Reactivity of the functional groups in functional polymers. Use of T-for-H exchange reaction

International Nuclear Information System (INIS)

Imaizumi, Hiroshi; Hasegawa, Shinobu.

1997-01-01

In order to reveal the reactivity of several functional polymers, the following two experiments were carried out: observing the hydrogen-isotope exchange reaction (T-for-H exchange reaction) between one of T-labeled functional polymers and 0.500 mol·l -1 aniline dissolved in p-xylene, observing the degree of the T dispersed from the surface area of the polymer under the several conditions. Consequently, the following six matters have been quantitatively obtained. The T-for-H exchange reaction occurred between each T-labeled polymer and aniline, and is more predominant than other chemical reactions within the range of 50-90degC. The reactivity of the polymers are strongly affected by their matrix structures. The degree of the T dispersed from the surface area of each T-labeled polymer is hardly affected by humidity. The higher the temperature is, the larger is the degree of the T dispersed from the surface area. At the same temperature, the degree of the T dispersed from the surface area of each polymer is strongly affected by the physical form of the polymer even if the polymer has the same functional group as the others, and the T existing in the surface area of a T-labeled glassy polymer is less dispersed than that of a porous one. The degree of the T dispersed from the surface area of a T-labeled polymer is small when the degree of the polymerization of the polymer is high. (author)

Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

KAUST Repository

Hong, Jongsup

2013-10-01

The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

KAUST Repository

Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

2013-01-01

The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

International Nuclear Information System (INIS)

Sato, S.

1987-01-01

Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

Electron exchange reaction in anion exchangers as observed in uranium isotope separation

International Nuclear Information System (INIS)

Obanawa, Heiichiro; Takeda, Kunihiko; Seko, Maomi

1991-01-01

The mechanism of electron exchange in an ion exchanger, as occurring between U 4+ and UO 2 2+ in uranium isotope separation, was investigated. The height of the separation unit (H q ) in the presence of metal ion catalysts, as obtained from the separation experiments, was found to be almost coincident with the theoretical value of H q as calculated on the basis of the intrasolution acceleration mechanism of the metal ion, suggesting that the electron exchange mechanism in the ion-exchanger is essentially the same as that in the solution when metal ion catalysts are present. Separation experiments with no metal ion catalyst, on the other hand, showed the electron exchange reaction in the ion exchanger to be substantially higher than that in the solution, suggesting an acceleration of the electron exchange reaction by the ion-exchanger which is due to the close existence of higher order Cl - complexes of UO 2 2+ and U 4+ in the vicinity of the ion-exchange group. (author)

Gaseous exchange reaction of deuterium between hydrogen and water on hydrophobic catalyst supporting platinum

International Nuclear Information System (INIS)

Izawa, Hirozumi; Isomura, Shohei; Nakane, Ryohei.

1979-01-01

The deuterium exchange reaction between hydrogen and water in the gas phase where the fed hydrogen gas is saturated with water vapor is studied experimentally by use of the proper hydrophobic catalysts supporting platinum. It is found that the activities of those catalysts for this reaction system are very high compared with the other known ones for the systems in which gas and liquid should coexist on catalyst surfaces, and that the apparent catalytic activity becomes larger as the amount of platinum supported on a catalyst particle increases. By analyses of the data the following informations are obtained. The exchange reaction can be expressed by a first order reversible reaction kinetics. The pore diffusion in the catalyst particles has significant effect on the overall reaction mechanisms. (author)

Study of isotopic exchange reactions of azidothymidine with tritium

International Nuclear Information System (INIS)

Sidorov, G.V.; Zverkov, Yu.B.; Myasoedov, N.F.

