state has a shallow well but as the bond angle increases the 3 B 1 states decreases in energy to become the state of lowest energy. Neither the collinear nor the perpendicular approaches give adiabatic pathways to the deep potential well of 3 B 1 (HNH) + . (auth.)

  11. Comprehensive characterisation of products from cobalt catalysed Fischer-Tropsch reaction

    Energy Technology Data Exchange (ETDEWEB)

    Marion, M.C.; Bertoncini, F.; Hugues, F.; Forestiere, A. [IFP, Vernaison (France)

    2006-07-01

    Fischer-Tropsch reaction synthesis has been studied in presence of supported cobalt catalysts. The experimental work has been performed by using a slurry pilot plant. All the gaseous and liquid products, including by-products recovered in the water phase produced, have been analysed in order to determine the whole products distribution and the catalyst selectivity. Apart from paraffin which are the main products obtained via cobalt-catalyzed Fischer-Tropsch synthesis, olefins and oxygenates by-products present also their own distribution. These detailed data are available thanks to new dedicated analytical methods developed in IFP laboratories. (orig.)

  12. Shaping surface of palladium nanospheres through the control of reaction parameters

    International Nuclear Information System (INIS)

    Wang Lianmeng; Tan Enzhong; Guo Lin; Wang Lihua; Han Xiaodong

    2011-01-01

    Solid, cracked, and flower-shaped surfaces of palladium nanospheres with high yields and good uniformity were successfully prepared by a wet chemical method. On the basis of the experimental data, the same size of palladium nanosphere with different surface morphologies can be regulated only by changing the amount of ammonium hydroxide and reductant in one experimental system. The as-prepared products were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and x-ray diffraction (XRD). In addition, surface-enhanced Raman scattering (SERS) spectra on the as-prepared different surface of palladium nanospheres exhibit high activity towards p-aminothiophenol (PATP) detection, and the result further reveals that the predominance of the a1 vibration mode in the SERS spectra via an electromagnetic (EM) mechanism is significant.

  13. GPM Mission Gridded Text Products Providing Surface Precipitation Retrievals

    Science.gov (United States)

    Stocker, Erich Franz; Kelley, Owen; Huffman, George; Kummerow, Christian

    2015-04-01

    In February 2015, the Global Precipitation Measurement (GPM) mission core satellite will complete its first year in space. The core satellite carries a conically scanning microwave imager called the GPM Microwave Imager (GMI), which also has 166 GHz and 183 GHz frequency channels. The GPM core satellite also carries a dual frequency radar (DPR) which operates at Ku frequency, similar to the Tropical Rainfall Measuring Mission (TRMM) Precipitation Radar), and a new Ka frequency. The precipitation processing system (PPS) is producing swath-based instantaneous precipitation retrievals from GMI, both radars including a dual-frequency product, and a combined GMI/DPR precipitation retrieval. These level 2 products are written in the HDF5 format and have many additional parameters beyond surface precipitation that are organized into appropriate groups. While these retrieval algorithms were developed prior to launch and are not optimal, these algorithms are producing very creditable retrievals. It is appropriate for a wide group of users to have access to the GPM retrievals. However, for reseachers requiring only surface precipitation, these L2 swath products can appear to be very intimidating and they certainly do contain many more variables than the average researcher needs. Some researchers desire only surface retrievals stored in a simple easily accessible format. In response, PPS has begun to produce gridded text based products that contain just the most widely used variables for each instrument (surface rainfall rate, fraction liquid, fraction convective) in a single line for each grid box that contains one or more observations. This paper will describe the gridded data products that are being produced and provide an overview of their content. Currently two types of gridded products are being produced: (1) surface precipitation retrievals from the core satellite instruments - GMI, DPR, and combined GMI/DPR (2) surface precipitation retrievals for the partner

  14. Organic photochemical reactions on solid surfaces: Enrichment and separation of isotopes. Final report. SBIR-1988, Phase 2

    International Nuclear Information System (INIS)

    Ruderman, W.; Fehlner, J.; Spencer, J.

    1988-01-01

    The objectives of the Phase II program were to: (1) investigate organic photochemical reactions on solid porous silica surfaces, (2) utilize the magnetic isotope effect to develop a (13)C enrichment process using a fluidized bed reactor, and (3) investigate the possibility of enrichment of heavier isotopes having a nuclear spin. Although researchers were able to demonstrate a continuous fluidized bed (13)C enrichment process, analysis showed that the process could not compete with low temperature distillation of CO because of the high cost of the starting material, dibenzylketone (DBK), and the difficulty of converting the photochemical decomposition products back to DBK. However, the process shows promise for the separation of heavier isotopes such as (29)Si. The photochemical studies led to the discovery that the selectivity for terminal chlorination of alkanes can be increased more than 25 fold by sorbing the alkanes on ZSM-5 zeolites in a fluidized bed. The selectivity is ascribed to the presence of interfaces within the crystals

  15. Toxicological analysis of limonene reaction products using an in vitro exposure system

    Science.gov (United States)

    Anderson, Stacey E.; Khurshid, Shahana S.; Meade, B. Jean; Lukomska, Ewa; Wells, J.R.

    2015-01-01

    Epidemiological investigations suggest a link between exposure to indoor air chemicals and adverse health effects. Consumer products contain reactive chemicals which can form secondary pollutants which may contribute to these effects. The reaction of limonene and ozone is a well characterized example of this type of indoor air chemistry. The studies described here characterize an in vitro model using an epithelial cell line (A549) or differentiated epithelial tissue (MucilAir™). The model is used to investigate adverse effects following exposure to combinations of limonene and ozone. In A549 cells, exposure to both the parent compounds and reaction products resulted in alterations in inflammatory cytokine production. A one hour exposure to limonene + ozone resulted in decreased proliferation when compared to cells exposed to limonene alone. Repeated dose exposures of limonene or limonene + ozone were conducted on MucilAir™ tissue. No change in proliferation was observed but increases in cytokine production were observed for both the parent compounds and reaction products. Factors such as exposure duration, chemical concentration, and sampling time point were identified to influence result outcome. These findings suggest that exposure to reaction products may produce more severe effects compared to the parent compound. PMID:23220291

  16. Electrodeposition of Pd based binary catalysts on Carbon paper via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Direct alcohol fuel cells (DAFCs) continue to extensive attention as potential power sources for portable and stationary applications. The oxygen reduction reaction (ORR) involving the four electron transfer remains a challenge for DAFCs due to its...

  17. A Monte Carlo simulation of the exchange reaction between gaseous molecules and the atoms on a heterogeneous solid surface

    International Nuclear Information System (INIS)

    Imai, Hisao

    1980-01-01

    A method of the Monte Carlo simulation of the isotopic exchange reaction between gaseous molecules and the atoms on an arbitrarily heterogeneous solid surface is described by employing hydrogen as an example. (author)

  18. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    Science.gov (United States)

    Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

    2018-05-01

    Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

  19. Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone.

    Science.gov (United States)

    Zheng, Ying; Chen, Zhuo; Zheng, Chengbin; Lee, Yong-Ill; Hou, Xiandeng; Wu, Li; Tian, Yunfei

    2016-08-01

    A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5mgL(-1) or 0.09mM (3σ). The relative standard deviation (RSD) for 80mgL(-1) acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Investigation Into Accessible Surface Vinyl Concentrations of Nonstoichiometric PDMS Microspheres from Hydrosilylation Reactions and Their Further Crosslinking Reactions

    DEFF Research Database (Denmark)

    Ma, Baoguang; Hansen, Jens Henrik; Hvilsted, Søren

    2015-01-01

    The introduction of surface vinyl groups to PDMS microspheres broadens the latter's applicability range since the microspheres can be further functionalized or crosslinked into elastomers. Quantification of the surface vinyl concentration of PDMS microspheres is therefore essential. Here, a novel...

  1. Microarc Oxidation of Product Surfaces without Using a Bath

    Directory of Open Access Journals (Sweden)

    V. K. Shatalov

    2015-01-01

    Full Text Available While using an electrochemical method to cover the large-sized work-pieces, units, and products up to 6 м3 by protective coating, there is a certain difficulty to apply traditional anodizing techniques in a plating vat, and it is necessary to find various processing techniques.To use the existing micro-arc oxide coating (MOC methods for work-pieces of various forms and sizes in a plating vat is complicated in case it is required to provide oxide layers in separate places rather than over entire surface of a work-piece. The challenge is to treat flat surfaces in various directions, external and internal surfaces of rotation bodies, profiled surfaces, intersections, closed and through holes, pipes, as well as spline and thread openings for ensuring anti-seize properties in individual or small-scale production to meet technical requirements and operational properties of products.A design of tools to provide MOC-process of all possible surfaces of various engineering box-type products depends on many factors and can be considerably different even when processing the surfaces of the same forms. An attachment to be used is fixed directly on a large-sized design (a work-piece, a product or fastened in the special tool. The features of technological process, design shape, and arrangement of the processed surfaces define a fastening method of the attachment. Therefore it is necessary to pay much attention to a choice of the processing pattern and a design of tools.The Kaluga-branch of Bauman Moscow State Technical University is an original proposer of methods to form MOC-coatings on the separate surfaces of large-sized work-pieces using the moved and stationary electrodes to solve the above listed tasks.The following results of work will have an impact on development of the offered processing methods and their early implementation in real production:1. To provide oxide coatings on the surfaces of large-sized products or assemblies in a single or small

  2. Effect of surface functionalisation on the interaction of iron oxide nanoparticles with polymerase chain reaction.

    Science.gov (United States)

    Aysan, Ayse Beyza; Knejzlík, Zdeněk; Ulbrich, Pavel; Šoltys, Marek; Zadražil, Aleš; Štěpánek, František

    2017-05-01

    The combination of nanoparticles with the polymerase chain reaction (PCR) can have benefits such as easier sample handling or higher sensitivity, but also drawbacks such as loss of colloidal stability or inhibition of the PCR. The present work systematically investigates the interaction of magnetic iron oxide nanoparticles (MIONs) with the PCR in terms of colloidal stability and potential PCR inhibition due to interaction between the PCR components and the nanoparticle surface. Several types of MIONs with and without surface functionalisation by sodium citrate, dextran and 3-aminopropyl-triethoxysilane (APTES) were prepared and characterised by Transmission Electron Microscopy (TEM), dynamic light scattering (DLS) and Fourier Transform Infrared (FT-IR) spectroscopy. Colloidal stability in the presence of the PCR components was investigated both at room temperature and under PCR thermo-cycling. Dextran-stabilized MIONs show the best colloidal stability in the PCR mix at both room and elevated temperatures. Citrate- and APTES-stabilised as well as uncoated MIONs show a comparable PCR inhibition near the concentration 0.1mgml -1 while the inhibition of dextran stabilized MIONs became apparent near 0.5mgml -1 . It was demonstrated that the PCR could be effectively carried out even in the presence of elevated concentration of MIONs up to 2mgml -1 by choosing the right coating approach and supplementing the reaction mix by critical components, Taq DNA polymerase and Mg 2+ ions. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.

    Science.gov (United States)

    Favaro, Marco; Abdi, Fatwa F; Lamers, Marlene; Crumlin, Ethan J; Liu, Zhi; van de Krol, Roel; Starr, David E

    2018-01-18

    Bismuth vanadate has recently drawn significant research attention as a light-absorbing photoanode due to its performance for photoelectrochemical water splitting. In this study, we use in situ ambient pressure X-ray photoelectron spectroscopy with "tender" X-rays (4.0 keV) to investigate a polycrystalline bismuth vanadate (BiVO 4 ) electrode in contact with an aqueous potassium phosphate (KPi) solution at open circuit potential under both dark and light conditions. This is facilitated by the creation of a 25 to 30 nm thick electrolyte layer using the "dip-and-pull" method. We observe that under illumination bismuth phosphate forms on the BiVO 4 surface leading to an increase of the surface negative charge. The bismuth phosphate layer may act to passivate surface states observed in photoelectrochemical measurements. The repulsive interaction between the negatively charged surface under illumination and the phosphate ions in solution causes a shift in the distribution of ions in the thin aqueous electrolyte film, which is observed as an increase in their photoelectron signals. Interestingly, we find that such changes at the BiVO 4 /KPi electrolyte interface are reversible upon returning to dark conditions. By measuring the oxygen 1s photoelectron peak intensities from the phosphate ions and liquid water as a function of time under dark and light conditions, we determine the time scales for the forward and reverse reactions. Our results provide direct evidence for light-induced chemical modification of the BiVO 4 /KPi electrolyte interface.

  4. Dietary Maillard reaction products and their fermented products reduce cardiovascular risk in an animal model.

    Science.gov (United States)

    Oh, N S; Park, M R; Lee, K W; Kim, S H; Kim, Y

    2015-08-01

    This study examined the effects of Maillard reaction products (MRP) and MRP fermented by lactic acid bacteria on antioxidants and their enhancement of cardiovascular health in ICR mouse and rat models. In previous in vitro studies, the selected lactic acid bacteria were shown to significantly affect the activity of MRP. The expression of genes (e.g., superoxide dismutase, catalase, and glutathione peroxidase) related to antioxidant activity was upregulated by Maillard-reacted sodium caseinate (cMRP), and cMRP fermented by Lactobacillus fermentum H9 (F-cMRP) synergistically increased the expression of catalase and superoxide dismutase when compared with the high-cholesterol-diet group. Bleeding time, the assay for determination of antithrombotic activity, was significantly prolonged by Maillard-reacted whey protein concentration (wMRP) and wMRP fermented by Lactobacillus gasseri H10 (F-wMRP), similar to the bleeding time of the aspirin group (positive control). In addition, the acute pulmonary thromboembolism-induced mice overcame severe body paralysis or death in both the wMRP and the F-wMRP groups. In the serum-level experiment, cMRP and F-cMRP significantly reduced the serum total and low-density lipoprotein cholesterol levels and triglycerides but had only a slight effect on high-density lipoprotein cholesterol. The levels of aspartate transaminase and alanine transaminase also declined in the cMRP and F-cMRP intake groups compared with the high-cholesterol-diet group. In particular, F-cMRP showed the highest reducing effects on triglycerides, aspartate transaminase, and alanine transaminase. Moreover, the expression of cholesterol-related genes in the F-cMRP group demonstrated greater effects than for the cMRP group in the level of cholesterol 7 α-hydroxylase (CYP7A1), 3-hydroxy-3-methylglutaryl-CoA reductase (HMGR), and low-density lipoprotein receptors compared with the high-cholesterol-diet group. The protective role of cMRP and F-cMRP in the high

  5. Production of krypton isotopes by (p,xn) reactions on bromine

    International Nuclear Information System (INIS)

    Chiengmai, S.N.; Hans, L.; Petter, M.

    1976-06-01

    Radioactive isotopes of the halogens are of great importance when preparing radiopharmaceuticals. 77 Br has mainly been produced by a direct reaction 75 As(α,2n) 77 Br. Recently an indirect way, producing 77 Kr which then decays to 77 Br, has been suggested. Since this provides a convenient method of separation this work develops this idea further making use of high energy protons on bromine Br(p,xn) 77 Kr→ 77 Br. The production cross-section for this reaction has been studied in the proton-energy interval of 20-80 MeV and the optimal production procedures considered. (Auth.)

  6. Production of lactic acid from C6-polyols by alkaline hydrothermal reactions

    International Nuclear Information System (INIS)

    Zhou Huazhen; Jin Fangming; Wu Bing; Cao Jianglin; Duan Xiaokun; Kishita, Atsushi

    2010-01-01

    Production of lactic acid from C6-polyols (Mannitol) under alkaline hydrothermal conditions was investigated. Experiments were performed to examine the difference in the production of lactic acid between C6-polyols and C3-polyols (glycerine), as well as C6-aldoses (glucose). Results showed that the yield of lactic acid from C6-polyols was lower than that from both glycerine and glucose. It indicated that long chain polyols might follow a different reaction pathway from that of glycerine. Further investigation is needed to clarify the reaction mechanism and improve the relatively low lactic acid acid yield from C6-polyols.

  7. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    International Nuclear Information System (INIS)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone; Chorkendorff, Ib

    2012-01-01

    Highlights: ► Impedance spectroscopy of Cu/Pt(1 1 1) near-surface alloy and Pt(1 1 1). ► Presence of oxygen changes little the adsorption dynamics. ► Adsorption dynamics similar on alloy and Pt(1 1 1). ► Electrosorption phenomena on alloy shifted in potential, relative to Pt(1 1 1). - Abstract: The adsorption dynamics of *OH and *O species at Pt(1 1 1) and Cu/Pt(1 1 1) near-surface alloy (NSA) surfaces in oxygen-free and O 2 -saturated 0.1 M HClO 4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(1 1 1) surface resulting in weaker bonding to adsorbates like *OH, *H or *O. This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16 V towards more positive potentials can be clearly monitored in absence of O 2 and under the oxygen reduction reaction (ORR) conditions for the Cu/Pt(1 1 1) NSA. In both cases, for Pt(1 1 1) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when oxygen reduction takes place at the surface. A ∼5-fold improvement in the ORR activity over the Pt(1 1 1) at 0.9 V (RHE) was measured for the Cu/Pt(1 1 1) near-surface alloy.

  8. Late Quaternary changes in surface productivity and oxygen ...

    Indian Academy of Sciences (India)

    Changes in the abundance of selected planktic foraminiferal species and some sedimentological parameters at ODP site 728A were examined to understand the fluctuations in the surface productivity and deep sea oxygenation in the NW Arabian Sea during last ∼540 kyr. The increased relative abundances of high fertility ...

  9. Quality Assessment of Landsat Surface Reflectance Products Using MODIS Data

    Science.gov (United States)

    Feng, Min; Huang, Chengquan; Channan, Saurabh; Vermote, Eric; Masek, Jeffrey G.; Townshend, John R.

    2012-01-01

    Surface reflectance adjusted for atmospheric effects is a primary input for land cover change detection and for developing many higher level surface geophysical parameters. With the development of automated atmospheric correction algorithms, it is now feasible to produce large quantities of surface reflectance products using Landsat images. Validation of these products requires in situ measurements, which either do not exist or are difficult to obtain for most Landsat images. The surface reflectance products derived using data acquired by the Moderate Resolution Imaging Spectroradiometer (MODIS), however, have been validated more comprehensively. Because the MODIS on the Terra platform and the Landsat 7 are only half an hour apart following the same orbit, and each of the 6 Landsat spectral bands overlaps with a MODIS band, good agreements between MODIS and Landsat surface reflectance values can be considered indicators of the reliability of the Landsat products, while disagreements may suggest potential quality problems that need to be further investigated. Here we develop a system called Landsat-MODIS Consistency Checking System (LMCCS). This system automatically matches Landsat data with MODIS observations acquired on the same date over the same locations and uses them to calculate a set of agreement metrics. To maximize its portability, Java and open-source libraries were used in developing this system, and object-oriented programming (OOP) principles were followed to make it more flexible for future expansion. As a highly automated system designed to run as a stand-alone package or as a component of other Landsat data processing systems, this system can be used to assess the quality of essentially every Landsat surface reflectance image where spatially and temporally matching MODIS data are available. The effectiveness of this system was demonstrated using it to assess preliminary surface reflectance products derived using the Global Land Survey (GLS) Landsat

  10. Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

    Science.gov (United States)

    Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

    1987-01-01

    The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

  11. Soil Carbon Dioxide Production and Surface Fluxes: Subsurface Physical Controls

    Science.gov (United States)

    Risk, D.; Kellman, L.; Beltrami, H.