2003-01-01

Different reactions of isotopic exchange of azidothymidine (3 - azido-3 - desoxythymidine) with tritium, such as solid- and liquid-phase catalytic isotopic exchange with gaseous tritium and isotopic exchange in solution with tritium water, are investigated. It is determined that catalytic reactions of azidothymidine with gaseous tritium in solution lead to practically full reduction of azido group up to amino group. In reactions of solid-phase catalytic hydrogenation this process takes place too and 3 - azido-3 - desoxythymidine yield is from 20 to 70 %. Molar radioactivity of labelled with tritium azidothymidine prepared in reactions of solid-phase catalytic isotopic exchange with gaseous tritium and so by isotopic exchange in solution with tritium water does not exceed 0.5 Cu/mmol [ru

Isotope exchange reactions on ceramic breeder materials and their effect on tritium inventory

Energy Technology Data Exchange (ETDEWEB)

Nishikawa, M; Baba, A [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Kawamura, Y; Nishi, M

1998-03-01

Though lithium ceramic materials such as Li{sub 2}O, LiAlO{sub 2}, Li{sub 2}ZrO{sub 3}, Li{sub 2}TiO{sub 3} and Li{sub 4}SiO{sub 4} are considered as breeding materials in the blanket of a D-T fusion reactor, the release behavior of the bred tritium in these solid breeder materials has not been fully understood. The isotope exchange reaction rate between hydrogen isotopes in the purge gas and tritium on the surface of breeding materials have not been quantified yet, although helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas in the recent blanket designs. The mass transfer coefficient representing the isotope exchange reaction between H{sub 2} and D{sub 2}O or that between D{sub 2} and H{sub 2}O in the ceramic breeding materials bed is experimentally obtained in this study. Effects of isotope exchange reactions on the tritium inventory in the bleeding blanket is discussed based on data obtained in this study where effects of diffusion of tritium in the grain, absorption of water in the bulk of grain, and adsorption of water on the surface of grain, together with two types of isotope exchange reactions are considered. The way to estimate the tritium inventory in a Li{sub 2}ZrO{sub 3} blanket used in this study shows a good agreement with data obtained in such in-situ experiments as MOZART, EXOTIC-5, 6 and TRINE experiments. (author)

Development of styrene divinyl benzene catalyst in isotopic exchange reaction of water and hydrogen

International Nuclear Information System (INIS)

Morishita, Teizo; Noda, Shigeyuki; Tan, Tsutomu; Noguchi, Hiroshi

1982-01-01

Styrene divinyl benzene copolymer (SDBC) is hydrophobic, and porous with large specific surface area. Utilizing these properties, the SDBC was used for the carrier of catalyst in water-hydrogen exchange reaction process, and the hydrophobic platinum catalyst with very high performance was able to be developed. However, the SDBC is usually fine particles smaller than 1 mm, and is not suitable as the filling catalyst for exchange reaction towers. Therefore, in this study, using only platinum as a catalyst metal, the improvement of the property of carriers was emphatically examined, and platinum bearing was proved with an optical or electron microscope. As the result, it was found that the SDBC catalyst showed high activity practically usable as the hydrophobic catalyst for heavy water or tritium exchange reaction. The characteristics of SDBC are explained. The manufacturing processes of the catalyst by making SDBC carriers with fine particles and letting them bear platinum are described. The results of the trial manufacture of spherical, extrusion-formed and honeycomb carrier catalysts are reported. Platinum must be dispersed over the large specific surface area of SDBC carriers. (Kako, I.)

Catalytic process for tritium exchange reaction

International Nuclear Information System (INIS)

Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

2001-01-01

The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

Excitation of giant resonances via charge exchange reactions

International Nuclear Information System (INIS)

Goodman, C.D.

1979-01-01

Charge-exchange reactions can be useful for identifying isovector resonances. At present the most promising use of charge-exchange reactions with respect to giant resonances is to locate and study Gamow-Teller (GT) resonances. Detailed comparisons between GT and M1 strengths can yield further structure information. 7 figures

Comparative study on bromide and iodide ion-isotopic exchange reactions using strongly basic anion exchange resin Duolite A-113

International Nuclear Information System (INIS)

Lokhande, R.S.; Dole, M.H.; Singare, P.U.