    Soil respiration is a critical determinant of landscape carbon balance. Variations in soil temperature and moisture patterns are important physical processes controlling soil respiration which need to be better understood. Relationships between soil respi- ration and physical controls are typically addressed using only surface flux data but other methods also exist which permit more rigorous interpretation of soil respira- tion processes. Here we use a combination of subsurface CO_{2} concentrations, surface CO_{2} fluxes and detailed physical monitoring of the subsurface envi- ronment to examine physical controls on soil CO_{2} production at four climate observatories in Eastern Canada. Results indicate that subsurface CO_{2} produc- tion is more strongly correlated to the subsurface thermal environment than the surface CO_{2} flux. Soil moisture was also found to have an important influence on sub- surface CO_{2} production, particularly in relation to the soil moisture - soil profile diffusivity relationship. Non-diffusive profile CO_{2} transport appears to be im- portant at these sites, resulting in a de-coupling of summertime surface fluxes from subsurface processes and violating assumptions that surface CO_{2} emissions are the result solely of diffusion. These results have implications for the study of soil respiration across a broad range of terrestrial environments.

  12. Application of response surface methodology for optimizing transesterification of Moringa oleifera oil: Biodiesel production

    International Nuclear Information System (INIS)

    Rashid, Umer; Anwar, Farooq; Ashraf, Muhammad; Saleem, Muhammad; Yusup, Suzana

    2011-01-01

    Highlights: → Biodiesel production from Moringa oil (MO) has been optimized for the first time using RSM. → RSM-optimized reaction conditions gave a high Moringa oil methyl esters (MOMEs) yield (94.3%). → Fuel properties of MOMEs yielded satisfied the ASTM D 6751 and EU 14214 specifications. → Present RSM-model can be useful for predicting optimum biodiesel yield from other oils. - Abstract: Response surface methodology (RSM), with central composite rotatable design (CCRD), was used to explore optimum conditions for the transesterification of Moringa oleifera oil. Effects of four variables, reaction temperature (25-65 deg. C), reaction time (20-90 min), methanol/oil molar ratio (3:1-12:1) and catalyst concentration (0.25-1.25 wt.% KOH) were appraised. The quadratic term of methanol/oil molar ratio, catalyst concentration and reaction time while the interaction terms of methanol/oil molar ratio with reaction temperature and catalyst concentration, reaction time with catalyst concentration exhibited significant effects on the yield of Moringa oil methyl esters (MOMEs)/biodiesel, p < 0.0001 and p < 0.05, respectively. Transesterification under the optimum conditions ascertained presently by RSM: 6.4:1 methanol/oil molar ratio, 0.80% catalyst concentration, 55 deg. C reaction temperature and 71.08 min reaction time offered 94.30% MOMEs yield. The observed and predicted values of MOMEs yield showed a linear relationship. GLC analysis of MOMEs revealed oleic acid methyl ester, with contribution of 73.22%, as the principal component. Other methyl esters detected were of palmitic, stearic, behenic and arachidic acids. Thermal stability of MOMEs produced was evaluated by thermogravimetric curve. The fuel properties such as density, kinematic viscosity, lubricity, oxidative stability, higher heating value, cetane number and cloud point etc., of MOMEs were found to be within the ASTM D6751 and EN 14214 biodiesel standards.

  13. Application of response surface methodology for optimizing transesterification of Moringa oleifera oil: Biodiesel production

    Energy Technology Data Exchange (ETDEWEB)

    Rashid, Umer, E-mail: umer.rashid@yahoo.com [Department of Chemistry and Biochemistry, University of Agriculture, Faisalabad 38040 (Pakistan); Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar 31750, Tronoh, Perak (Malaysia); Anwar, Farooq, E-mail: fqanwar@yahoo.com [Department of Chemistry and Biochemistry, University of Agriculture, Faisalabad 38040 (Pakistan); Ashraf, Muhammad, E-mail: ashrafbot@yahoo.com [Department of Botany, University of Agriculture, Faisalabad 38040 (Pakistan); Department of Botany and Microbiology, King Saud University, Riyadh (Saudi Arabia); Saleem, Muhammad [Department of Statistics, Government College University, Faisalabad 38000 (Pakistan); Yusup, Suzana, E-mail: drsuzana_yusuf@petronas.com.my [Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar 31750, Tronoh, Perak (Malaysia)

    2011-08-15

    Highlights: {yields} Biodiesel production from Moringa oil (MO) has been optimized for the first time using RSM. {yields} RSM-optimized reaction conditions gave a high Moringa oil methyl esters (MOMEs) yield (94.3%). {yields} Fuel properties of MOMEs yielded satisfied the ASTM D 6751 and EU 14214 specifications. {yields} Present RSM-model can be useful for predicting optimum biodiesel yield from other oils. - Abstract: Response surface methodology (RSM), with central composite rotatable design (CCRD), was used to explore optimum conditions for the transesterification of Moringa oleifera oil. Effects of four variables, reaction temperature (25-65 deg. C), reaction time (20-90 min), methanol/oil molar ratio (3:1-12:1) and catalyst concentration (0.25-1.25 wt.% KOH) were appraised. The quadratic term of methanol/oil molar ratio, catalyst concentration and reaction time while the interaction terms of methanol/oil molar ratio with reaction temperature and catalyst concentration, reaction time with catalyst concentration exhibited significant effects on the yield of Moringa oil methyl esters (MOMEs)/biodiesel, p < 0.0001 and p < 0.05, respectively. Transesterification under the optimum conditions ascertained presently by RSM: 6.4:1 methanol/oil molar ratio, 0.80% catalyst concentration, 55 deg. C reaction temperature and 71.08 min reaction time offered 94.30% MOMEs yield. The observed and predicted values of MOMEs yield showed a linear relationship. GLC analysis of MOMEs revealed oleic acid methyl ester, with contribution of 73.22%, as the principal component. Other methyl esters detected were of palmitic, stearic, behenic and arachidic acids. Thermal stability of MOMEs produced was evaluated by thermogravimetric curve. The fuel properties such as density, kinematic viscosity, lubricity, oxidative stability, higher heating value, cetane number and cloud point etc., of MOMEs were found to be within the ASTM D6751 and EN 14214 biodiesel standards.

  14. Regulatory Notes on Impact of Excipients on Drug Products and the Maillard Reaction.

    Science.gov (United States)

    Chowdhury, Dipak K; Sarker, Haripada; Schwartz, Paul

    2018-02-01

    In general, it is an important criterion that excipients remain inert throughout the shelf life of the formulated pharmaceutical product. However, depending on the functionality in chemical structure of active drug and excipients, they may undergo interaction. The well-known Maillard reaction occurs between a primary amine with lactose at high temperature to produce brown pigments. The reactivity of Maillard reaction may vary depending on the concentration as well as other conditions. Commercially, there are products where the active pharmaceutical ingredient is a primary amine and contains less than 75% lactose along with inactive excipients. This product does not show Maillard reaction during its shelf life of around 2 years at ambient conditions. However, when the same type of product contains more than 95 % lactose as an excipient, then there is a possibility of interactions though it is not visible in the initial year. Therefore, this regulatory note discusses involvement of different factors of a known drug-excipient interactions with case studies and provides an overview on how the concentration of lactose in the pharmaceutical product is important in addition to temperature and moisture in Maillard reaction.

  15. Worldwide withdrawal of medicinal products because of adverse drug reactions: a systematic review and analysis.

    Science.gov (United States)

    Onakpoya, Igho J; Heneghan, Carl J; Aronson, Jeffrey K

    2016-07-01

    We have systematically identified medicinal products withdrawn worldwide because of adverse drug reactions, assessed the level of evidence used for making the withdrawal decisions, and explored the patterns of withdrawals over time. We searched PubMed, the WHO database of withdrawn products, and selected texts. We included products that were withdrawn after launch from 1950 onwards, excluding non-human and over-the-counter medicines. We assessed the levels of evidence on which withdrawals were based using the Oxford Center for Evidence Based Medicine Levels of Evidence. Of 353 medicinal products withdrawn from any country, only 40 were withdrawn worldwide. Anecdotal reports were cited as evidence for withdrawal in 30 (75%) and deaths occurred in 27 (68%). Hepatic, cardiac, and nervous system toxicity accounted for over 60% of withdrawals. In 28 cases, the first withdrawal was initiated by the manufacturer. The median interval between the first report of an adverse drug reaction that led to withdrawal and the first withdrawal was 1 year (range 0-43 years). Worldwide withdrawals occurred within 1 year after the first withdrawal in any country. In conclusion, the time it takes for drugs to be withdrawn worldwide after reports of adverse drug reactions has shortened over time. However, there are inconsistencies in current withdrawal procedures when adverse drug reactions are suspected. A uniform method for establishing worldwide withdrawal of approved medicinal products when adverse drug reactions are suspected should be developed, to facilitate global withdrawals. Rapid synthesis of the evidence on harms should be a priority when serious adverse reactions are suspected.

  16. Role of (n,2n) reactions in transmutation of long-lived fission products

    Energy Technology Data Exchange (ETDEWEB)

    Apse, V. A.; Kulikov, G. G., E-mail: ggkulikov@mephi.ru; Kulikov, E. G. [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) (Russian Federation)

    2016-12-15

    The conditions under which (n,γ) and (n,2n) reactions can help or hinder each other in neutron transmutation of long-lived fission products (LLFPs) are considered. Isotopic and elemental transmutation for the main long-lived fission products, {sup 79}Se, {sup 93}Zr, {sup 99}Tc, {sup 107}Pd, {sup 126}Sn, {sup 129}I, and {sup 135}Cs, are considered. The effect of (n,2n) reactions on the equilibrium amount of nuclei of the transmuted isotope and the neutron consumption required for the isotope processing is estimated. The aim of the study is to estimate the influence of (n,2n) reactions on efficiency of neutron LLFP transmutation. The code TIME26 and the libraries of evaluated nuclear data ABBN-93, JEF-PC, and JANIS system are applied. The following results are obtained: (1) The effect of (n,2n) reactions on the minimum number of neutrons required for transmutation and the equilibrium amount of LLFP nuclei is estimated. (2) It is demonstrated that, for three LLFP isotopes ({sup 126}Sn, {sup 129}I, and {sup 135}Cs), (n,γ) and (n,2n) reactions are partners facilitating neutron transmutation. The strongest effect of (n,2n) reaction is found for {sup 126}Sn transmutation (reduction of the neutron consumption by 49% and the equilibrium amount of nuclei by 19%).

  17. [Optimization of ethylene production from ethanol dehydration using Zn-Mn-Co/HZSM-5 by response surface methodology].

    Science.gov (United States)

    Wang, Wei; Cheng, Keke; Xue, Jianwei; Zhang, Jian'an

    2011-03-01

    The effects of reaction temperature, ethanol concentration and weight hourly space velocity (WHSV) on the ethylene production from ethanol dehydration using zinc, manganese and cobalt modified HZSM-5 catalyst were investigated by response surface methodology (RSM). The results showed that the most significant effect among factors was reaction temperature and the factors had interaction. The optimum conditions were found as 34.4% ethanol concentration, 261.3 0 degrees C of reaction temperature and 1.18 h(-1) of WHSV, under these conditions the yield of ethylene achieved 98.69%.

  18. The study of biodiesel production using CaO as a heterogeneous catalytic reaction

    Directory of Open Access Journals (Sweden)

    Kamila Colombo

    2017-06-01

    Full Text Available With the aim of developing a process of biodiesel production that is environmentally benign much interest has been focused on the use of solid base catalysts, such as calcium oxide, for the transesterification of vegetable oils with methanol. In the study reported herein a recycling reactor was used in bench scale, with the capacity to produce 3 L of biodiesel. The reactor was designed especially for this research study. A full 23 factorial plan was used to evaluate the process parameters related to this study, in particular, the catalyst concentration, the alcohol to oil molar ratio and the reaction time. Using this equipment for the transesterification reaction resulted in the recovery of the excess alcohol. The reaction products were characterized using gas chromatography and liquid analysis to determine the ester and calcium concentrations, respectively. The main conclusions drawn were that the best conversion percentage (100% of biodiesel was reached when the methanol:oil molar ratio was 6:1, the reaction time was 75 min and the catalyst mass was 3% in relation to the oil mass used in this process. The CaO concentration determined exceeded the limit of concentration defined by legislation and thus a secondary operation was carried out to purify the reaction products obtained. The results of this study showed a high performance, and the proposed experiment could be used as a new and innovative way to produce biodiesel in the future.

  19. Effect of γ-ray emission on transuranium element production cross sections in heavy ion reactions

    International Nuclear Information System (INIS)

    Il'inov, A.S.; Oganesyan, Yu.Ts.; Cherepanov, E.A.

    1980-01-01

    The effect of competition of the γ ray emission with neutron evaporation and of compound nuclei fission induced by heavy ion reactions on the production cross sections for transuranium elements is considered. It is shown that taking account of γ ray emission leads to the broadening of the excitation functions of the (HI, xny) reactions such as 18 O+ 238 U, 40 Ar+ 206 Pb, 40 Ar+ 207 Pb and 40 Ar+ 208 Pb reactions and to the displacement of their maximum toward the higher energies as well as to an increase of the absolute cross sections which is especially strong close to the fusion barrier. Cross sections for the radiative capture of heavy ions by a heavy target nucleus in 40 Ar+ 206 Pb, 40 Ar+ 208 Pb, 48 Ca+ 204 Pb and 48 Ca+ 208 Pb reactions are estimated

  20. Food Processing and Maillard Reaction Products: Effect on Human Health and Nutrition

    Directory of Open Access Journals (Sweden)

    Nahid Tamanna

    2015-01-01

    Full Text Available Maillard reaction produces flavour and aroma during cooking process; and it is used almost everywhere from the baking industry to our day to day life to make food tasty. It is often called nonenzymatic browning reaction since it takes place in the absence of enzyme. When foods are being processed or cooked at high temperature, chemical reaction between amino acids and reducing sugars leads to the formation of Maillard reaction products (MRPs. Depending on the way the food is being processed, both beneficial and toxic MRPs can be produced. Therefore, there is a need to understand the different types of MRPs and their positive or negative health effects. In this review we have summarized how food processing effects MRP formation in some of the very common foods.

  1. Food Processing and Maillard Reaction Products: Effect on Human Health and Nutrition

    Science.gov (United States)

    Tamanna, Nahid; Mahmood, Niaz

    2015-01-01

    Maillard reaction produces flavour and aroma during cooking process; and it is used almost everywhere from the baking industry to our day to day life to make food tasty. It is often called nonenzymatic browning reaction since it takes place in the absence of enzyme. When foods are being processed or cooked at high temperature, chemical reaction between amino acids and reducing sugars leads to the formation of Maillard reaction products (MRPs). Depending on the way the food is being processed, both beneficial and toxic MRPs can be produced. Therefore, there is a need to understand the different types of MRPs and their positive or negative health effects. In this review we have summarized how food processing effects MRP formation in some of the very common foods. PMID:26904661

  2. Structural brain aging and speech production: a surface-based brain morphometry study.

    Science.gov (United States)

    Tremblay, Pascale; Deschamps, Isabelle

    2016-07-01

    While there has been a growing number of studies examining the neurofunctional correlates of speech production over the past decade, the neurostructural correlates of this immensely important human behaviour remain less well understood, despite the fact that previous studies have established links between brain structure and behaviour, including speech and language. In the present study, we thus examined, for the first time, the relationship between surface-based cortical thickness (CT) and three different behavioural indexes of sublexical speech production: response duration, reaction times and articulatory accuracy, in healthy young and older adults during the production of simple and complex meaningless sequences of syllables (e.g., /pa-pa-pa/ vs. /pa-ta-ka/). The results show that each behavioural speech measure was sensitive to the complexity of the sequences, as indicated by slower reaction times, longer response durations and decreased articulatory accuracy in both groups for the complex sequences. Older adults produced longer speech responses, particularly during the production of complex sequence. Unique age-independent and age-dependent relationships between brain structure and each of these behavioural measures were found in several cortical and subcortical regions known for their involvement in speech production, including the bilateral anterior insula, the left primary motor area, the rostral supramarginal gyrus, the right inferior frontal sulcus, the bilateral putamen and caudate, and in some region less typically associated with speech production, such as the posterior cingulate cortex.

  3. Determination of the shapes and sizes of the regions in which in hadron-nucleus collisions reactions leading to the nucleon emission, particle production, and fragment evaporation occur

    International Nuclear Information System (INIS)

    Strugalski, Z.

    1985-01-01

    Shapes and sizes of the regions in target-nuclei in which reactions leading to the nucleon emission, particle production and fragment evaporation occur are determined. The region of nucleon emission is of cylindrical shape, with the diameter as large as two nucleon diameters, centered on the incident hadron course. The reactions leading to the particle production happen predominantly along the incident hadron course in nuclear matter. The fragment evaporation goes from the surface layer of the part of the target-nucleus damaged in nucleon emission process

  4. Solidification of highly active fission products by a thermite reaction. Pt. 1

    International Nuclear Information System (INIS)

    Rudolph, G.; Hild, W.

    1976-07-01

    To solidify high-level fission products a process was developed according to which a high-melting ceramic product is obtained as a solidification matrix in a thermite reaction. With a constant content of fission product oxides reaction mixtures consisting of 35 to 55 wt.% of manganese dioxide, 24 to 32 wt.% of aluminum shot and 17 to 36 wt.% of sand give suitable products. In the thermite reactiom some components contained in the reactic mixture volatilize partly by evaporation (alkali oxides, manganese oxide, and others) and partly by the formation of volatile oxides having lower valencies (silicon and aluminum oxide). The smoke generated can be easily collected in filters made of glass wool fibers. (orig./HR) [de

  5. Synthesis of most polyene natural product motifs using just 12 building blocks and one coupling reaction.

    Science.gov (United States)

    Woerly, Eric M; Roy, Jahnabi; Burke, Martin D

    2014-06-01

    The inherent modularity of polypeptides, oligonucleotides and oligosaccharides has been harnessed to achieve generalized synthesis platforms. Importantly, like these other targets, most small-molecule natural products are biosynthesized via iterative coupling of bifunctional building blocks. This suggests that many small molecules also possess inherent modularity commensurate with systematic building block-based construction. Supporting this hypothesis, here we report that the polyene motifs found in >75% of all known polyene natural products can be synthesized using just 12 building blocks and one coupling reaction. Using the same general retrosynthetic algorithm and reaction conditions, this platform enabled both the synthesis of a wide range of polyene frameworks that covered all of this natural-product chemical space and the first total syntheses of the polyene natural products asnipyrone B, physarigin A and neurosporaxanthin b-D-glucopyranoside. Collectively, these results suggest the potential for a more generalized approach to making small molecules in the laboratory.

  6. Synthesis of most polyene natural product motifs using just twelve building blocks and one coupling reaction

    Science.gov (United States)

    Woerly, Eric M.; Roy, Jahnabi; Burke, Martin D.

    2014-01-01

    The inherent modularity of polypeptides, oligonucleotides, and oligosaccharides has been harnessed to achieve generalized building block-based synthesis platforms. Importantly, like these other targets, most small molecule natural products are biosynthesized via iterative coupling of bifunctional building blocks. This suggests that many small molecules also possess inherent modularity commensurate with systematic building block-based construction. Supporting this hypothesis, here we report that the polyene motifs found in >75% of all known polyene natural products can be synthesized using just 12 building blocks and one coupling reaction. Using the same general retrosynthetic algorithm and reaction conditions, this platform enabled the synthesis of a wide range of polyene frameworks covering all of this natural product chemical space, and first total syntheses of the polyene natural products asnipyrone B, physarigin A, and neurosporaxanthin β-D-glucopyranoside. Collectively, these results suggest the potential for a more generalized approach for making small molecules in the laboratory. PMID:24848233

  7. Mass and angular distributions of the reaction products in heavy ion collisions

    Science.gov (United States)

    Nasirov, A. K.; Giardina, G.; Mandaglio, G.; Kayumov, B. M.; Tashkhodjaev, R. B.

    2018-05-01

    The optimal reactions and beam energies leading to synthesize superheavy elements is searched by studying mass and angular distributions of fission-like products in heavy-ion collisions since the evaporation residue cross section consists an ignorable small part of the fusion cross section. The intensity of the yield of fission-like products allows us to estimate the probability of the complete fusion of the interacting nuclei. The overlap of the mass and angular distributions of the fusion-fission and quasifission products causes difficulty at estimation of the correct value of the probability of the compound nucleus formation. A study of the mass and angular distributions of the reaction products is suitable key to understand the interaction mechanism of heavy ion collisions.

  8. Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

    Science.gov (United States)

    Luca, Oana R; Fenwick, Aidan Q

    2015-11-01

    The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Library of Antifouling Surfaces Derived From Natural Amino Acids by Click Reaction.

    Science.gov (United States)

    Xu, Chen; Hu, Xin; Wang, Jie; Zhang, Ye-Min; Liu, Xiao-Jiu; Xie, Bin-Bin; Yao, Chen; Li, Yi; Li, Xin-Song

    2015-08-12

    Biofouling is of great concern in numerous applications ranging from ophthalmological implants to catheters, and from bioseparation to biosensors. In this report, a general and facile strategy to combat surface fouling is developed by grafting of amino acids onto polymer substrates to form zwitterionic structure through amino groups induced epoxy ring opening click reaction. First of all, a library of poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) hydrogels with zwitterionic surfaces were prepared, resulting in the formation of pairs of carboxyl anions and protonated secondary amino cations. The analysis of attenuated total reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed the successful immobilization of amino acids on the hydrogel surfaces. After that, the contact angle and equilibrium water content of the modified hydrogels showed that the hydrogels exhibited improved hydrophilicity compared with the parent hydrogel. Furthermore, the protein deposition was evaluated by bicinchoninic acid assay using bovine serum albumin (BSA) and lysozyme as models. The results indicated that the performance of the hydrogels was determined by the nature of incorporated amino acid: the hydrogels incorporated with neutral amino acids had nonspecific antiadsorption capability to both BSA and lysozyme; the hydrogels incorporated with charged amino acids showed antiadsorption behaviors against protein with same charge and enhanced adsorption to the protein with opposite charge; the optimal antiadsorption performance was observed on the hydrogels incorporated with polar amino acids with a hydroxyl residual. The improvement of antiprotein fouling of the neutral amino acids grafted hydrogels can be ascribed to the formation of zwitterionic surfaces. Finally, a couple of soft contact lenses grafted with amino acids were fabricated having improved antifouling property and hydrophilicity. The result demonstrated the success of

  10. Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

    Directory of Open Access Journals (Sweden)

    J. A. Thornton

    2012-06-01

    Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

  11. Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

    Science.gov (United States)

    Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

    2017-03-03

    Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

  12. Characterization of ionic liquid‐based biocatalytic two‐phase reaction system for production of biodiesel

    DEFF Research Database (Denmark)

    Prabhavathi Devi, Bethala Lakshmi Anu; Guo, Zheng; Xu, Xuebing

    2011-01-01

    The property of a variety of ionic liquids (ILs) as reaction media was evaluated for the production of biodiesel by enzymatic methanolysis of rapeseed oil. The IL Ammoeng 102, containing tetraaminum cation with C18 acyl and oligoethyleneglycol units, was found to be capable of forming oil....../IL biphasic reaction system by mixing with substrates, which is highly effective for the production of biodiesel with more than 98% biodiesel yield and nearly 100% conversion of oil. Conductor‐like screening model for real solvent (COSMO‐RS) in silico prediction of substrate solubility and simulation...... of partition coefficient change vs. reaction evolution indicated that the amphiphilic property of Ammoeng 102 might be responsible for creating efficient interaction of immiscible substrates; while big difference of partition coefficients of generated biodiesel and glycerol between the two phases suggests...

  13. Parameterization of pion production and reaction cross sections at LAMPF energies

    International Nuclear Information System (INIS)

    Burman, R.L.; Smith, E.S.

    1989-05-01

    A parameterization of pion production and reaction cross sections is developed for eventual use in modeling neutrino production by protons in a beam stop. Emphasis is placed upon smooth parameterizations for proton energies up to 800 MeV, for all pion energies and angles, and for a wide range of materials. The resulting representations of the data are well-behaved and can be used for extrapolation to regions where there are no measurements. 22 refs., 16 figs., 2 tabs

  14. IVO, a device for In situ Volatilization and On-line detection of products from heavy ion reactions

    CERN Document Server

    Duellmann, C E; Eichler, R; Gäggeler, H W; Jost, D T; Piguet, D; Türler, A

    2002-01-01

    A new gaschromatographic separation system to rapidly isolate heavy ion reaction products in the form of highly volatile species is described. Reaction products recoiling from the target are stopped in a gas volume and converted in situ to volatile species, which are swept by the carrier gas to a chromatography column. Species that are volatile under the given conditions pass through the column. In a cluster chamber, which is directly attached to the exit of the column, the isolated volatile species are chemically adsorbed to the surface of aerosol particles and transported to an on-line detection system. The whole set-up was tested using short-lived osmium (Os) and mercury (Hg) nuclides produced in heavy ion reactions to model future chemical studies with hassium (Hs, Z=108) and element 112. By varying the temperature of the isothermal section of the chromatography column between room temperature and -80 deg. C, yield measurements of given species can be conducted, yielding information about the volatility o...

  15. Chlorination and oxidation of sulfonamides by free chlorine: Identification and behaviour of reaction products by UPLC-MS/MS.

    Science.gov (United States)

    Gaffney, Vanessa de Jesus; Cardoso, Vitor Vale; Benoliel, Maria João; Almeida, Cristina M M

    2016-01-15

    Sulfonamides (SAs) are one class of the most widely used antibiotics around the world and have been frequently detected in municipal wastewater and surface water in recent years. Their transformation in waste water treatment plants (WWTP) and in water treatment plants (WTP), as well as, their fate and transport in the aquatic environment are of concern. The reaction of six sulfonamides (sulfamethoxazole, sulfapyridine, sulfamethazine, sulfamerazine, sulfathiazole and sulfadiazine) with free chlorine was investigated at a laboratory scale in order to identify the main chlorination by-products. A previously validated method, liquid chromatography/mass spectrometry, was used to analyse SAs and their chlorination by-products. At room temperature, pH 6-7, reaction times of up to 2 h and an initial concentration of 2 mg/L of free chlorine, the majority of SAs suffered degradation of around 65%, with the exception of sulfamethoxazole and sulfathiazole (20%). The main reaction of SAs with free chlorine occurred in the first minute. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Surface chemical reactions during electron beam irradiation of nanocrystalline CaS:Ce3+ phosphor

    International Nuclear Information System (INIS)

    Kumar, Vinay; Pitale, Shreyas S.; Nagpure, I. M.; Coetsee, E.; Ntwaeaborwa, O. M.; Terblans, J. J.; Swart, H. C.; Mishra, Varun

    2010-01-01

    The effects of accelerating voltage (0.5-5 keV) on the green cathodoluminescence (CL) of CaS:Ce 3+ nanocrystalline powder phosphors is reported. An increase in the CL intensity was observed from the powders when the accelerating voltage was varied from 0.5 to 5 keV, which is a relevant property for a phosphor to be used in field emission displays (FEDs). The CL degradation induced by prolonged electron beam irradiation was analyzed using CL spectroscopy, x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The AES data showed the decrease in the S peak intensity and an increase in the O peak intensity during electron bombardment. The CL intensity was found to decrease to 30% of its original intensity after about 50 C/cm 2 . XPS was used to study the chemical composition of the CaS:Ce 3+ nanophosphor before and after degradation. The XPS data confirms that a nonluminescent CaSO 4 layer has formed on the surface during the degradation process, which may partially be responsible for the CL degradation. The electron stimulated surface chemical reaction mechanism was used to explain the effects of S desorption and the formation of the nonluminescent CaSO 4 layer on the surface.

  17. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    DEFF Research Database (Denmark)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

    2012-01-01

    The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *O....... This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16V towards more positive potentials can be clearly monitored in absence of O2 and under the oxygen reduction reaction (ORR) conditions...... for the Cu/Pt(111) NSA. In both cases, for Pt(111) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when...

  18. Reactions and Surface Transformations of a Bone-Bioactive Material in a Simulated Microgravity Environment

    Science.gov (United States)

    Radin, S.; Ducheyne, P.; Ayyaswamy, P. S.

    1999-01-01

    A comprehensive program to investigate the expeditious in vitro formation of three-dimensional bone-like tissue is currently underway at the University of Pennsylvania. The study reported here forms a part of that program. Three-dimensional bone-like tissue structures may be grown under the simulated microgravity conditions of NASA designed Rotating Wall Bioreactor Vessels (RWV's). Such tissue growth will have wide clinical applications. In addition, an understanding of the fundamental changes that occur to bone cells under simulated microgravity would yield important information that will help in preventing or minimizing astronaut bone loss, a major health issue with travel or stay in space over long periods of time. The growth of three-dimensional bone-like tissue structures in RWV's is facilitated by the use of microcarriers which provide structural support. If the microcarrier material additionally promotes bone cell growth, then it is particularly advantageous to employ such microcarriers. We have found that reactive, bone-bioactive glass (BBG) is an attractive candidate for use as microcarrier material. Specifically, it has been found that BBG containing Ca- and P- oxides upregulates osteoprogenitor cells to osteoblasts. This effect on cells is preceded by BBG reactions in solution which result in the formation of a Ca-P surface layer. This surface further transforms to a bone-like mineral (i.e., carbonated crystalline hydroxyapatite (c-HA)). At normal gravity, time-dependent, immersion-induced BBG reactions and transformations are greatly affected both by variations in the composition of the milieu in which the glass is immersed and on the immersion conditions. However, the nature of BBG reactions and phase transformations under the simulated microgravity conditions of RWV's are unknown, and must be understood in order to successfully use BBG as microcarrier material in RWV'S. In this paper, we report some of our recent findings in this regard using

  19. Production of carbon nanotubes using mechanical milling in the presence of an exothermic reaction

    International Nuclear Information System (INIS)

    Karimi, E.Z.; Zebarjad, S.M.; Khaki, J. Vahdati; Izadi, H.

    2010-01-01

    Carbon nanotubes (CNTs) have shown promising potential for many applications in field of engineering due to their unusual significant properties. A major challenge for the industrial applications of CNTs is the large-quantity production. In this field, one new method for CNT production is annealing the ball milled graphite powder. The annealing process should be done in high temperature (1200-1400 o C) and needs time more than 6 h. The novel process introduced in this paper is elimination the annealing stage thorough a thermite reaction. The necessity heat for the conversion of milling products to CNTs was generated in the milling chamber by an exothermic reaction. In addition, the reaction products acted as catalysts to the CNT formation process. The adiabatic temperatures of 1809, 2000 and 2325 K were selected according to balancing graphite and thermite mixture (Aluminum + Iron oxide powders) for exothermic reaction. The results of thermo gravimetric analysis (TGA) test proved that CNT formation strongly depends on adiabatic temperature. The results of microscopic evaluation done by transition electron microscope (TEM) showed that at higher adiabatic temperature CNTs could be produced.

  20. Possibilities of production of neutron-rich Md isotopes in multi-nucleon transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Mun, Myeong-Hwan; Lee, Young-Ouk [Korea Atomic Energy Research Institue, Daejeon (Korea, Republic of); Adamian, G.G.; Antonenko, N.V. [Joint Institute for Nuclear Research, Dubna (Russian Federation)

    2016-12-15

    The possibilities of production of yet unknown neutron-rich isotopes of Md are explored in several multi-nucleon transfer reactions with actinide targets and stable and radioactive beams. The projectile-target combinations and bombarding energies are suggested to produce new neutron-rich isotopes of Md in future experiments. (orig.)

  1. Age-related accumulation of Maillard reaction products in human articular cartilage collagen

    NARCIS (Netherlands)

    Verzijl, N.; Degroot, J.; Oldehinkel, E.; Bank, R. A.; Thorpe, S. R.; Baynes, J. W.; Bayliss, M. T.; Bijlsma, J. W.; Lafeber, F. P.; TeKoppele, J. M.

    2000-01-01

    Non-enzymic modification of tissue proteins by reducing sugars, the so-called Maillard reaction, is a prominent feature of aging. In articular cartilage, relatively high levels of the advanced glycation end product (AGE) pentosidine accumulate with age. Higher pentosidine levels have been associated

  2. Enantioselective H-atom transfer reaction: a strategy to synthesize formaldehyde aldol products.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2005-04-14

    [reaction: see text] Enantioselective radical alkylation of Baylis-Hillman adducts furnished aldol products in good yield and selectivity. The results illustrate that the selectivity in the hydrogen atom transfer is dependent on the size of the ester substituent, with smaller substituents providing better enantioselectivity.

  3. Hyperon production in photonuclear reactions on protons and deuterons : The Kappa(0)Sigma(+) channel

    NARCIS (Netherlands)

    Lohner, H; Bacelar, J; Castelijns, R; Messchendorp, J; Shende, S; Maeda, K; Tamura, H; Nakamura, SN; Hashimoto, O

    2004-01-01

    With the combined setup of the Crystal Barrel and TAPS photonspectrometers at ELSA in Bonn we have studied photonuclear reactions on protons and deuterons. From the series of experiments on single and multiple neutral meson emission we concentrate here on the hyperon production off protons and

  4. Characterization of cement minerals, cements and their reaction products at the atomic and nano scale

    DEFF Research Database (Denmark)

    Skibsted, Jørgen; Hall, Christopher

    2008-01-01

    Recent advances and highlights in characterization methods are reviewed for cement minerals, cements and their reaction products. The emphasis is on X-ray and neutron diffraction, and on nuclear magnetic resonance methods, although X-ray absorption and Raman spectroscopies are discussed briefly...

  5. Production of 11Li in the (11B,11Li) reaction on 232Th

    International Nuclear Information System (INIS)

    Scott, D.K.; Buenerd, M.; Hendrie, D.L.; KeKelis, G.; Mahoney, J.; Menchaca-Rocha, A.; Olmer, C.

    1975-01-01

    Production of the neutron-rich nucleus 11 Li in the bombardment of 232 Th by 11 B at 114 MeV suggests that multinucleon transfer reactions induced by neutron excess heavy ions on heavy targets present a feasible method of measuring the mass excess of exotic light nuclei in the limit of stability

  6. Characterization of cement minerals, cements and their reaction products at the atomic and nano scale

    International Nuclear Information System (INIS)

    Skibsted, Jorgen; Hall, Christopher

    2008-01-01

    Recent advances and highlights in characterization methods are reviewed for cement minerals, cements and their reaction products. The emphasis is on X-ray and neutron diffraction, and on nuclear magnetic resonance methods, although X-ray absorption and Raman spectroscopies are discussed briefly

  7. The hydrogen abstraction reaction O(3P) + CH4: A new analytical potential energy surface based on fit to ab initio calculations

    International Nuclear Information System (INIS)

    González-Lavado, Eloisa; Corchado, Jose C.; Espinosa-Garcia, Joaquin

    2014-01-01

    Based exclusively on high-level ab initio calculations, a new full-dimensional analytical potential energy surface (PES-2014) for the gas-phase reaction of hydrogen abstraction from methane by an oxygen atom is developed. The ab initio information employed in the fit includes properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, points on the reaction path, and points on the reaction swath, taking especial caution respecting the location and characterization of the intermediate complexes in the entrance and exit channels. By comparing with the reference results we show that the resulting PES-2014 reproduces reasonably well the whole set of ab initio data used in the fitting, obtained at the CCSD(T) = FULL/aug-cc-pVQZ//CCSD(T) = FC/cc-pVTZ single point level, which represents a severe test of the new surface. As a first application, on this analytical surface we perform an extensive dynamics study using quasi-classical trajectory calculations, comparing the results with recent experimental and theoretical data. The excitation function increases with energy (concave-up) reproducing experimental and theoretical information, although our values are somewhat larger. The OH rotovibrational distribution is cold in agreement with experiment. Finally, our results reproduce experimental backward scattering distribution, associated to a rebound mechanism. These results lend confidence to the accuracy of the new surface, which substantially improves the results obtained with our previous surface (PES-2000) for the same system

  8. 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.

  9. Eta products, BPS states and K3 surfaces

    Energy Technology Data Exchange (ETDEWEB)

    He, Yang-Hui [Department of Mathematics, City University,London, EC1V 0HB (United Kingdom); School of Physics, NanKai University,Tianjin, 300071 (China); Merton College, University of Oxford,Oxford, OX14JD (United Kingdom); McKay, John [Department of Mathematics and Statistics, Concordia University,1455 de Maisonneuve Blvd. West, Montreal, Quebec, H3G 1M8 (Canada)

    2014-01-22

    Inspired by the multiplicative nature of the Ramanujan modular discriminant, Δ, we consider physical realizations of certain multiplicative products over the Dedekind eta-function in two parallel directions: the generating function of BPS states in certain heterotic orbifolds and elliptic K3 surfaces associated to congruence subgroups of the modular group. We show that they are, after string duality to type II, the same K3 surfaces admitting Nikulin automorphisms. In due course, we will present identities arising from q-expansions as well as relations to the sporadic Mathieu group M{sub 24}.