2006-01-01

Kinetics of ion-isotopic exchange reaction was studied using industrial grade ion exchange resin Duolite A-113. The radioactive isotopes 131 I and 82 Br were used to trace the ion-isotopic exchange reaction. The experiments were performed in the temperature range of 26.0degC to 43.0degC and the concentration of external ionic solution varying from 0.005 M to 0.100 M. For bromide ion-isotopic exchange reaction, the calculated values of specific reaction rate, initial rate of bromide ion exchange, and amount of bromide ions exchanged were obtained higher than that for iodide ion-isotopic exchange reaction under identical experimental conditions. The observed variation in the results for two ion-isotopic exchange reactions was due to the difference in the ionic size of bromide and iodide ions. (author)

Exchange of deuterium with hydrogen of zeolite catalyst surface

International Nuclear Information System (INIS)

Minachev, Kh.M.; Dmitriev, R.V.; Penchev, V.; Kanazirev, V.; Minchev, Kh.; Kasimov, Ch.K.; Bylgarska Akademiya na Naukite, Sofia. Inst. za Obshta i Organichna Khimiya; AN Azerbajdzhanskoj SSR, Baku. Inst. Neftekhimicheskikh Protsessov)

1981-01-01

Isotope heteromolecular exchange of hydrogen on the reduced nickel-containing zeolites takes places at the temperatures above 100 deg and it is controlled by activated hydrogen transfer from metal particles on the substrate surface. High-temperature redox treatment of nickel-containing zeolites results in the formation of large nickel crystallites on zeolite external faces. The rest part of nickel remains in zeolite pores and conditions a high promoting effect in the exchange reaction. Catalytic activity of reduced zeolites NiCaNaY in toluene disproportionation increases considerably only in the cases when nickel is introduced into zeolite by means of ion exchange. Close spatial location of nickel particles and OH groups promotes the procedure of both isotope exchange and disproportionation of toluene [ru

The reactivity of anion-exchange resins by applying OT-for-OH exchange reaction in the equilibrium state

International Nuclear Information System (INIS)

Kano, Naoki; Nihei, Makoto; Imaizumi, Hiroshi

1996-01-01

In order to reveal the behavior of hydroxyl group in isotope exchange reaction, OT-for-OH exchange reaction between each anion-exchange resin (OH - form) and tritiated water (abbreviated as HTO water below) was observed at 80degC under the equilibrium. Anion-exchange resins used were Amberlite IRA-400, IRA-410 (both strongly basic), and IRA-94S (weakly basic). It can be thought that an HTO molecule dissociates into H + +OT - (or T + +OH - ). The activity of each resin based on OT-for-OH exchange reaction was measured with a liquid scintillation counter. From the above-mentioned, the following five were found. Isotope exchange reaction as 'atomic group' occurred between the OH group in each anion-exchange resin and the OT group in HTO water. The reactivity of strongly basic anion-exchange resin is larger than that of weakly basic one. The ratio of the reactivity of these resins can roughly be expressed as follows: (IRA-410): (IRA-400): (IRA-94S)=42: 7: 1. The degree of OT-for-OH exchange reaction may be smaller than that of T-for-H exchange reaction. The method used and results obtained in this work may be helpful to obtain the data for the prevention of T-contamination, especially to obtain the data from certain atomic groups including T. (author)

Competition between abstraction and exchange channels in H + HCN reaction: Full-dimensional quantum dynamics

Energy Technology Data Exchange (ETDEWEB)

Jiang, Bin; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

2013-12-14

Dynamics of the title reaction is investigated on an ab initio based potential energy surface using a full-dimensional quantum wave packet method within the centrifugal sudden approximation. It is shown that the reaction between H and HCN leads to both the hydrogen exchange and hydrogen abstraction channels. The exchange channel has a lower threshold and larger cross section than the abstraction channel. It also has more oscillations due apparently to quantum resonances. Both channels are affected by long-lived resonances supported by potential wells. Comparison with experimental cross sections indicates underestimation of the abstraction barrier height.