  10. A study of reactions of sulfur dioxide in the gaseous phase. Production and evolution of aerosols resulting from these reactions

    International Nuclear Information System (INIS)

    Boulaud, Denis

    1977-01-01

    The reactions of sulfur dioxide in the gaseous phase with atmospheric pollutants (NO x ; hydrocarbons) were studied. Experiments showed that NO 2 contribution was significant and suggested that SO 2 transformation into sulfuric acid and sulfates might occur through oxidising agents mainly hydroxyl (OH) and hydro-peroxyl (HO 2 ) radicals. The production and evolution of the resulting aerosols was also studied. It was demonstrated that the effect of water vapour on particle production was significant and that primary embryos were formed from the hetero-molecular homogeneous nucleation acting on water vapour and very likely on sulfuric acid. There was a semi-quantitative agreement between our experimental results and some theoretical investigations on nucleation rate of the system (H 2 O - H 2 SO 4 ). The subsequent growth of particles was studied in a simulation chamber. Finally a model of sulfuric acid vapour evolution in presence of atmospheric aerosols made it possible to extend the previous results as far as possible to the case of atmosphere and then to compare the importance of homogeneous and heterogeneous nucleation of the vapours according to atmospheric conditions. (author) [fr

  11. NATO Advanced Research Workshop on the Mechanisms of Reactions of Organometallic Compounds with Surfaces

    CERN Document Server

    Williams, J

    1989-01-01

    A NATO Advanced Research Workshop on the "Mechanisms of Reactions of Organometallic Compounds with Surfaces" was held in St. Andrews, Scotland in June 1988. Many of the leading international researchers in this area were present at the workshop and all made oral presentations of their results. In addition, significant amounts of time were set aside for Round Table discussions, in which smaller groups considered the current status of mechanistic knowledge, identified areas of dispute or disagreement, and proposed experiments that need to be carried out to resolve such disputes so as to advance our understanding of this important research area. All the papers presented at the workshop are collected in this volume, together with summaries of the conclusions reached at the Round Table discussions. The workshop could not have taken place without financial support from NATO, and donations were also received from Associated Octel, Ltd., STC Ltd., and Epichem Ltd., for which the organisers are very grateful. The orga...

  12. Formation of porous surface layers in reaction bonded silicon nitride during processing

    Science.gov (United States)

    Shaw, N. J.; Glasgow, T. K.

    1979-01-01

    Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

  13. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    International Nuclear Information System (INIS)

    Shibata, T; Nishiyama, H

    2014-01-01

    Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water. (paper)

  14. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    Science.gov (United States)

    Shibata, T.; Nishiyama, H.

    2014-03-01

    Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water.

  15. Production of Heat Sensitive Monoacylglycerols by Enzymatic Glycerolysis in Tert-pentanol: Process Optimization by Response Surface Methodology

    DEFF Research Database (Denmark)

    Damstrup, Marianne L.; Jensen, Tine; Sparsø, Flemming V.

    2006-01-01

    The aim of this study was to optimize production of MAG by lipase-catalyzed glycerolysis in a tert-pentanol system. Twenty-nine batch reactions consisting of glycerol, sunflower oil, tert-pentanol, and commercially available lipase (Novozym®435) were carried out, with four process parameters being...... varied: Enzyme load, reaction time, substrate ratio of glycerol to oil, and solvent amount. Response surface methodology was applied to optimize the reaction system based on the experimental data achieved. MAG, DAG, and TAG contents, measured after a selected reaction time, were used as model responses....... Well-fitting quadratic models were obtained for MAG, DAG, and TAG contents as a function of the process parameters with determination coefficients (R2) of 0.89, 0.88, and 0.92, respectively. Of the main effects examined, only enzyme load and reaction time significantly influenced MAG, DAG, and TAG...

  16. Effect of surface reaction layer on grindability of cast titanium alloys.

    Science.gov (United States)

    Ohkubo, Chikahiro; Hosoi, Toshio; Ford, J Phillip; Watanabe, Ikuya

    2006-03-01

    The purpose of this study was to investigate the effect of the cast surface reaction layer on the grindability of titanium alloys, including free-machining titanium alloy (DT2F), and to compare the results with the grindability of two dental casting alloys (gold and Co-Cr). All titanium specimens (pure Ti, Ti-6Al-4V and DT2F) were cast using a centrifugal casting machine in magnesia-based investment molds. Two specimen sizes were used to cast the titanium metals so that the larger castings would be the same size as the smaller gold and Co-Cr alloy specimens after removal of the surface reaction layer (alpha-case). Grindability was measured as volume loss ground from a specimen for 1 min using a handpiece engine with a SiC abrasive wheel at 0.1 kgf and four circumferential wheel speeds. For the titanium and gold alloys, grindability increased as the rotational speed increased. There was no statistical difference (p>0.05) in grindability for all titanium specimens either with or without the alpha-case. Of the titanium metals tested, Ti-6 Al-4V had the greatest grindability at higher speeds, followed by DT2F and CP Ti. The grindability of the gold alloy was similar to that of Ti-6 Al-4V, whereas the Co-Cr alloy had the lowest grindability. The results of this study indicated that the alpha-case did not significantly affect the grindability of the titanium alloys. The free-machining titanium alloy had improved grindability compared to CP Ti.

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

    Science.gov (United States)

    Zhou, Yong; Zhang, Dong H

    2014-11-21

    Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

  18. The influence of oscillations on product selectivity during the palladium-catalysed phenylacetylene oxidative carbonylation reaction.

    Science.gov (United States)

    Novakovic, Katarina; Grosjean, Christophe; Scott, Stephen K; Whiting, Andrew; Willis, Mark J; Wright, Allen R

    2008-02-07

    This paper reports on the influence of oscillations on product selectivity as well as the dynamics of product formation during the palladium-catalysed phenylacetylene oxidative carbonylation reaction in a catalytic system (PdI2, KI, Air, NaOAc in methanol). The occurrence of the pH oscillations is related to PdI2 granularity and the initial pH drop after phenylacetylene addition. To achieve pH and reaction exotherm oscillations regulation of the amount of PdI2 is required, ensuring that the initial pH does not fall significantly below 1 after phenylacetylene addition. Experiments in both oscillatory and non-oscillatory pH regimes were performed in an HEL SIMULAR reaction calorimeter with the concentration-time profiles measured using a GC-MS. It is demonstrated that when operating in an oscillatory pH regime product formation may be suppressed until oscillations occur after which there is a steep increase in the formation of Z-2-phenyl-but-2-enedioic acid dimethyl ester. When operating in non-oscillatory pH mode the products are formed steadily over time with the main products being Z-2-phenyl-but-2-enedioic acid dimethyl ester, 2-phenyl-acrylic acid methyl ester and E-3-phenyl-acrylic acid methyl ester.

  19. Formation of N-nitrosodimethylamine (NDMA) from reaction of monochloramine: a new disinfection by-product.

    Science.gov (United States)

    Choi, Junghoon; Valentine, Richard L

    2002-02-01

    Studies have been conducted specifically to investigate the hypothesis that N-nitrosodimethylamine (NDMA) can be produced by reactions involving monochloramine. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed from the reaction between DMA and monochloramine indicating that it should be considered a potential disinfection by-product. The formation of NDMA increased with increased monochloramine concentration and showed maximum in yield when DMA was varied at fixed monochloramine concentrations. The mass spectra of the NDMA formed from DMA and 15N isotope labeled monochloramine (15NH2Cl) showed that the source of one of the nitrogen atoms in the nitroso group in NDMA was from monochloramine. Addition of 0.05 and 0.5 mM of preformed monochloramine to a secondarily treated wastewater at pH 7.2 also resulted in the formation of 3.6 and 111 ng/L of NDMA, respectively, showing that this is indeed an environmentally relevant NDMA formation pathway. The proposed NDMA formation mechanism consists of (i) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (ii) the oxidation of UDMH by monochloramine to NDMA, and (iii) the reversible chlorine transfer reaction between monochloramine and DMA which is parallel to (i). We conclude that reactions involving monochloramine in addition to classical nitrosation reactions are potentially important pathways for NDMA formation.

  20. Investigation of the use of Maillard reaction inhibitors for the production of patatin-carbohydrate conjugates.

    Science.gov (United States)

    Seo, Sooyoun; Karboune, Salwa

    2014-12-17

    Selected Maillard reaction inhibitors, including aminoguanidine, cysteine, pyridoxamine, and sodium bisulfite, were evaluated for their effect on the production of carbohydrate conjugated proteins with less cross-linking/browning. Patatin (PTT), a major potato protein, was glycated with galactose, xylose, galactooligosaccharides, xylooligosaccharides, galactan, and xylan under controlled conditions. The effectiveness of the inhibitors to control the glycation reaction was assessed by monitoring the glycation extent, the protein cross-linking, and the formation of dicarbonyl compounds. Sodium bisulfite was the most effective inhibitor for PTT-galactose and PTT-xylan reaction systems (reaction control ratios of 210.0 and 12.8). On the other hand, aminoguanidine and cysteine led to the highest reaction control ratios for the PTT-xylose/xylooligosaccharide (160.0 and 143.0) and PTT-galactooligosaccharides/galactan (663.0 and 71.0) reaction systems, respectively. The use of cysteine and aminoguanidine as inhibitors led to 1.7-99.4% decreases in the particle size distribution of the PTT conjugates and to 0.4-9.3% increases in their relative digestibility, per 5% blocked lysine.

  1. Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

    Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

  2. SAM-dependent enzyme-catalysed pericyclic reactions in natural product biosynthesis

    Science.gov (United States)

    Ohashi, Masao; Liu, Fang; Hai, Yang; Chen, Mengbin; Tang, Man-Cheng; Yang, Zhongyue; Sato, Michio; Watanabe, Kenji; Houk, K. N.; Tang, Yi

    2017-09-01

    Pericyclic reactions—which proceed in a concerted fashion through a cyclic transition state—are among the most powerful synthetic transformations used to make multiple regioselective and stereoselective carbon-carbon bonds. They have been widely applied to the synthesis of biologically active complex natural products containing contiguous stereogenic carbon centres. Despite the prominence of pericyclic reactions in total synthesis, only three naturally existing enzymatic examples (the intramolecular Diels-Alder reaction, and the Cope and the Claisen rearrangements) have been characterized. Here we report a versatile S-adenosyl-L-methionine (SAM)-dependent enzyme, LepI, that can catalyse stereoselective dehydration followed by three pericyclic transformations: intramolecular Diels-Alder and hetero-Diels-Alder reactions via a single ambimodal transition state, and a retro-Claisen rearrangement. Together, these transformations lead to the formation of the dihydropyran core of the fungal natural product, leporin. Combined in vitro enzymatic characterization and computational studies provide insight into how LepI regulates these bifurcating biosynthetic reaction pathways by using SAM as the cofactor. These pathways converge to the desired biosynthetic end product via the (SAM-dependent) retro-Claisen rearrangement catalysed by LepI. We expect that more pericyclic biosynthetic enzymatic transformations remain to be discovered in naturally occurring enzyme ‘toolboxes’. The new role of the versatile cofactor SAM is likely to be found in other examples of enzyme catalysis.

  3. Thin layer chromatography coupled with surface-enhanced Raman scattering as a facile method for on-site quantitative monitoring of chemical reactions.

    Science.gov (United States)

    Zhang, Zong-Mian; Liu, Jing-Fu; Liu, Rui; Sun, Jie-Fang; Wei, Guo-Hua

    2014-08-05

    By coupling surface-enhanced Raman spectroscopy (SERS) with thin layer chromatography (TLC), a facile and powerful method was developed for on-site monitoring the process of chemical reactions. Samples were preseparated on a TLC plate following a common TLC procedure, and then determined by SERS after fabricating a large-area, uniform SERS substrate on the TLC plate by spraying gold nanoparticles (AuNPs). Reproducible and strong SERS signals were obtained with substrates prepared by spraying 42-nm AuNPs at a density of 5.54 × 10(10) N/cm(2) on the TLC plate. The capacity of this TLC-SERS method was evaluated by monitoring a typical Suzuki coupling reaction of phenylboronic acid and 2-bromopyridine as a model. Results showed that this proposed method is able to identify reaction product that is invisible to the naked eye, and distinguish the reactant 2-bromopyridine and product 2-phenylpyridine, which showed almost the same retention factors (R(f)). Under the optimized conditions, the peak area of the characteristic Raman band (755 cm(-1)) of the product 2-phenylpyridine showed a good linear correlation with concentration in the range of 2-200 mg/L (R(2) = 0.9741), the estimated detection limit (1 mg/L 2-phenylpyridine) is much lower than the concentration of the chemicals in the common organic synthesis reaction system, and the product yield determined by the proposed TLC-SERS method agreed very well with that by UPLC-MS/MS. In addition, a new byproduct in the reaction system was found and identified through continuous Raman detection from the point of sample to the solvent front. This facile TLC-SERS method is quick, easy to handle, low-cost, sensitive, and can be exploited in on-site monitoring the processes of chemical reactions, as well as environmental and biological processes.

  4. Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere

    Science.gov (United States)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

  5. A triple telescope for the simultaneous identification of light and heavy reaction products

    CERN Document Server

    Moura, M M D; Alonso, E E; Souza, F A; Fujii, R J; Morais, O B D; Szanto, E M; Szanto de Toledo, A; Carlin, N

    2001-01-01

    Sixteen triple telescopes were developed to be used in the study of light heavy-ion nuclear reactions at the University of Sao Paulo Pelletron Laboratory, with the purpose of providing simultaneous identification of light and heavy reaction products. Each telescope consists of one ionization chamber, one Si detector and one CsI detector with photodiode readout. The telescopes are encapsulated in such a way that they can be utilized in different setup geometries depending on the kind of experiment being performed. Results for the ionization chambers energy loss resolution, Si and CsI detectors energy resolution and general performance are presented.

  6. Transfer products from the reactions of heavy ions with heavy nuclei

    International Nuclear Information System (INIS)

    Thomas, K.E. III.

    1979-11-01

    Production of nuclides heavier than the target from 86 Kr- and 136 Xe-induced reactions with 181 Ta and 238 U was investigated. Attempts were made to produce new neutron-excess Np and Pu isotopes by the deep inelastic mechanism. No evidence was found for 242 Np or 247 Pu. Estimates were made for the production of 242 Np, 247 Pu, and 248 Am from heavy-ion reactions with uranium targets. Comparisons of reactions of 86 Kr and 136 Xe ions with thick 181 Ta targets and 86 Kr, 136 Xe and 238 U ions with thick 238 U targets indicate that the most probable products are not dependent on the projectile. The most probable products can be predicted by the equation Z - Z/sub target/ = 0.43 (A - A/sub target/) + 1.0. The major effect of the projectile is the magnitude of the production cross section of the heavy products. Based on these results, estimates are made of the most probable mass of element 114 produced from heavy-ion reactions with 248 Cm and 254 Es targets. These estimates give the mass number of element 114 as approx. 287 if produced in heavy-ion reactions with these very heavy targets. Excitation functions of gold and bismuth isotopes arising from 86 Kr- and 136 Xe-induced reactions with thin 181 Ta targets were measured. These results indicate that the shape and location (in Z and A above the target) of the isotopic distributions are not strongly dependent on the projectile incident energy. Also, the nuclidic cross sections are found to increase with an increase in projectile energy to a maximum at approximately 1.4 to 1.5 times the Coulomb barrier. Above this maximum, the nuclidic cross sections are found to decrease with an increase in projectile energy. This decrease in cross section is believed to be due to fission of the heavy products caused by high excitation energy and angular momentum. 111 references, 39 figures, 34 tables

  7. An Investigation of the Complexity of Maillard Reaction Product Profiles from the Thermal Reaction of Amino Acids with Sucrose Using High Resolution Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Agnieszka Golon

    2014-08-01

    Full Text Available Thermal treatment of food changes its chemical composition drastically with the formation of “so-called” Maillard reaction products, being responsible for the sensory properties of food, along with detrimental and beneficial health effects. In this contribution, we will describe the reactivity of several amino acids, including arginine, lysine, aspartic acid, tyrosine, serine and cysteine, with carbohydrates. The analytical strategy employed involves high and ultra-high resolution mass spectrometry followed by chemometric-type data analysis. The different reactivity of amino acids towards carbohydrates has been observed with cysteine and serine, resulting in complex MS spectra with thousands of detectable reaction products. Several compounds have been tentatively identified, including caramelization reaction products, adducts of amino acids with carbohydrates, their dehydration and hydration products, disproportionation products and aromatic compounds based on molecular formula considerations.

  8. S-Nitroglutathione, a product of the reaction between peroxynitrite and glutathione that generates nitric oxide.

    Science.gov (United States)

    Balazy, M; Kaminski, P M; Mao, K; Tan, J; Wolin, M S

    1998-11-27

    Peroxynitrite (ONOO-) has been shown in studies on vascular relaxation and guanylate cyclase activation to react with glutathione (GSH), generating an intermediate product that promotes a time-dependent production of nitric oxide (NO). In this study, reactions of ONOO- with GSH produced a new substance, which was characterized by liquid chromatography, ultraviolet spectroscopy, and electrospray tandem mass spectrometry. The mass spectrometric data provided evidence that the product of this reaction was S-nitroglutathione (GSNO2) and that S-nitrosoglutathione (GSNO) was not a detectable product of this reaction. Further evidence was obtained by comparison of the spectral and chromatographic properties with synthetic standards prepared by reaction of GSH with nitrosonium or nitronium borofluorates. Both the synthetic and ONOO-/GSH-derived GSNO2 generated a protonated ion, GSNO2H+, at m/z 353, which was unusually resistant to decomposition under collision activation, and no fragmentation was observed at collision energy of 25 eV. In contrast, an ion at m/z 337 (GSNOH+), generated from the synthetic GSNO, readily fragmented with the abundant loss of NO at 9 eV. Reactions of ONOO- with GSH resulted in the generation of NO, which was detected by the head space/NO-chemiluminescence analyzer method. The generation of NO was inhibited by the presence of glucose and/or CO2 in the buffers employed. Synthetic GSNO2 spontaneously generated NO in a manner that was not significantly altered by glucose or CO2. Thus, ONOO- reacts with GSH to form GSNO2, and GSNO2 decomposes in a manner that generates NO.

  9. Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions.

    Science.gov (United States)

    Arenillas, Ana; Rubiera, Fernando; Pis, José J

    2002-12-15

    Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

  10. Surface-enhanced Raman scattering active gold nanostructure fabricated by photochemical reaction of synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, Akinobu, E-mail: yamaguti@lasti.u-hyogo.ac.jp [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Matsumoto, Takeshi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Okada, Ikuo; Sakurai, Ikuya [Synchrotoron Radiation Research Center, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Utsumi, Yuichi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan)

    2015-06-15

    The deposition of gold nanoparticles in an electroplating solution containing gold (I) trisodium disulphite under synchrotron X-ray radiation was investigated. The nanoparticles grew and aggregated into clusters with increasing radiation time. This behavior is explained by evaluating the effect of Derjaguin-Landau-Verweyand-Overbeek (DLVO) interactions combining repulsive electrostatic and attractive van der Waals forces on the particle deposition process. The surface-enhanced Raman scattering (SERS) of 4,4′ -bipyridine (4bpy) in aqueous solution was measured using gold nanoparticles immobilized on silicon substrates under systematically-varied X-ray exposure. The substrates provided an in situ SERS spectrum for 1 nM 4bpy. This demonstration creates new opportunities for chemical and environmental analyses through simple SERS measurements. - Highlights: • Gold nanoparticles were produced by photochemical reaction of synchrotron radiation. • The gold nanoparticles grew and aggregated into the higher-order nanostructure. • The behavior is qualitatively explained by analytical estimation. • The surface-enhanced Raman spectroscopy of 4,4′-bipyridine (4bpy) was demonstrated. • The substrate fabricated in a suitable condition provides in situ SERS for 1 nM 4bpy.

  11. Surface modification of highly oriented pyrolytic graphite by reaction with atomic nitrogen at high temperatures

    International Nuclear Information System (INIS)

    Zhang Luning; Pejakovic, Dusan A.; Geng Baisong; Marschall, Jochen

    2011-01-01

    Dry etching of {0 0 0 1} basal planes of highly oriented pyrolytic graphite (HOPG) using active nitridation by nitrogen atoms was investigated at low pressures and high temperatures. The etching process produces channels at grain boundaries and pits whose shapes depend on the reaction temperature. For temperatures below 600 deg. C, the majority of pits are nearly circular, with a small fraction of hexagonal pits with rounded edges. For temperatures above 600 deg. C, the pits are almost exclusively hexagonal with straight edges. The Raman spectra of samples etched at 1000 deg. C show the D mode near 1360 cm -1 , which is absent in pristine HOPG. For deep hexagonal pits that penetrate many graphene layers, neither the surface number density of pits nor the width of pit size distribution changes substantially with the nitridation time, suggesting that these pits are initiated at a fixed number of extended defects intersecting {0 0 0 1} planes. Shallow pits that penetrate 1-2 graphene layers have a wide size distribution, which suggests that these pits are initiated on pristine graphene surfaces from lattice vacancies continually formed by N atoms. A similar wide size distribution of shallow hexagonal pits is observed in an n-layer graphene sample after N-atom etching.

  12. Chemical reactions of fission products with ethylene using the gas jet technique

    International Nuclear Information System (INIS)

    Contis, E.T.; Rengan, Krish; Griffin, Henry C.

    1994-01-01

    An understanding of the nature of the chemical reactions taking place between fission products and their carrier gases, and the designing of a fast separation procedure were the purposes of this investigation. Chemical reactions of short-lived (less than one minute half-life) fission products with carrier gases lead to various chemical species which can be separated in the gas phase. The Gas Jet Facility at the Ford Nuclear Reactor was used to study the yields of volatile selenium and bromine fission products of 235 U using a semi-automatic batch solvent extraction technique. Heptane and water were used as organic and inorganic solvents. A carrier gas mixture of ethylene to pre-purified nitrogen (1 : 3) was used to sweep the fission products from the target to the chemistry area for analysis. The results indicated that the volatile selenium products generated by the interaction of selenium fission fragments with ethylene were predominantly organic in nature (84%), possibly organoselenides. The selenium values were used to resolve the fractions of the bromine nuclides, which come from two major sources, viz., directly from fission and from the beta-decay of selenium. The data showed that the fractions of independent bromine fission products in the organic phase were much lower compared to selenium; the bromine values range from 10 to 22% and varied with mass number. Results indicated that the bromine products were inorganic in nature, as possibly hydrogen chloride. ((orig.))

  13. SALTS AND RADIATION PRODUCTS ON THE SURFACE OF EUROPA

    International Nuclear Information System (INIS)

    Brown, M. E.; Hand, K. P.

    2013-01-01

    The surface of Europa could contain the compositional imprint of an underlying interior ocean, but competing hypotheses differ over whether spectral observations from the Galileo spacecraft show the signature of ocean evaporates or simply surface radiation products unrelated to the interior. Using adaptive optics at the W. M. Keck Observatory, we have obtained spatially resolved spectra of most of the disk of Europa at a spectral resolution ∼40 times higher than seen by the Galileo spacecraft. These spectra show a previously undetected distinct signature of magnesium sulfate salts on Europa, but the magnesium sulfate is confined to the trailing hemisphere and spatially correlated with the presence of radiation products like sulfuric acid and SO 2 . On the leading, less irradiated, hemisphere, our observations rule out the presence of many of the proposed sulfate salts, but do show the presence of distorted water ice bands. Based on the association of the potential MgSO 4 detection on the trailing side with other radiation products, we conclude that MgSO 4 is also a radiation product, rather than a constituent of a Europa ocean brine. Based on ocean chemistry models, we hypothesize that, prior to irradiation, magnesium is primarily in the form of MgCl 2 , and we predict that NaCl and KCl are even more abundant, and, in fact, dominate the non-ice component of the leading hemisphere. We propose observational tests of this new hypothesis.

  14. SALTS AND RADIATION PRODUCTS ON THE SURFACE OF EUROPA

    Energy Technology Data Exchange (ETDEWEB)

    Brown, M. E. [Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 (United States); Hand, K. P., E-mail: mbrown@caltech.edu [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States)

    2013-04-15

    The surface of Europa could contain the compositional imprint of an underlying interior ocean, but competing hypotheses differ over whether spectral observations from the Galileo spacecraft show the signature of ocean evaporates or simply surface radiation products unrelated to the interior. Using adaptive optics at the W. M. Keck Observatory, we have obtained spatially resolved spectra of most of the disk of Europa at a spectral resolution {approx}40 times higher than seen by the Galileo spacecraft. These spectra show a previously undetected distinct signature of magnesium sulfate salts on Europa, but the magnesium sulfate is confined to the trailing hemisphere and spatially correlated with the presence of radiation products like sulfuric acid and SO{sub 2}. On the leading, less irradiated, hemisphere, our observations rule out the presence of many of the proposed sulfate salts, but do show the presence of distorted water ice bands. Based on the association of the potential MgSO{sub 4} detection on the trailing side with other radiation products, we conclude that MgSO{sub 4} is also a radiation product, rather than a constituent of a Europa ocean brine. Based on ocean chemistry models, we hypothesize that, prior to irradiation, magnesium is primarily in the form of MgCl{sub 2}, and we predict that NaCl and KCl are even more abundant, and, in fact, dominate the non-ice component of the leading hemisphere. We propose observational tests of this new hypothesis.

  15. Ab initio chemical kinetics for the ClOO + NO reaction: Effects of temperature and pressure on product branching formation

    Science.gov (United States)

    Raghunath, P.; Lin, M. C.

    2012-07-01

    The kinetics and mechanism for the reaction of ClOO with NO have been investigated by ab initio molecular orbital theory calculations based on the CCSD(T)/6-311+G(3df)//PW91PW91/6-311+G(3df) method, employed to evaluate the energetics for the construction of potential energy surfaces and prediction of reaction rate constants. The results show that the reaction can produce two key low energy products ClNO + 3O2 via the direct triplet abstraction path and ClO + NO2 via the association and decomposition mechanism through long-lived singlet pc-ClOONO and ClONO2 intermediates. The yield of ClNO + O2 (1△) from any of the singlet intermediates was found to be negligible because of their high barriers and tight transition states. As both key reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our transition state theory and Rice-Ramspergen-Kassel-Marcus/master equation calculations. The rate constants for ClNO + 3O2 and ClO + NO2 production from ClOO + NO can be given by 2.66 × 10-16 T1.91 exp(341/T) (200-700 K) and 1.48 × 10-24 T3.99 exp(1711/T) (200-600 K), respectively, independent of pressure below atmospheric pressure. The predicted total rate constant and the yields of ClNO and NO2 in the temperature range of 200-700 K at 10-760 Torr pressure are in close agreement with available experimental results.

  16. Reaction of diazepam and related benzodiazepines with chlorine. Kinetics, transformation products and in-silico toxicological assessment.

    Science.gov (United States)

    Carpinteiro, Inmaculada; Rodil, Rosario; Quintana, José Benito; Cela, Rafael

    2017-09-01

    In this work, the reaction of four benzodiazepines (diazepam, oxazepam, nordazepam and temazepam) during water chlorination was studied by means of liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS). For those compounds that showed a significant degradation, i.e. diazepam, oxazepam and nordazepam, parameters affecting to the reaction kinetics (pH, chlorine and bromide level) were studied in detail and transformation products were tentatively identified. The oxidation reactions followed pseudofirst-order kinetics with rate constants in the range of 1.8-42.5 M -1  s -1 , 0.13-1.16 M -1  s -1 and 0.04-20.4 M -1  s -1 corresponding to half-life values in the range of 1.9-146 min, 1.8-87 h and 2.5-637 h for oxazepam, nordazepam and diazepam, respectively, depending of the levels of studied parameters. Chlorine and pH affected significantly the reaction kinetics, where an increase of the pH resulted into a decrease of the reaction rate, whereas higher chlorine dosages led to faster kinetics, as expected in this case. The transformation of the studied benzodiazepines occurs mainly at the 1,4-diazepine 7-membered-ring, resulting in ring opening to form benzophenone derivatives or the formation of a 6-membered pyrimidine ring, leading to quinazoline derivatives. The formation of these by-products was also tested in real surface water samples observing kinetics of oxazepam degradation slower in river than in creek water, while the degradation of the two other benzodiazepines occurred only in the simpler sample (creek water). Finally, the acute and chronical toxicity and mutagenicity of precursors and transformation products were estimated using quantitative structure-activity relationship (QSAR) software tools: Ecological Structure Activity Relationships (ECOSAR) and Toxicity Estimation Software Tool (TEST), finding that some transformation products could be more toxic/mutagenic than the precursor drug, but additional test would be needed

  17. Localized surface grafting reactions on carbon nanofibers induced by gamma and e-beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Evora, M.C., E-mail: cecilia@ieav.cta.br [Institute for Advanced Studies-IEAV/DCTA, Av. Cel Jose Alberto Albano do Amarante, 1-Putim, 12228-001 São Jose dos Campos, SP (Brazil); Araujo, J.R., E-mail: jraraujo@inmetro.gov.br [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Ferreira, E.H.M. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Strohmeier, B.R. [Thermo Fisher Scientific, 5225 Verona Road, Madison, WI 53711 (United States); Silva, L.G.A., E-mail: lgasilva@ipen.br [Institute for Nuclear and Energy Research- IPEN, Av. Prof lineu Prestes, 2242- Cidade Universitaria, 05508-000 SP (Brazil); Achete, C.A. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil)

    2015-04-30

    Graphical abstract: - Highlights: • Methodology for the functionalization of carbon nanofibers was investigated. • Two radiation sources were used to promote grafting reactions: gamma and electron beam. • We report the optimum inhibitor concentration to achieve the functionalization. • Surface of carbon nanofibers showed an increase of oxygen content after irradiation. • The radiation-induced graphitization did not damage the overall sp{sup 2} structure. - Abstract: Electron beam and gamma-ray irradiation have potential application to modify the carbon fiber nanostructures in order to produce useful defects in the graphitic structure and create reactive sites. In this study, the methodology to functionalize carbon nanofiber (CNF), via a radiation process and using acrylic acid as a source of oxygen functional groups, was investigated. The samples were submitted to a direct grafting radiation process with electron beam and gamma-ray source. Several parameters were changed such as: acrylic acid concentration, radiation dose and percentage of inhibitor necessary to achieve functionalization, with higher percentage of oxygen functional groups on CNF surface, and better dispersion. The better results achieved were when mixing CNF in a solution of acrylic acid with 6% of inhibitor (FeSO{sub 4}·7H{sub 2}O) and irradiated at 100 kGy. The samples were characterized by X-ray photoelectron spectroscopy and the surface composition (atomic%) showed a significant increase of oxygen content for the samples after irradiation. Also, the dispersion of the functionalized CNF in water was stable during months which may be a good indication that the functionalization process of CNF via ionizing radiation was successful.

  18. Localized surface grafting reactions on carbon nanofibers induced by gamma and e-beam irradiation

    International Nuclear Information System (INIS)

    Evora, M.C.; Araujo, J.R.; Ferreira, E.H.M.; Strohmeier, B.R.; Silva, L.G.A.; Achete, C.A.

    2015-01-01

    Graphical abstract: - Highlights: • Methodology for the functionalization of carbon nanofibers was investigated. • Two radiation sources were used to promote grafting reactions: gamma and electron beam. • We report the optimum inhibitor concentration to achieve the functionalization. • Surface of carbon nanofibers showed an increase of oxygen content after irradiation. • The radiation-induced graphitization did not damage the overall sp 2 structure. - Abstract: Electron beam and gamma-ray irradiation have potential application to modify the carbon fiber nanostructures in order to produce useful defects in the graphitic structure and create reactive sites. In this study, the methodology to functionalize carbon nanofiber (CNF), via a radiation process and using acrylic acid as a source of oxygen functional groups, was investigated. The samples were submitted to a direct grafting radiation process with electron beam and gamma-ray source. Several parameters were changed such as: acrylic acid concentration, radiation dose and percentage of inhibitor necessary to achieve functionalization, with higher percentage of oxygen functional groups on CNF surface, and better dispersion. The better results achieved were when mixing CNF in a solution of acrylic acid with 6% of inhibitor (FeSO 4 ·7H 2 O) and irradiated at 100 kGy. The samples were characterized by X-ray photoelectron spectroscopy and the surface composition (atomic%) showed a significant increase of oxygen content for the samples after irradiation. Also, the dispersion of the functionalized CNF in water was stable during months which may be a good indication that the functionalization process of CNF via ionizing radiation was successful

  19. Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

    Directory of Open Access Journals (Sweden)

    M. M. Chim

    2017-12-01

    Full Text Available Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4 droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5 hydroxyl functionalization product (C5H8O5 and a C4 fragmentation product (C4H6O3. These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from

  20. In situ Raman scattering study on a controllable plasmon-driven surface catalysis reaction on Ag nanoparticle arrays

    International Nuclear Information System (INIS)

    Dai, Z G; Xiao, X H; Zhang, Y P; Ren, F; Wu, W; Zhang, S F; Zhou, J; Jiang, C Z; Mei, F

    2012-01-01

    Control of the plasmon-driven chemical reaction for the transformation of 4-nitrobenzenethiol to p,p′-dimercaptoazobenzene by Ag nanoparticle arrays was studied. The Ag nanoparticle arrays were fabricated by means of nanosphere lithography. By changing the PS particle size, the localized surface plasmon resonance (LSPR) peaks of the Ag nanoparticle arrays can be tailored from 460 to 560 nm. The controlled reaction process was monitored by in situ surface-enhanced Raman scattering. The reaction can be dramatically influenced by varying the duration of laser exposure, Ag nanoparticle size, laser power and laser excitation wavelength. The maximum reaction speed was achieved when the LSPR wavelength of the Ag nanoparticle arrays matched the laser excitation wavelength. The experimental results reveal that the strong LSPR can effectively drive the transfer of the ‘hot’ electrons that decay from the plasmon to the reactants. The experimental results were confirmed by theoretical calculations. (paper)

  1. 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.

  2. [Vigilance for veterinary medicinal products: declarations of adverse reactions in the year 2009].

    Science.gov (United States)

    Müntener, C R; Bruckner, L; Stürer, A; Althaus, F R; Caduff-Janosa, P

    2010-12-01

    During the year 2009, 134 reports of suspected adverse drug reactions (ADRs) to veterinary medicinal products (VMPs) were received (106 in the year 2008). The distribution according to species and drug classes remained in line with previous years. Companion animals were involved in most of the reports (46 % dogs, 19 % cats), followed by cattle or calves (22 %). Antiparasitic drugs made the biggest part with 30 % of the reports, followed by antiinfectives (19 %) and hormones (13 %). Some reactions following their use are specifically discussed. 95 additional enquiries about ADRs of VMPs were received by the Swiss Toxicological Information Centre in Zürich. Most of them concerned dogs or cats and antiparasitics or anti-inflammatory drugs. In the vaccinovigilance program, a total of 1020 reports were received, of which 1000 were related to the vaccination against blue tongue disease. The most frequently reported adverse reactions were aborts, mastitis or alterations of milk quality and they are specifically discussed.

  3. Determination of Free Fatty Acid by FT-NIR Spectroscopy in Esterification Reaction for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Djéssica Tatiana Raspe

    2013-01-01

    Full Text Available This work reports the use of FT-NIR spectroscopy coupled with multivariate calibration to determine the percentage of free fatty acids (FFA in samples obtained by the esterification of FFA in vegetable oils. The analytical method used as calibration matrix samples of the reaction medium of esterification of oleic acid in soybean oil in proportions of 0.3 to 40 wt% (by weight of oleic acid obtained under different experimental conditions and utilized the partial least squares (PLS regression. The efficiency of the method was tested to predict the content of FFA in reactions of esterification of oleic acid in soybean oil catalysed by KSF clay and Amberlyst 15 commercial resin, both in a batch mode. Good Correlations were observed between the FT-NIR/PLS method and the reference method (AOCS. The results confirm that FT-NIR spectroscopy, in combination with multivariate calibration, is a promising technique for monitoring esterification reaction for biodiesel production.

  4. FOBOS - a 4π-fragment spectrometer for heavy-ion reaction products

    International Nuclear Information System (INIS)

    Ortlepp, H.G.; Schilling, K.D.

    1992-06-01

    The FOBOS detector presently under construction at Dubna is intended for heavy ion reaction studies in the bombarding energy range of 10...100 AMeV. It will consist of a 'gas-ball' of 30 position-sensitive avalanche counters and 30 axial ionization chambers behind them, a shell of 190 scintillation counters surrounding the gas ball and a forward phoswich array. All charged reaction products may be measured in a wide dynamic range and in a geometry covering a substantial part of 4π. Special developments were necessary concerning the mechanical construction, the detector design, the evacuation and gas supply and the electronics. Presently individual detector modules are being tested at the beam of the U-400 heavy ion cyclotron of the Laboratory of nuclear reactions. (orig.)

  5. Product differentiation by analysis of DNA melting curves during the polymerase chain reaction.

    Science.gov (United States)

    Ririe, K M; Rasmussen, R P; Wittwer, C T

    1997-02-15

    A microvolume fluorometer integrated with a thermal cycler was used to acquire DNA melting curves during polymerase chain reaction by fluorescence monitoring of the double-stranded DNA specific dye SYBR Green I. Plotting fluorescence as a function of temperature as the thermal cycler heats through the dissociation temperature of the product gives a DNA melting curve. The shape and position of this DNA melting curve are functions of the GC/AT ratio, length, and sequence and can be used to differentiate amplification products separated by less than 2 degrees C in melting temperature. Desired products can be distinguished from undesirable products, in many cases eliminating the need for gel electrophoresis. Analysis of melting curves can extend the dynamic range of initial template quantification when amplification is monitored with double-stranded DNA specific dyes. Complete amplification and analysis of products can be performed in less than 15 min.

  6. Prediction of bakery products nutritive value based on mathematical modeling of biochemical reactions

    Directory of Open Access Journals (Sweden)

    E. I. Ponomareva

    2013-01-01

    Full Text Available Researches are devoted to identifying changes in the chemical composition of whole-grain wheat bread during baking and to forecasting of food value of bakery products by mathematical modeling of biochemical transformations. The received model represents the invariant composition, considering speed of biochemical reactions at a batch of bakery products, and allowing conduct virtual experiments to develop new types of bread for various categories of the population, including athletes. The offered way of modeling of biochemical transformations at a stage of heat treatment allows to predict food value of bakery products, without spending funds for raw materials and large volume of experiment that will provide possibility of economy of material resources at a stage of development of new types of bakery products and possibility of production efficiency increase.