Using reactive artificial muscles to determine water exchange during reactions

International Nuclear Information System (INIS)

Otero, T F; Martínez, J G; Zaifoglu, B

2013-01-01

Artificial muscles based on films of conducting polymers translate film volume variations, driven by electrochemical reactions (Faradaic motors), into macroscopic movements with generation of mechanical energy. The reaction promotes exchange of counterions (anions here) and solvent molecules with the electrolyte. Attributing here both the film volume variation and the movement originated by these exchanges of ions and solvent, the described angles can be used to quantify the exchanged solvent. Different angles described by bending muscles consuming equal driving charges in electrolytes having the same cation and different anions were measured. The number of exchanged counterions is given by the consumed charge and the ion valence: this is a Faradaic reaction. The described angle fraction due to the exchanged anions is given by the number of anions and the crystallographic radius. Taking as reference the anion giving the shorter angle, whatever the consumed charge, the relative number of solvent molecules exchanged by the polymeric membrane during a reversible reaction was determined. Actuators and artificial muscles can be used as useful tools for, at least, an initial study of the solvent exchange during reactions in reactive gels. (paper)

Comparative study on ion-isotopic exchange reaction kinetics by application of tracer technique

International Nuclear Information System (INIS)

Lokhande, R.S.; Singare, P.U.

2007-01-01

The radioactive isotopes 131 I and 82 Br were used to trace the ion-isotopic exchange reactions using industrial grade ion exchange resins Amberlite IRA-400. The experiments were performed to understand the effect of temperature and concentration of ionic solution on kinetics of exchange reactions. Both the exchange reactions were greatly influenced by rise in temperature, which result in higher percentage of ions exchanged. For bromide ion-isotopic exchange reactions, the calculated values of specific reaction rate/min -1 , and amount of ions exchanged/mmol were obtained higher than that for iodide ion-isotopic exchange reactions under identical experimental conditions. The observed variation in the results for two ion-isotopic exchange reactions was due to the difference in the ionic size of bromide and iodide ions. (orig.)

Ion-Isotopic Exchange Reaction Kinetics using Anion Exchange Resins Dowex 550A LC and Indion-930A

Directory of Open Access Journals (Sweden)

P.U. Singare

2014-06-01

Full Text Available The present paper deals with the characterization of ion exchange resins Dowex 550A LC and Indion-930A based on kinetics of ion-isotopic exchange reactions for which the short lived radioactive isotopes 131I and 82Br were used as a tracers. The study was performed for different concentration of ionic solution varying from 0.001 mol/L to 0.004 mol/L and temperature in the range of 30.0 °C to 45.0 °C. The results indicate that as compared to bromide ion-isotopic exchange reaction, iodide exchange reaction take place at the faster rate. For both the ion-isotopic exchange reactions, under identical experimental conditions, the values of specific reaction rate increases with increase in the ionic concentration and decreases with rise in temperature. It was observed that at 35.00C, 1.000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution for iodide ion-isotopic exchange reaction, the values of specific reaction rate (min-1, amount of ion exchanged (mmol, initial rate of ion exchange (mmol/min and log Kd were 0.270, 0.342, 0.092 and 11.8 respectively for Dowex 550A LC resin, which was higher than the respective values of 0.156, 0.241, 0.038 and 7.4 as that obtained for Indion-930A resins. From the results, it appears that Dowex 550A LC resins show superior performance over Indion-930A resins under identical experimental conditions.