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

    Science.gov (United States)

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

    2014-10-09

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

  8. Use of Helium Production to Screen Glow Discharges for Low Energy Nuclear Reactions (LENR)

    Science.gov (United States)

    Passell, Thomas O.

    2011-03-01

    My working hypothesis of the conditions required to observe low energy nuclear reactions (LENR) follows: 1) High fluxes of deuterium atoms through interfaces of grains of metals that readily accommodate movement of hydrogen atoms interstitially is the driving variable that produces the widely observed episodes of excess heat above the total of all input energy. 2) This deuterium atom flux has been most often achieved at high electrochemical current densities on highly deuterium-loaded palladium cathodes but is clearly possible in other experimental arrangements in which the metal is interfacing gaseous deuterium, as in an electrical glow discharge. 3) Since the excess heat episodes must be producing the product(s) of some nuclear fusion reaction(s) screening of options may be easier with measurement of those ``ashes'' than the observance of the excess heat. 4) All but a few of the exothermic fusion reactions known among the first 5 elements produce He-4. Hence helium-4 appearance in an experiment may be the most efficient indicator of some fusion reaction without commitment on which reaction is occurring. This set of hypotheses led me to produce a series of sealed tubes of wire electrodes of metals known to absorb hydrogen and operate them for 100 days at the 1 watt power level using deuterium gas pressures of ~ 100 torr powered by 40 Khz AC power supplies. Observation of helium will be by measurement of helium optical emission lines through the glass envelope surrounding the discharge. The results of the first 18 months of this effort will be described.

  9. Advances in the production of freeform optical surfaces

    Science.gov (United States)

    Tohme, Yazid E.; Luniya, Suneet S.

    2007-05-01

    Recent market demands for free-form optics have challenged the industry to find new methods and techniques to manufacture free-form optical surfaces with a high level of accuracy and reliability. Production techniques are becoming a mix of multi-axis single point diamond machining centers or deterministic ultra precision grinding centers coupled with capable measurement systems to accomplish the task. It has been determined that a complex software tool is required to seamlessly integrate all aspects of the manufacturing process chain. Advances in computational power and improved performance of computer controlled precision machinery have driven the use of such software programs to measure, visualize, analyze, produce and re-validate the 3D free-form design thus making the process of manufacturing such complex surfaces a viable task. Consolidation of the entire production cycle in a comprehensive software tool that can interact with all systems in design, production and measurement phase will enable manufacturers to solve these complex challenges providing improved product quality, simplified processes, and enhanced performance. The work being presented describes the latest advancements in developing such software package for the entire fabrication process chain for aspheric and free-form shapes. It applies a rational B-spline based kernel to transform an optical design in the form of parametrical definition (optical equation), standard CAD format, or a cloud of points to a central format that drives the simulation. This software tool creates a closed loop for the fabrication process chain. It integrates surface analysis and compensation, tool path generation, and measurement analysis in one package.

  10. Limonene and its ozone-initiated reaction products attenuate allergic lung inflammation in mice.

    Science.gov (United States)

    Hansen, Jitka S; Nørgaard, Asger W; Koponen, Ismo K; Sørli, Jorid B; Paidi, Maya D; Hansen, Søren W K; Clausen, Per Axel; Nielsen, Gunnar D; Wolkoff, Peder; Larsen, Søren Thor

    2016-11-01

    Inhalation of indoor air pollutants may cause airway irritation and inflammation and is suspected to worsen allergic reactions. Inflammation may be due to mucosal damage, upper (sensory) and lower (pulmonary) airway irritation due to activation of the trigeminal and vagal nerves, respectively, and to neurogenic inflammation. The terpene, d-limonene, is used as a fragrance in numerous consumer products. When limonene reacts with the pulmonary irritant ozone, a complex mixture of gas and particle phase products is formed, which causes sensory irritation. This study investigated whether limonene, ozone or the reaction mixture can exacerbate allergic lung inflammation and whether airway irritation is enhanced in allergic BALB/cJ mice. Naïve and allergic (ovalbumin sensitized) mice were exposed via inhalation for three consecutive days to clean air, ozone, limonene or an ozone-limonene reaction mixture. Sensory and pulmonary irritation was investigated in addition to ovalbumin-specific antibodies, inflammatory cells, total protein and surfactant protein D in bronchoalveolar lavage fluid and hemeoxygenase-1 and cytokines in lung tissue. Overall, airway allergy was not exacerbated by any of the exposures. In contrast, it was found that limonene and the ozone-limonene reaction mixture reduced allergic inflammation possibly due to antioxidant properties. Ozone induced sensory irritation in both naïve and allergic mice. However, allergic but not naïve mice were protected from pulmonary irritation induced by ozone. This study showed that irritation responses might be modulated by airway allergy. However, aggravation of allergic symptoms was observed by neither exposure to ozone nor exposure to ozone-initiated limonene reaction products. In contrast, anti-inflammatory properties of the tested limonene-containing pollutants might attenuate airway allergy.

  11. Effect of Solvents on the Product Distribution and Reaction Rate of a Buchwald-Hartwig Amination Reaction

    DEFF Research Database (Denmark)

    Christensen, H.; Kiil, Søren; Dam-Johansen, Kim

    2006-01-01

    The Buchwald-Hartwig amination reaction between p-bromotoluene and piperazine in the presence of the homogeneous catalytic system Pd(dba)(2)/(+/-)-BINAP and the base NaO-t-Bu was investigated in two different classes of solvents: aprotic, nonpolar and aprotic, polar. The reaction was carried out...... solvent for the Buchwald-Hartwig amination reaction under the conditions applied was m-xylene....

  12. 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.

  13. State of the art and prospective of lipase-catalyzed transesterification reaction for biodiesel production

    International Nuclear Information System (INIS)

    Amini, Zeynab; Ilham, Zul; Ong, Hwai Chyuan; Mazaheri, Hoora; Chen, Wei-Hsin

    2017-01-01

    Highlights: • Enzymatic transesterification process is less energy intensive and robust. • Nano-materials are promising immobilization supports for lipase. • Packed-bed reactors are appropriate for scale-up use. • Potential recombinant, whole cell and recombinant whole cell lipases were enlisted. • Genetic engineering is a promising prospect in biodiesel area. - Abstract: The world demand for fuel as energy sources have arisen the need for generating alternatives such as biofuel. Biodiesel is a renewable fuel used particularly in diesel engines. Currently, biodiesel is mainly produced through transesterification reactions catalyzed by chemical catalysts, which produces higher fatty acid alkyl esters in shorter reaction time. Although extensive investigations on enzymatic transesterification by downstream processing were carried out, enzymatic transesterification has yet to be used in scale-up since commercial lipases are chiefly limited to the cost as well as long reaction time. While numerous lipases were studied and proven to have the high catalytic capacity, still enzymatic reaction requires more investigation. To fill this gap, finding optimal conditions for the reaction such as alcohol and oil choice, water content, reaction time and temperature through proper reaction modelling and simulations as well as the appropriate design and use of reactors for large scale production are crucial issues that need to be accurately addressed. Furthermore, lipase concentration, alternative lipase resources through whole cell technology and genetic engineering, recent immobilizing materials including nanoparticles, and the capacity of enzyme to be reused are important criteria to be neatly investigated. The present work reviews the current biodiesel feedstock, catalysis, general and novel immobilizing materials, bioreactors for enzymatic transesterification, potential lipase resources, intensification technics, and process modelling for enzymatic

  14. Zeolite Membrane Reactor for Water Gas Shift Reaction for Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Jerry Y.S. [Arizona State Univ., Mesa, AZ (United States)

    2013-01-29

    Gasification of biomass or heavy feedstock to produce hydrogen fuel gas using current technology is costly and energy-intensive. The technology includes water gas shift reaction in two or more reactor stages with inter-cooling to maximize conversion for a given catalyst volume. This project is focused on developing a membrane reactor for efficient conversion of water gas shift reaction to produce a hydrogen stream as a fuel and a carbon dioxide stream suitable for sequestration. The project was focused on synthesizing stable, hydrogen perm-selective MFI zeolite membranes for high temperature hydrogen separation; fabricating tubular MFI zeolite membrane reactor and stable water gas shift catalyst for membrane reactor applications, and identifying experimental conditions for water gas shift reaction in the zeolite membrane reactor that will produce a high purity hydrogen stream. The project has improved understanding of zeolite membrane synthesis, high temperature gas diffusion and separation mechanisms for zeolite membranes, synthesis and properties of sulfur resistant catalysts, fabrication and structure optimization of membrane supports, and fundamentals of coupling reaction with separation in zeolite membrane reactor for water gas shift reaction. Through the fundamental study, the research teams have developed MFI zeolite membranes with good perm-selectivity for hydrogen over carbon dioxide, carbon monoxide and water vapor, and high stability for operation in syngas mixture containing 500 part per million hydrogen sulfide at high temperatures around 500°C. The research teams also developed a sulfur resistant catalyst for water gas shift reaction. Modeling and experimental studies on the zeolite membrane reactor for water gas shift reaction have demonstrated the effective use of the zeolite membrane reactor for production of high purity hydrogen stream.

  15. Coherent production of two and three pions in pd reactions at 19 GeV/c

    International Nuclear Information System (INIS)

    Bakken, V.; Gennow, H.; Lundborg, P.; Maekelae, J.; Moellerud, R.; Pimiae, M.; Sellden, B.; Sundell, E.; Tuominemi, J.K.

    1976-10-01

    The coherent reactions pd→pdπ + π - , pd→pdπ + π - π 0 and pd→ndπ + π + π - are studied. In the two first reactions strong production of Δ ++ (1236) is observed. Production of d* 0 and d* + is observed in the first and second reactions respectively. The forward slope of the t-distribution of the pπ + π - system in the pd→pdπ + π - channel decreases with increasing mass. The 1500 and 1700 MeV enhancements in the pπ + π - mass spectrum of this channel are studied. Assuming that the Gribov-Morrison rule holds, it is found that by analysing the moments of the decay angular distributions that the resonances N(1470), N(1520) and N(1688) are the most likely resonances to be identified with these enhancements. Evidence is found against s-channel helicity conservation and some evidence against t-channel helicity conservation. The decay parameters of the Δ ++ (1236) in the reaction pd→Δ ++ π - d are in good agreement with the predictions of a one-pion exchange model. (Auth.)

  16. Demonstration of physical phenomenas and scavenging activity from d-psicose and methionine maillard reaction products

    Directory of Open Access Journals (Sweden)

    Arum Tiyas Suminar

    2017-01-01

    Full Text Available Maillard reaction has been well understood as a non-enzymatic reaction between reducing sugars and amino acids to generate the Maillard reaction products (MRPs. This study is aimed to demonstrate the browning intensity, color development, spectra measurements, scavenging activity, and the correlation between browning intensity and scavenging activity of the MRPs generated from D-Psicose and Methionine (Psi-Met at 50℃. The browning intensity of MRPs was investigated based on the absorbance using spectrophotometer at 420 nm, the color development was observed using digital colorimeter to gained L*a*b* value then calculated as browning index, the spectra development was analyzed using spectrophotometer at 190 - 750 nm, and the scavenging activity was determined with ABTS method using spectrophotometer at 734 nm. The browning intensity, color development, and scavenging activity were improved along with the increase in heating process. Based on spectra analysis, MRPs from Psi-Met was initially detected at 21 h and Psi at 24 h of heating treatment, which indicating that Psi-Met have faster and better reaction than Psi during heating process. Positive non-linear and significant correlation between browning intensity and scavenging activity were assigned. This finding may provide beneficial information of D-psicose and MRPs to the next scientific research and to the food industries which applies MRPs in their products.

  17. Applications of computer simulation, nuclear reactions and elastic scattering to surface analysis of materials

    Directory of Open Access Journals (Sweden)

    Pacheco de Carvalho, J. A.

    2008-08-01

    Full Text Available This article involves computer simulation and surface analysis by nuclear techniques, which are non-destructive. Both the “energy method of analysis” for nuclear reactions and elastic scattering are used. Energy spectra are computer simulated and compared with experimental data, giving target composition and concentration profile information. The method is successfully applied to thick flat targets of graphite, quartz and sapphire and targets containing thin films of aluminium oxide. Depth profiles of 12C and 16O nuclei are determined using (d,p and (d,α deuteron induced reactions. Rutherford and resonance elastic scattering of (4He+ ions are also used.

    Este artículo trata de simulación por ordenador y del análisis de superficies mediante técnicas nucleares, que son no destructivas. Se usa el “método de análisis en energia” para reacciones nucleares, así como el de difusión elástica. Se simulan en ordenador espectros en energía que se comparan com datos experimentales, de lo que resulta la obención de información sobre la composición y los perfiles de concentración de la muestra. Este método se aplica con éxito em muestras espesas y planas de grafito, cuarzo y zafiro y muestras conteniendo películas finas de óxido de aluminio. Se calculan perfiles en profundidad de núcleos de 12C y de 16O a través de reacciones (d,p y (d,α inducidas por deuterones. Se utiliza también la difusión elástica de iones (4He+, tanto a Rutherford como resonante.

  18. Production of heavy evaporation residues in the reactions induced by an extracted 48Ca beam on a 208Pb target

    International Nuclear Information System (INIS)

    Eremin, A.V.; Chepigin, V.I.; Itkis, M.G.

    1998-01-01

    The production cross sections of the isotopes 253-255 No were measured for the heavy ion complete fusion reaction 48 Ca + 208 Pb using the electrostatic recoil separator VASSILISSA. The obtained excitation functions for the reaction products formed after the evaporation of 1-3 neutrons from the compound nucleus are discussed and compared with the data obtained earlier and with the results of the statistical model calculations. The background conditions at the extraction of the correlated events of the reaction product decay are also considered from the point of view of future experiments on the superheavy element synthesis in the complete fusion reactions induced by 48 Ca projectiles

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

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  20. Potential of water surface-floating microalgae for biodiesel production: Floating-biomass and lipid productivities.

    Science.gov (United States)

    Muto, Masaki; Nojima, Daisuke; Yue, Liang; Kanehara, Hideyuki; Naruse, Hideaki; Ujiro, Asuka; Yoshino, Tomoko; Matsunaga, Tadashi; Tanaka, Tsuyoshi

    2017-03-01

    Microalgae have been accepted as a promising feedstock for biodiesel production owing to their capability of converting solar energy into lipids through photosynthesis. However, the high capital and operating costs, and high energy consumption, are hampering commercialization of microalgal biodiesel. In this study, the surface-floating microalga, strain AVFF007 (tentatively identified as Botryosphaerella sudetica), which naturally forms a biofilm on surfaces, was characterized for use in biodiesel production. The biofilm could be conveniently harvested from the surface of the water by adsorbing onto a polyethylene film. The lipid productivity of strain AVFF007 was 46.3 mg/L/day, allowing direct comparison to lipid productivities of other microalgal species. The moisture content of the surface-floating biomass was 86.0 ± 1.2%, which was much lower than that of the biomass harvested using centrifugation. These results reveal the potential of this surface-floating microalgal species as a biodiesel producer, employing a novel biomass harvesting and dewatering strategy. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  1. Products of aqueous vitamin B5 (pantothenic acid) formed by free radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Schittl, H. [Section of Radiation Biology, Department of Nutritional Sciences, University of Vienna, Althanstr. 14, UZA II, A-1090 Vienna (Austria); Quint, R.M. [Section of Radiation Biology, Department of Nutritional Sciences, University of Vienna, Althanstr. 14, UZA II, A-1090 Vienna (Austria); Getoff, N. [Section of Radiation Biology, Department of Nutritional Sciences, University of Vienna, Althanstr. 14, UZA II, A-1090 Vienna (Austria)]. E-mail: nikola.getoff@univie.ac.at

    2007-10-15

    The radiolysis of aqueous vitamin B5 (pantothenic acid) has been investigated under various experimental conditions. The highest vitamin degradation (G=3.22) was observed in solutions saturated with N{sub 2}O, where 90% OH radicals are operating. As final products, the following were established: aldehydes, carboxylic acids and ammonia. Their yield strongly depends on the presence/absence of air as well as on N{sub 2}O (used to convert e{sub aq} {sup -} into OH) and was determined as a function of absorbed radiation dose. HPLC-analysis showed that in all media, a main product is formed, having the highest yield in aerated solutions. Based on the chemical analysis, it appears that the OH radicals are most involved in the degradation process. A precise sequence of the reaction steps could not be given presently, because of the implication of many simultaneous reactions.

  2. Products of aqueous vitamin B5 (pantothenic acid) formed by free radical reactions

    International Nuclear Information System (INIS)

    Schittl, H.; Quint, R.M.; Getoff, N.

    2007-01-01

    The radiolysis of aqueous vitamin B5 (pantothenic acid) has been investigated under various experimental conditions. The highest vitamin degradation (G=3.22) was observed in solutions saturated with N 2 O, where 90% OH radicals are operating. As final products, the following were established: aldehydes, carboxylic acids and ammonia. Their yield strongly depends on the presence/absence of air as well as on N 2 O (used to convert e aq - into OH) and was determined as a function of absorbed radiation dose. HPLC-analysis showed that in all media, a main product is formed, having the highest yield in aerated solutions. Based on the chemical analysis, it appears that the OH radicals are most involved in the degradation process. A precise sequence of the reaction steps could not be given presently, because of the implication of many simultaneous reactions

  3. A Further Study of the Products of Sc and Dioxygen Reactions

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Zhou, Mingfei; Andrews, Lester; Johnson, J. R. Tobias; Panas, Itai; Snis, Anders; Roos, Bjoern O.; Arnold, James O. (Technical Monitor)

    1999-01-01

    The products of the reaction of Sc and dioxygen have been reinvestigated. By adding the electron-trapping molecule CC14, additional information about the IR spectra has been obtained, as well as the observation of new bands. New ab initio calculations are also performed on possible products of the Sc plus O2 reaction. The previously observed band at 722.5 per cm is assigned as the b2 mode of ScO2(-). Bands arising from ScO(+), Sc(O2)(+), and(O2)ScO are also assigned. We are still unable to assign any bands to OScO. The problems associated with the computational study of ScO2 are discussed.

  4. Basic studies on coal liquefaction reaction, reforming and utilization of liquefaction products

    Energy Technology Data Exchange (ETDEWEB)

    Shiraishi, M. (National Institute for Resources and Environment, Tsukuba (Japan))

    1993-09-01

    This report describes the achievement of research and development of coal liquefaction technologies in the Sunshine Project for FY 1992, regarding the coal liquefaction reaction, reforming and utilization of liquefaction products. For the fundamental study on coal liquefaction reaction, were investigated effect of asphaltene in petroleum residue on coprocessing, pretreatment effect in coprocessing of Taiheiyo coal and tarsand bitumen using oil soluble catalyst, solubilization and liquefaction of Taiheiyo coal at mild conditions with the aid of super acid, and flash hydropyrolysis of finely pulverized swollen coal under high hydrogen pressure. On the other hand, for the study on hydrotreatment of coal derived liquid, were investigated catalytic hydroprocessing of Wandoan coal liquids, production of gasoline from coal liquids by fluid catalytic cracking, solvent extraction of phenolic compounds from coal liquids, and separation of hetero compounds in coal liquid by means of high pressure crystallization. Further progress in these studies has been confirmed. 9 figs., 6 tabs.