Nucleon charge-exchange reactions at intermediate energy

Energy Technology Data Exchange (ETDEWEB)

Alford, W.P. [Western Ontario Univ., London, ON (Canada). Dept. of Physics]|[TRIUMF, Vancouver, BC (Canada); Spicer, B.M. [Melbourne Univ., Parkville, VIC (Australia). School of Physics

1997-12-31

An historical review of the development of ideas pertaining to Gamow-Teller giant resonances is given, and a description of the emergence of techniques for the study of charge exchange reactions - particularly the technical advances which yielded the recent volume of new date. The present status of charge exchange reactions is reviewed and assessed. Evidence is presented from the {sup 14}C(p,n) reaction for the dominance of the spin-isospin component of the nucleon-nucleon interaction in intermediate energy reactions. In (p,n) reactions the Gamow-Teller giant resonance dominates the spectra, with higher multipoles contributing. By contrast, in (n,p) reactions in the heavier nuclei, the Gamow-Teller transitions are substantially Pauli-blocked and the spin dipole resonance dominates, with contributions from higher multipoles. Discussions of the multipole decomposition process, used to obtain from the data the contributions of the different multipoles, and the contributions of the multipoles, are given. 226 refs., 19 figs.

Nucleon charge-exchange reactions at intermediate energy

International Nuclear Information System (INIS)

Alford, W.P.; Spicer, B.M.

1997-01-01

An historical review of the development of ideas pertaining to Gamow-Teller giant resonances is given, and a description of the emergence of techniques for the study of charge exchange reactions - particularly the technical advances which yielded the recent volume of new date. The present status of charge exchange reactions is reviewed and assessed. Evidence is presented from the 14 C(p,n) reaction for the dominance of the spin-isospin component of the nucleon-nucleon interaction in intermediate energy reactions. In (p,n) reactions the Gamow-Teller giant resonance dominates the spectra, with higher multipoles contributing. By contrast, in (n,p) reactions in the heavier nuclei, the Gamow-Teller transitions are substantially Pauli-blocked and the spin dipole resonance dominates, with contributions from higher multipoles. Discussions of the multipole decomposition process, used to obtain from the data the contributions of the different multipoles, and the contributions of the multipoles, are given

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.

Charge-exchange reactions on 36 S

International Nuclear Information System (INIS)

Fifield, L.K.; Catford, W.N.; Orr, N.A.; Ophel, T.R.; Etchegoyen, A.; Etchegoyen, M.C.

1992-11-01

A series of charge-exchange reactions on 36 S targets have been investigated at beam energies ∼7 MeV/A. Pronounced selectivities to different final states in 36 P are observed which depend on the projectile employed. An interpretation of the data in terms of one- and two-step pictures of the reaction mechanism is presented. At least two, and probably all, of the reactions have a significant 1-step contribution to the reaction mechanism at these energies. 22 refs., 5 tabs., 5 figs

Hydrogen/Chlorine exchange reactions of gaseous carbanions.

Science.gov (United States)

Chen, Hao; Cooks, R Graham; Meurer, Eduardo C; Eberlin, Marcos N

2005-12-01

Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.

Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

International Nuclear Information System (INIS)

Xuelei Chu; Ohmoto, Hiroshi

1991-01-01

For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

Isotope exchange reaction in uranous-uranyl-sulphuric acid system

International Nuclear Information System (INIS)

Ling Daren; Yue Tingsheng; Mu Dehai; Wang Yani

1990-01-01

The kinetics of the isotope exchange reaction between U(IV) and U(VI) has been studied in low concentrations of sulphuric acid. A minimum exchange rate appears at 0.25 M H 2 SO 4 . From the rates at different temperatures ranging from 20deg to 35deg C, an apparent activation energy of 86 kcal/mole was calculated. The exchange rate was found to be accelerated by the addition of ferrous ions, and a half-life of less than 1 s, was obtained. Probable mechanisms for the acceleration of the uranium isotope exchange reactions by acidity and ferrous ions are proposed. (orig.)

The dynamics of the Hg + Br2 reaction: elucidation of the reaction mechanism for the Br exchange reaction.