  5. Perspectives of Scalar- and Vector- Meson Production in Hadron-Nucleus Reactions

    International Nuclear Information System (INIS)

    Cassing, W.

    2000-01-01

    The production and decay of vector mesons (ρ, ω) in pA reactions at COSY energies is studied with particular emphasis on their in-medium spectral functions. It is explored within transport calculations, if hadronic in-medium decays like π + π - or π 0 γ might provide complementary information to their dilepton (e + e - ) decays. Whereas the π + π - signal from the ρ-meson is found to be strongly distorted by pion rescattering, the ω- meson Dalitz decay to π 0 γ appears promising even for more heavy nuclei. The perspectives of scalar meson ( f 0 , a 0 ) production in pp reactions are investigated within a boson-exchange model indicating that the f 0 -meson might hardly be detected in these collisions in the K(anti)K or ππ decay channels whereas the exclusive channel pp→da 0 + looks very promising. (author)

  6. A quark-antiquark formation model for meson production in low transverse momentum hadron-hadron reactions

    International Nuclear Information System (INIS)

    Friebel, W.; Kriegel, U.; Nahnhauer, R.

    1979-01-01

    Introducing quark transverse momenta and masses it is proposed a 3-dimensional generalization of the quark recombination and the quark fusion model for meson production in low transverse momentum hadron-hadron reactions. A consistent description of vector meson production in proton-proton and proton-antiproton reactions from 12 - 405 GeV/c has been achieved. (author)

  7. Hoof accelerations and ground reaction forces of Thoroughbred racehorses measured on dirt, synthetic, and turf track surfaces.

    Science.gov (United States)

    Setterbo, Jacob J; Garcia, Tanya C; Campbell, Ian P; Reese, Jennifer L; Morgan, Jessica M; Kim, Sun Y; Hubbard, Mont; Stover, Susan M

    2009-10-01

    To compare hoof acceleration and ground reaction force (GRF) data among dirt, synthetic, and turf surfaces in Thoroughbred racehorses. 3 healthy Thoroughbred racehorses. Forelimb hoof accelerations and GRFs were measured with an accelerometer and a dynamometric horseshoe during trot and canter on dirt, synthetic, and turf track surfaces at a racecourse. Maxima, minima, temporal components, and a measure of vibration were extracted from the data. Acceleration and GRF variables were compared statistically among surfaces. The synthetic surface often had the lowest peak accelerations, mean vibration, and peak GRFs. Peak acceleration during hoof landing was significantly smaller for the synthetic surface (mean + or - SE, 28.5g + or - 2.9g) than for the turf surface (42.9g + or - 3.8g). Hoof vibrations during hoof landing for the synthetic surface were dirt and turf surfaces. Peak GRF for the synthetic surface (11.5 + or - 0.4 N/kg) was 83% and 71% of those for the dirt (13.8 + or - 0.3 N/kg) and turf surfaces (16.1 + or - 0.7 N/kg), respectively. The relatively low hoof accelerations, vibrations, and peak GRFs associated with the synthetic surface evaluated in the present study indicated that synthetic surfaces have potential for injury reduction in Thoroughbred racehorses. However, because of the unique material properties and different nature of individual dirt, synthetic, and turf racetrack surfaces, extending the results of this study to encompass all track surfaces should be done with caution.

  8. Multiple particles production for hadron-hadron reactions with finite hadronization time

    International Nuclear Information System (INIS)

    Arbex, N.

    1991-01-01

    Experimental data on multiple particle production for proton-proton reaction are analysed in the context of a very simple analytical model. The model exhibits the essential features of hydrodynamical calculations as, e.g., the formation of an intermediate object, which undergoes expansion. The simultaneous analysis of different types of data allows for the conclusion that such data reflect the dynamics of this intermediate object and have a very deem connection to the elementary processes. (author)

  9. Experiences on removal of sodium-water reaction products in SWAT-3

    International Nuclear Information System (INIS)

    Tanabe, H.; Hiroi, H.; Sato, M.; Otaka, J.

    2002-01-01

    This report summarizes experiences and information concerning the removal of sodium water reaction products (SMRP) obtained through large leak tests of the Steam Generator Safety Test Facility (SWAT-3) at PNC/OEC, which were conducted to validate the safety design of steam generators of a prototype LMFBR Monju. The following three problems are discussed here: (1) drainability of SWRP, (2) removal of SWRP by using a cold trap, and (3) steam cleaning of SWRP. (author)

  10. Measurement of reaction cross sections of fission products induced by DT neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Nakano, Daisuke; Murata, Isao; Takahashi, Akito [Osaka Univ., Suita (Japan)

    1998-03-01

    With the view of future application of fusion reactor to incineration of fission products, we have measured the {sup 129}I(n,2n){sup 128}I reaction cross section by DT neutrons with the activation method. The measured cross section was compared with the evaluated nuclear data of JENDL-3.2. From the result, it was confirmed that the evaluation overestimated the cross section by about 20-40%. (author)

  11. Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rubio-Pereda, Pamela, E-mail: rubio.pereda@gmail.com [Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California (Mexico); Takeuchi, Noboru, E-mail: takeuchi@cnyn.unam.mx [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California (Mexico)

    2016-08-30

    Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

  12. Velocity map imaging of ion-molecule reaction products: Co+(3F4)+isobutane

    Science.gov (United States)

    Reichert, Emily L.; Thurau, Gert; Weisshaar, James C.

    2002-07-01

    The velocity map imaging technique is applied to mass-selected CoC3H6++CH4 and CoC4H8++H2 elimination products from the Co+(3F4)+isobutane reaction studied under crossed-beam conditions at 0.21 eV collision energy. For both reactions we obtain the joint scattering probability distribution P(E,Θ), where E and Θ are the product translational energy and scattering angle. The fraction of available energy deposited into product translation is 0.4 for H2, compared with 0.1 for CH4. For the CH4 product, the angular distribution is forward-backwards symmetric and sharply peaked at Θ=0 and 180°. P(E,Θ) is not separable into the product of an energy and an angular function; rather, the angular distribution peaks more sharply at higher translational energy. Evidently, incipient CoC3H6++CH4 products equilibrate in the Co+(C3H6)(CH4) exit-channel well, from which they decay statistically. The product translational energy distribution P(E) is consistent with orbiting-transition state phase-space theory with no exit-channel barrier. In addition, the energy-integrated angular distribution T(Θ) is consistent with the predictions of the early statistical complex decay model of Miller and Herschbach for fragmentation from a transition state that is a prolate top. In sharp contrast, P(E) for the CoC4H8++H2 products exhibits a substantial hot, nonstatistical tail towards high energy. Perhaps the H2 channel has a late potential energy barrier some 0.5 eV above products, but we view this explanation as highly unlikely. Instead, we suggest that the potential energy from an earlier multicenter transition state is funneled efficiently, and highly nonstatistically, into product translation. This surprising conclusion may apply to H2 products for the entire family of reactions of the late-3D series transition metal cations Fe+, Co+, and Ni+ with alkanes.

  13. Surface analytical investigations of the thermal behaviour of passivated Zircaloy-4 surfaces and of the reaction behaviour of iodine with Zircaloy-4 surfaces

    International Nuclear Information System (INIS)

    Kaufmann, R.

    1988-07-01

    In the first part of the present work the thermal behaviour of atmospherically oxidized Zircaloy-4 samples was investigated at various temperatures. In a next step the amount of iodine adsorbed at the metallic surface was determined as well at room temperature with varying iodine exposures as for constant exposure but varying temperatures. Furthermore, the zirconium iodide species resulting from the interaction of iodine with the Zircaloy-4 and desorbed at higher temperatures were identified by means of residual gas analysis. During these studies it was found that the oxidic overlayer of the passivated Zircaloy-4 samples is decomposed at temperatures above 200 0 C. The iodine uptake at metallic surfaces (cleaned by Ar-ion sputtering) at room temperature slows markedly down after formation of a closed zirconium-iodide overlayer and consequently the further reaction proceeds diffusion-controlled. At 200 0 C ZrI 4 is formed being the thermodynamically most stable Zr-iodide. During desorption experiments using iodine exposed Zircaloy-4 samples the release of ZrI 4 was proved. The results obtained from the various experiments are finally discussed with respect to the iodine-induced stress corrosion cracking process and the underlying basic mechanisms and a transport mechanism for the SCC in nuclear fuel rods is proposed. (orig./RB) [de

  14. Crystal structure of an EAL domain in complex with reaction product 5'-pGpG.

    Directory of Open Access Journals (Sweden)

    Julien Robert-Paganin

    Full Text Available FimX is a large multidomain protein containing an EAL domain and involved in twitching motility in Pseudomonas aeruginosa. We present here two crystallographic structures of the EAL domain of FimX (residues 438-686: one of the apo form and the other of a complex with 5'-pGpG, the reaction product of the hydrolysis of c-di-GMP. In both crystal forms, the EAL domains form a dimer delimiting a large cavity encompassing the catalytic pockets. The ligand is trapped in this cavity by its sugar phosphate moiety. We confirmed by NMR that the guanine bases are not involved in the interaction in solution. We solved here the first structure of an EAL domain bound to the reaction product 5'-pGpG. Though isolated FimX EAL domain has a very low catalytic activity, which would not be significant compared to other catalytic EAL domains, the structure with the product of the reaction can provides some hints in the mechanism of hydrolysis of the c-di-GMP by EAL domains.

  15. Crystal structure of an EAL domain in complex with reaction product 5'-pGpG.

    Science.gov (United States)

    Robert-Paganin, Julien; Nonin-Lecomte, Sylvie; Réty, Stéphane

    2012-01-01

    FimX is a large multidomain protein containing an EAL domain and involved in twitching motility in Pseudomonas aeruginosa. We present here two crystallographic structures of the EAL domain of FimX (residues 438-686): one of the apo form and the other of a complex with 5'-pGpG, the reaction product of the hydrolysis of c-di-GMP. In both crystal forms, the EAL domains form a dimer delimiting a large cavity encompassing the catalytic pockets. The ligand is trapped in this cavity by its sugar phosphate moiety. We confirmed by NMR that the guanine bases are not involved in the interaction in solution. We solved here the first structure of an EAL domain bound to the reaction product 5'-pGpG. Though isolated FimX EAL domain has a very low catalytic activity, which would not be significant compared to other catalytic EAL domains, the structure with the product of the reaction can provides some hints in the mechanism of hydrolysis of the c-di-GMP by EAL domains.

  16. Effects of extrusion, infrared and microwave processing on Maillard reaction products and phenolic compounds in soybean.

    Science.gov (United States)

    Zilić, Slađana; Mogol, Burçe Ataç; Akıllıoğlu, Gül; Serpen, Arda; Delić, Nenad; Gökmen, Vural

    2014-01-15

    The Maillard reaction indicators furosine, hydroxymethylfurfural (HMF), acrylamide and color were determined to evaluate heat effects induced during extrusion, infrared and microwave heating of soybean. In addition, the present paper aimed to study changes in the phenolic compounds, as well as in the overall antioxidant properties of different soybean products in relation to heating at 45-140 °C during the processes. Soybean proteins were highly sensible to Maillard reaction and furosine was rapidly formed under slight heating conditions during extrusion and infrared heating. Microwave heating at lower temperatures for a longer time yielded lower acrylamide levels in the final soybean products, as a result of its partial degradation. However, during infrared heating, acrylamide formation greatly increased with decreasing moisture content. After a short time of extrusion and infrared heating at 140 °C and microwave heating at 135 °C for 5 min, concentrations of HMF increased to 11.34, 26.21 and 34.97 µg g(-1), respectively. The heating conditions caused formation of acrylamide, HMF and furosine in high concentration. The results indicate that the complex structure of soybeans provides protection of phenolic compounds from thermal degradation, and that Maillard reaction products improved the antioxidant properties of heat-treated soybean. © 2013 Society of Chemical Industry.

  17. Polymerase-endonuclease amplification reaction (PEAR for large-scale enzymatic production of antisense oligonucleotides.

    Directory of Open Access Journals (Sweden)

    Xiaolong Wang

    Full Text Available Antisense oligonucleotides targeting microRNAs or their mRNA targets prove to be powerful tools for molecular biology research and may eventually emerge as new therapeutic agents. Synthetic oligonucleotides are often contaminated with highly homologous failure sequences. Synthesis of a certain oligonucleotide is difficult to scale up because it requires expensive equipment, hazardous chemicals and a tedious purification process. Here we report a novel thermocyclic reaction, polymerase-endonuclease amplification reaction (PEAR, for the amplification of oligonucleotides. A target oligonucleotide and a tandem repeated antisense probe are subjected to repeated cycles of denaturing, annealing, elongation and cleaving, in which thermostable DNA polymerase elongation and strand slipping generate duplex tandem repeats, and thermostable endonuclease (PspGI cleavage releases monomeric duplex oligonucleotides. Each round of PEAR achieves over 100-fold amplification. The product can be used in one more round of PEAR directly, and the process can be further repeated. In addition to avoiding dangerous materials and improved product purity, this reaction is easy to scale up and amenable to full automation. PEAR has the potential to be a useful tool for large-scale production of antisense oligonucleotide drugs.

  18. Mass resolved angular distribution of fission products in 20Ne + 232Th reaction

    International Nuclear Information System (INIS)

    Tripathi, R.; Sodaye, S.; Sudarshan, K.; Kumar, Amit; Guin, R.

    2011-01-01

    Mass resolved angular distribution of fission products was measured in 20 Ne + 232 Th reaction at beam energy of 120 MeV. A preliminary analysis of the angular distribution data of fission products shows higher average anisotropy compared to that calculated using statistical theory. A signature of rise in anisotropy near symmetry, as reported in earlier studies in literature, is also seen. Further study is in progress to get more detailed information about the contribution from non-compound nucleus fission and dependence of angular anisotropy on asymmetry of mass division

  19. The direct oxidative diene cyclization and related reactions in natural product synthesis

    Directory of Open Access Journals (Sweden)

    Juliane Adrian

    2016-09-01

    Full Text Available The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (diastereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

  20. Estimate of production of medical isotopes by photo-neutron reaction at the Canadian Light Source

    Science.gov (United States)

    Szpunar, B.; Rangacharyulu, C.; Daté, S.; Ejiri, H.

    2013-11-01

    In contrast to conventional bremsstrahlung photon beam sources, laser backscatter photon sources at electron synchrotrons provide the capability to selectively tune photons to energies of interest. This feature, coupled with the ubiquitous giant dipole resonance excitations of atomic nuclei, promises a fertile method of nuclear isotope production. In this article, we present the results of simulations of production of the medical/industrial isotopes 196Au, 192Ir and 99Mo by (γ,n) reactions. We employ FLUKA Monte Carlo code along with the simulated photon flux for a beamline at the Canadian Light Source in conjunction with a CO2 laser system.

  1. Product inhibition of enzymatic hydrolysis of cellulose: are we running the reactions all wrong?

    DEFF Research Database (Denmark)

    Meyer, Anne S.

    2012-01-01

    cellobiose and glucose. The reported KI for glucose on the T. reesei cellulases and -glucosidase varies from 0.04 to 5 g/L. The type of inhibition is debated, and probably varies for different -glucosidases, but with a required goal of sufficient glucose concentration to support ethanol concentrations....... This is because the currently used Trichoderma reesei derived cellulases, i.e. exoglucanases (mainly the cellobiohydrolases Cel7A and Cel6A), endo-1,4--glucanases, and now boosted with -glucosidase and other enzymes, now considered the “industry standard” enzymes, are significantly inhibited by the products...... of minimum ∼5–6% v/v, the glucose product concentrations exceed the critical limit for product inhibition. Hence, regardless of the recent progress in enzyme development for cellulose hydrolysis, the glucose product inhibition remains an issue, which is exacerbated as the reaction progresses, especially...

  2. Solvent-resistant nanofiltration for product purification and catalyst recovery in click chemistry reactions.

    Science.gov (United States)

    Cano-Odena, Angels; Vandezande, Pieter; Fournier, David; Van Camp, Wim; Du Prez, Filip E; Vankelecom, Ivo F J

    2010-01-18

    The quickly developing field of "click" chemistry would undoubtedly benefit from the availability of an easy and efficient technology for product purification to reduce the potential health risks associated with the presence of copper in the final product. Therefore, solvent-resistant nanofiltration (SRNF) membranes have been developed to selectively separate "clicked" polymers from the copper catalyst and solvent. By using these solvent-stable cross-linked polyimide membranes in diafiltration, up to 98 % of the initially present copper could be removed through the membrane together with the DMF solvent, the polymer product being almost completely retained. This paper also presents the first SRNF application in which the catalyst permeates through the membrane and the reaction product is retained.

  3. Hydrogenation/Deoxygenation (H/D Reaction of Furfural-Acetone Condensation Product using Ni/Al2O3-ZrO2 Catalyst

    Directory of Open Access Journals (Sweden)

    Adam Mahfud

    2016-08-01

    Full Text Available The catalytic hydrogenation/deoxygenation (H/D reaction was carried out using Ni/Al2O3-ZrO2 catalyst. The 10% (wt/wt of Ni were impregnated on Al2O3-ZrO2 (10NiAZ by wet impregnation method followed by calcination and reduction. X-Ray diffraction analysis showed that Nideposited on the surface, with specific surface areas (SBET was 48.616 m2/g. Catalyst performance were evaluated for H/D reaction over furfural-acetone condensation products, mixture of 2-(4-furyl-3-buten-2-on and 1,5-bis-(furan-2-yl-pentan-3-one. The reaction was carried out in a batch, performed at 150°C for 8 hours. The H/D reaction gave alkane derivatives C8 and C10 by hydrogenation process followed by ring opening of furan in 15.2% yield. While, oxygenated product C10-C13 were also detected in 17.2% yield. The increasing of pore volume of 10NiAZ might enhance catalyst activity over H/D reaction. The alkene C=C bond was easy to hydrogenated under this condition by the lower bond energy gap.

  4. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities.

    Science.gov (United States)

    Van Wyngarden, A L; Pérez-Montaño, S; Bui, J V H; Li, E S W; Nelson, T E; Ha, K T; Leong, L; Iraci, L T

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H 2 SO 4 ) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1 H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal

  5. Gas-Solid Reaction Route toward the Production of Intermetallics from Their Corresponding Oxide Mixtures

    Directory of Open Access Journals (Sweden)

    Hesham Ahmed

    2016-08-01

    Full Text Available Near-net shape forming of metallic components from metallic powders produced in situ from reduction of corresponding pure metal oxides has not been explored to a large extent. Such a process can be probably termed in short as the “Reduction-Sintering” process. This methodology can be especially effective in producing components containing refractory metals. Additionally, in situ production of metallic powder from complex oxides containing more than one metallic element may result in in situ alloying during reduction, possibly at lower temperatures. With this motivation, in situ reduction of complex oxides mixtures containing more than one metallic element has been investigated intensively over a period of years in the department of materials science, KTH, Sweden. This review highlights the most important features of that investigation. The investigation includes not only synthesis of intermetallics and refractory metals using the gas solid reaction route but also study the reaction kinetics and mechanism. Environmentally friendly gases like H2, CH4 and N2 were used for simultaneous reduction, carburization and nitridation, respectively. Different techniques have been utilized. A thermogravimetric analyzer was used to accurately control the process conditions and obtain reaction kinetics. The fluidized bed technique has been utilized to study the possibility of bulk production of intermetallics compared to milligrams in TGA. Carburization and nitridation of nascent formed intermetallics were successfully carried out. A novel method based on material thermal property was explored to track the reaction progress and estimate the reaction kinetics. This method implies the dynamic measure of thermal diffusivity using laser flash method. These efforts end up with a successful preparation of nanograined intermetallics like Fe-Mo and Ni-W. In addition, it ends up with simultaneous reduction and synthesis of Ni-WN and Ni-WC from their oxide mixtures

  6. Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

    Science.gov (United States)

    Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

    2018-05-22

    Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

  7. Extensive validation of CM SAF surface radiation products over Europe.

    Science.gov (United States)

    Urraca, Ruben; Gracia-Amillo, Ana M; Koubli, Elena; Huld, Thomas; Trentmann, Jörg; Riihelä, Aku; Lindfors, Anders V; Palmer, Diane; Gottschalg, Ralph; Antonanzas-Torres, Fernando

    2017-09-15

    This work presents a validation of three satellite-based radiation products over an extensive network of 313 pyranometers across Europe, from 2005 to 2015. The products used have been developed by the Satellite Application Facility on Climate Monitoring (CM SAF) and are one geostationary climate dataset (SARAH-JRC), one polar-orbiting climate dataset (CLARA-A2) and one geostationary operational product. Further, the ERA-Interim reanalysis is also included in the comparison. The main objective is to determine the quality level of the daily means of CM SAF datasets, identifying their limitations, as well as analyzing the different factors that can interfere in the adequate validation of the products. The quality of the pyranometer was the most critical source of uncertainty identified. In this respect, the use of records from Second Class pyranometers and silicon-based photodiodes increased the absolute error and the bias, as well as the dispersion of both metrics, preventing an adequate validation of the daily means. The best spatial estimates for the three datasets were obtained in Central Europe with a Mean Absolute Deviation (MAD) within 8-13 W/m 2 , whereas the MAD always increased at high-latitudes, snow-covered surfaces, high mountain ranges and coastal areas. Overall, the SARAH-JRC's accuracy was demonstrated over a dense network of stations making it the most consistent dataset for climate monitoring applications. The operational dataset was comparable to SARAH-JRC in Central Europe, but lacked of the temporal stability of climate datasets, while CLARA-A2 did not achieve the same level of accuracy despite predictions obtained showed high uniformity with a small negative bias. The ERA-Interim reanalysis shows the by-far largest deviations from the surface reference measurements.

  8. PRODUCTION OF MEDIUM-CHAIN ACYLGLYCEROLS BY LIPASE ESTERIFICATION IN PACKED BED REACTOR: PROCESS OPTIMIZATION BY RESPONSE SURFACE METHODOLOGY

    Directory of Open Access Journals (Sweden)

    ZANARIAH MOHD DOM

    2014-06-01

    Full Text Available Medium-chain acylglycerols (or glycerides are formed of mono-, di- and triacylglycerol classes. In this study, an alternative method to produce MCA from esterifying palm oil fatty acid distillate (PFAD with the presence of oil palm mesocarp lipase (OPML which is a plant-sourced lipase and PFAD is also cheap by-product is developed in a packed bed reactor. The production of medium-chain acylglycerols (MCA by lipase-catalysed esterification of palm oil fatty acid distillate with glycerol are optimize in order to determine the factors that have significant effects on the reaction condition and high yield of MCA. Response surface methodology (RSM was applied to optimize the reaction conditions. The reaction conditions, namely, the reaction time (30-240 min, enzyme load (0.5-1.5 kg, silica gel load (0.2-1.0 kg, and solvent amount (200-600 vol/wt. Reaction time, enzyme loading and solvent amount strongly effect MCA synthesis (p0.05 influence on MCA yield. Best-fitting models were successfully established for MCA yield (R 2 =0.9133. The optimum MCA yield were 75% from the predicted value and 75.4% from the experimental data for 6 kg enzyme loading, a reaction time of 135min and a solvent amount of 350 vol/wt at 65ºC reaction temperature. Verification of experimental results under optimized reaction conditions were conducted, and the results agreed well with the predicted range. Esterification products (mono-, di- and triacylglycerol from the PBR were identified using Thin Layer Chromatography method. The chromatograms showed the successful fractionation of esterified products in this alternative method of process esterification.

  9. Final Report: Molecular Basis for Microbial Adhesion and Geochemical Surface Reactions: A Study Across Scales

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-06-27

    Computational chemistry was used to help provide a molecular level description of the interactions of Gram-negative microbial membranes with subsurface materials. The goal is to develop a better understanding of the molecular processes involved in microbial metal binding, microbial attachment to mineral surfaces, and, eventually, oxidation/reduction reactions (electron transfer) that can occur at these surfaces and are mediated by the bacterial exterior surface. The project focused on the interaction of the outer microbial membrane, which is dominated by an exterior lipopolysaccharide (LPS) portion, of Pseudomonas aeruginosa with the mineral goethite and with solvated ions in the environment. This was originally a collaborative project with T.P. Straatsma and B. Lowery of the Pacific Northwest National Laboratory. The University of Alabama effort used electronic structure calculations to predict the molecular behavior of ions in solution and the behavior of the sugars which form a critical part of the LPS. The interactions of the sugars with metal ions are expected to dominate much of the microscopic structure and transport phenomena in the LPS. This work, in combination with the molecular dynamics simulations of Straatsma and the experimental electrochemistry and microscopy measurements of Lowry, both at PNNL, is providing new insights into the detailed molecular behavior of these membranes in geochemical environments. The effort at The University of Alabama has three components: solvation energies and structures of ions in solution, prediction of the acidity of the critical groups in the sugars in the LPS, and binding of metal ions to the sugar anions. An important aspect of the structure of the LPS membrane as well as ion transport in the LPS is the ability of the sugar side groups such as the carboxylic acids and the phosphates to bind positively charged ions. We are studying the acidity of the acidic side groups in order to better understand the ability of

  10. Mechanisms and energetics of surface reactions at the copper-water interface. A critical literature review with implications for the debate on corrosion of copper in anoxic water

    Energy Technology Data Exchange (ETDEWEB)

    Johansson, Adam Johannes; Brinck, Tore [Applied Physical Chemistry, KTH Royal Inst. of Technology, Stockholm (Sweden)

    2012-06-15

    In order to make a critical analysis of the discussion of corrosion of copper in pure anoxic water it is necessary to understand the chemical reactivity at the copper-water interface. Even though the most fundamental issue, i.e. the nature and existence of a hypothetical product that is thermodynamically stable, is still under debate, it is clear that if anoxic corrosion really exists, it must be initiated through oxidative surface reactions at the copper-water interface. This report presents a survey of the peer reviewed literature on the reactivity of copper surfaces in water. Reactions discussed involve molecular adsorption of water, dissociation of the OH-bonds in adsorbed water molecules and hydroxyl groups, the disproportionation/synproportionation equilibrium between hydroxyl groups/hydroxide ions, water molecules and atomic oxygen, the surface diffusion of adsorbed species, and the formation of hydrogen gas (molecular hydrogen). Experimental, as well as theoretical (quantum chemical) studies are reviewed. It is concluded that a limited amount of hydrogen gas (H{sub 2}) should be formed as the result of dissociative water adsorption at certain copper surfaces. Quantitative estimates of the amounts of H2 that could form at the copper-water interface are made. Assuming that the water-cleavage/hydrogen-formation reaction proceeds on an ideal [110] or [100] surface until a hydroxyl monolayer (ML) is reached, the amount of H{sub 2} formed is {approx} 2.4 ng cm{sup -2} copper surface. Based on the literature cited, this is most likely possible, thermodynamically as well as kinetically. Although not proven, it is not unlikely that the reaction can proceed until an oxide ML is formed, which would give 4.8 ng cm{sup -2}. If the formation of an oxide ML is thermodynamically feasible the surface will probably react further, since Cu{sub 2}O(s) is known to activate and cleave the water molecule when it adsorbs at the Cu{sub 2}O(s) surface. Assuming the formation of a

  11. Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O((3)P) + Ethylene Reaction at High Collision Energy.

    Science.gov (United States)

    Balucani, Nadia; Leonori, Francesca; Casavecchia, Piergiorgio; Fu, Bina; Bowman, Joel M

    2015-12-17

    The combustion relevant O((3)P) + C2H4 reaction stands out as a prototypical multichannel nonadiabatic reaction involving both triplet and singlet potential energy surfaces (PESs), which are strongly coupled. Crossed molecular beam (CMB) scattering experiments with universal soft electron ionization mass spectrometric detection have been used to characterize the dynamics of this reaction at the relatively high collision energy Ec of 13.7 kcal/mol, attained by crossing the reactant beams at an angle of 135°. This work is a full report of the data at the highest Ec investigated for this reaction. From laboratory product angular and velocity distribution measurements, angular and translational energy distributions in the center-of-mass system have been obtained for the five observed exothermic competing reaction channels leading to H + CH2CHO, H + CH3CO, CH3 + HCO, CH2 + H2CO, and H2 + CH2CO. The product branching ratios (BRs) have been derived. The elucidation of the reaction dynamics is assisted by synergic full-dimensional quasiclassical trajectory surface-hopping calculations of the reactive differential cross sections on coupled ab initio triplet/singlet PESs. This joint experimental/theoretical study extends and complements our previous combined CMB and theoretical work at the lower collision energy of 8.4 kcal/mol. The theoretically derived BRs and extent of intersystem crossing (ISC) are compared with experimental results. In particular, the predictions of the QCT results for the three main channels (those leading to vinoxy + H, methyl + HCO and methylene + H2CO formation) are compared directly with the experimental data in the laboratory frame. Good overall agreement is noted between theory and experiment, although some small, yet significant shortcomings of the theoretical differential cross section are noted. Both experiment and theory find almost an equal contribution from the triplet and singlet surfaces to the reaction, with a clear tendency of the

  12. Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

    Science.gov (United States)

    DeGregorio, Nicole; Iyengar, Srinivasan S

    2018-01-09

    We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

  13. Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling

    International Nuclear Information System (INIS)

    Schaefer, C.; Jansen, A. P. J.

    2013-01-01

    We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

  14. Response Surface Methodology for Biodiesel Production Using Calcium Methoxide Catalyst Assisted with Tetrahydrofuran as Cosolvent

    Directory of Open Access Journals (Sweden)

    Nichaonn Chumuang

    2017-01-01

    Full Text Available The present study was performed to optimize a heterogeneous calcium methoxide (Ca(OCH32 catalyzed transesterification process assisted with tetrahydrofuran (THF as a cosolvent for biodiesel production from waste cooking oil. Response surface methodology (RSM with a 5-level-4-factor central composite design was applied to investigate the effect of experimental factors on the percentage of fatty acid methyl ester (FAME conversion. A quadratic model with an analysis of variance obtained from the RSM is suggested for the prediction of FAME conversion and reveals that 99.43% of the observed variation is explained by the model. The optimum conditions obtained from the RSM were 2.83 wt% of catalyst concentration, 11.6 : 1 methanol-to-oil molar ratio, 100.14 min of reaction time, and 8.65% v/v of THF in methanol concentration. Under these conditions, the properties of the produced biodiesel satisfied the standard requirement. THF as cosolvent successfully decreased the catalyst concentration, methanol-to-oil molar ratio, and reaction time when compared with biodiesel production without cosolvent. The results are encouraging for the application of Ca(OCH32 assisted with THF as a cosolvent for environmentally friendly and sustainable biodiesel production.

  15. Production of isomers in compound and transfer reactions with 4He ions

    International Nuclear Information System (INIS)

    Karamyan, S.A.; Aksenov, N.V.; Albin, Yu.A.; Bozhikov, G.A.; Dmitriev, S.N.; Starodub, G.Ya.; Vostokin, G.K.; Carroll, J.J.

    2011-01-01

    A well-known island of nuclear isomerism appears near A = 175-180 due to the deformation alignment of single-particle orbits at high angular momentum. This sometimes results in the formation of multi-quasiparticle states with record spin that are long-lived because of 'K-hindrance', i.e., symmetry rearrangement. Production methods and spectroscopic studies of these isomers remain a challenge for modern nuclear reaction and nuclear structure physics. Activities were produced by irradiation of 176 Yb(97.6%) enriched and nat Lu targets with 35-MeV 4 He ions from the internal beam of the U200 cyclotron. Induced activities were analyzed applying methods of radiochemistry and gamma spectroscopy. Yields of compound and nucleon-transfer reactions were measured and the isomer-to-ground state ratios were deduced. Calculated results were obtained using standard procedures to reproduce the (α, xn) cross sections, and the systematic behavior of the nucleon-transfer yields was established. The isomer-to-ground state ratios for direct reactions with 4 He ions were examined, resulting in a new characterization of the reaction mechanism

  16. Deuteron-induced reactions generated by intense lasers for PET isotope production

    Science.gov (United States)

    Kimura, Sachie; Bonasera, Aldo

    2011-05-01

    We investigate the feasibility of using laser accelerated protons/deuterons for positron emission tomography (PET) isotope production by means of the nuclear reactions 11B(p, n) 11C and 10B(d, n) 11C. The second reaction has a positive Q-value and no energy threshold. One can, therefore, make use of the lower energy part of the laser-generated deuterons, which includes the majority of the accelerated deuterons. By assuming that the deuteron spectra are similar to the proton spectra, the 11C produced from the reaction 10B(d, n) 11C is estimated to be 7.4×10 9 per laser-shot at the Titan laser at Lawrence Livermore National Laboratory. Meanwhile a high-repetition table-top laser irradiation is estimated to generate 3.5×10 711C per shot from the same reaction. In terms of the 11C activity, it is about 2×10 4 Bq per shot. If this laser delivers kHz, the activity is integrated to 1 GBq after 3 min. The number is sufficient for the practical application in medical imaging for PET.

  17. Structural Analysis of Substrate, Reaction Intermediate, and Product Binding in Haemophilus influenzae Biotin Carboxylase

    Science.gov (United States)

    Broussard, Tyler C.; Pakhomova, Svetlana; Neau, David B.; Bonnot, Ross; Waldrop, Grover L.

    2015-01-01

    Acetyl-CoA carboxylase catalyzes the first and regulated step in fatty acid synthesis. In most Gram-negative and Gram-positive bacteria, the enzyme is composed of three proteins: biotin carboxylase, a biotin carboxyl carrier protein (BCCP), and carboxyltransferase. The reaction mechanism involves two half-reactions with biotin carboxylase catalyzing the ATP-dependent carboxylation of biotin-BCCP in the first reaction. In the second reaction, carboxyltransferase catalyzes the transfer of the carboxyl group from biotin-BCCP to acetyl-CoA to form malonyl-CoA. In this report, high-resolution crystal structures of biotin carboxylase from Haemophilus influenzae were determined with bicarbonate, the ATP analogue AMPPCP; the carboxyphosphate intermediate analogues, phosphonoacetamide and phosphonoformate; the products ADP and phosphate; and the carboxybiotin analogue N1′-methoxycarbonyl biotin methyl ester. The structures have a common theme in that bicarbonate, phosphate, and the methyl ester of the carboxyl group of N1′-methoxycarbonyl biotin methyl ester all bound in the same pocket in the active site of biotin carboxylase and as such utilize the same set of amino acids for binding. This finding suggests a catalytic mechanism for biotin carboxylase in which the binding pocket that binds tetrahedral phosphate also accommodates and stabilizes a tetrahedral dianionic transition state resulting from direct transfer of CO2 from the carboxyphosphate intermediate to biotin. PMID:26020841

  18. Unique Pattern of Protein-Bound Maillard Reaction Products in Manuka (Leptospermum scoparium) Honey.

    Science.gov (United States)

    Hellwig, Michael; Rückriemen, Jana; Sandner, Daniel; Henle, Thomas

    2017-05-03

    As a unique feature, honey from the New Zealand manuka tree (Leptospermum scoparium) contains substantial amounts of dihydroxyacetone (DHA) and methylglyoxal (MGO). Although MGO is a reactive intermediate in the Maillard reaction, very little is known about reactions of MGO with honey proteins. We hypothesized that the abundance of MGO should result in a particular pattern of protein-bound Maillard reaction products (MRPs) in manuka honey. A protein-rich high-molecular-weight fraction was isolated from 12 manuka and 8 non-manuka honeys and hydrolyzed enzymatically. By HPLC-MS/MS, 8 MRPs, namely, N-ε-fructosyllysine, N-ε-maltulosyllysine, carboxymethyllysine, carboxyethyllysine (CEL), pyrraline, formyline, maltosine, and methylglyoxal-derived hydroimidazolone 1 (MG-H1), were quantitated. Compared to non-manuka honeys, the manuka honeys were characterized by high concentrations of CEL and MG-H1, whereas the formation of N-ε-fructosyllysine was suppressed, indicating concurrence reactions of glucose and MGO at the ε-amino group of protein-bound lysine. Up to 31% of the lysine and 8% of the arginine residues, respectively, in the manuka honey protein can be modified to CEL and MG-H1, respectively. CEL and MG-H1 concentrations correlated strongly with the MGO concentration of the honeys. Manuka honey possesses a special pattern of protein-bound MRPs, which might be used to prove the reliability of labeled MGO levels in honeys and possibly enable the detection of fraudulent MGO or DHA addition to honey.

  19. Reactions of clofibric acid with oxidative and reductive radicals—Products, mechanisms, efficiency and toxic effects

    International Nuclear Information System (INIS)

    Csay, Tamás; Rácz, Gergely; Salik, Ádám; Takács, Erzsébet; Wojnárovits, László

    2014-01-01

    The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O 2 −∙ /HO 2 ∙ reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O 2 −∙ /HO 2 ∙ . Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC–MS method was developed based on 18 O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid. - Highlights: • Clofibric acid is effectively degraded by OH radical. • Main primary and secondary products are hydroxylated and dihydroxylated phenyl type derivatives of clofibric acid. • In air saturated aqueous solutions O 2 plays an important role in decomposition of the aromatic structure. • A new LC–MS method with 18 O-labeling was developed. • Early stage reaction products are more toxic to bacteria Vibrio fischeri than clofibric acid

  20. Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions

    Science.gov (United States)

    Omae, Iwao

    2016-01-01

    In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO2 and H2, and hydrogen production from the formic acid. This formic acid can be a useful agent for H2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g., dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO2. 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N,N-dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds. PMID:28503084