Science.gov (United States)

Jambrina, P G; Menéndez, M; Aoiz, F J

2017-06-28

In spite of its importance in the Hg atmospheric chemistry, the dynamics of the Hg + Br 2 → HgBr + Br reaction is poorly understood. In this article, we have carried out a comprehensive study of the reaction mechanism of this reaction by means of quasiclassical trajectories (QCTs) on an existing ab initio potential energy surface (PES). The reaction has a non trivial dynamics, as a consequence of its large endothermicity, the presence of a deep potential well, and the competition between the Br exchange and the collision induced dissociation processes. Our calculations demonstrate that insertion is only relevant at energies just above the reaction threshold and that, at energies above 2.3 eV, HgBr formation typically takes place via a sort of frustrated dissociation. In order to compare directly with the results obtained in extensive cross molecular beam experiments for the homologous reaction with I 2 , angular distributions in the laboratory frame for Hg + Br 2 have been simulated under similar experimental conditions. The lack of agreement at the highest energies considered suggests that either the two reactions have substantially different mechanisms or that calculations on a single PES cannot account for the dynamics at those energies.

Exchange reaction between tritiated hydrogen and water vapor

International Nuclear Information System (INIS)

Yamada, Koichi; Takano, Kenichi; Watanabe, Tamaki.

1979-01-01

Exchange reaction of tritiated hydrogen to water vapor under the condition of tritium gas concentration between 1 μCi/l and 1 mCi/l was studied. Tritium gas with hydrogen gas of 5 Torr and water of 20 mg were enclosed in a Pyrex glass ampule with volume of about 100 ml. The mixed gas with water vapor was heated with electric furnace. The heating time was between 2 and 100 hr, and the temperature was 776, 725, 675, 621, and 570.5 0 K. After heating, tritiated water was trapped with liquid nitrogen, and counted with a liquid scintillation counter. The radioactive concentration of initial tritiated hydrogen was measured with a calibrated ionization chamber. The main results obtained are as follows; 1) the concentration of produced tritiated water is well proportioned to that of initial tritiated hydrogen, 2) the activation energy of exchange reaction from tritiated hydrogen to tritiated water is 26.2 kcal/mol and that of inverse reaction is 27.4 kcal/mol, 3) the reaction rate at room temperature which calculated with activation energy is 1.04 x 10 -13 day -1 , and then exchange reaction at room temperature is negligible. (author)

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

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

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.)

Theoretical study of the Cs isotope exchange reaction of CsI + Cs' → Cs + ICs' (Contract research)

International Nuclear Information System (INIS)

Kobayashi, Takanori; Hashimoto, Masashi; Yokoyama, Keiichi

2015-12-01

To discuss the exchange reaction of Cs isotope by CsI + Cs' → Cs + ICs', the structure and chemical properties of Cs 2 I intermediate and potential energy surface of the entrance reaction are calculated using M06/def2-TZVPPD density functional calculation. The calculation shows that the reaction to the intermediate has no barrier and the two Cs-I bonds of Cs 2 I are chemically equivalent. These results suggest that the rate of the Cs exchange reaction of CsI + Cs' → Cs + ICs' is as high as the collision rate. (author)

Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

Science.gov (United States)

Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

2015-01-01

Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

Thermoneutral isotope exchange reactions of cations in the gas phase

International Nuclear Information System (INIS)

Ausloos, P.; Lias, S.G.

1981-01-01

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

In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

International Nuclear Information System (INIS)

Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

2017-01-01

Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ . In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage. (topical review)

Forward pion-nucleon charge exchange reaction and Regge constraints

International Nuclear Information System (INIS)

Huang Fei; Sibirtsev, A.; Krewald, S.; Hanhart, C.; Haidenbauer, J.; Meibner, U.-G.

2009-01-01

We present our recent study of pion-nucleon charge exchange amplitudes above 2 GeV. We analyze the forward pion-nucleon charge exchange reaction data in a Regge model and compare the resulting amplitudes with those from the Karlsruhe-Helsinki and George-Washington-University partial-wave analyses. We explore possible high-energy constraints for theoretical baryon resonance analyses in the energy region above 2 GeV. Our results show that for the pion-nucleon charge exchange reaction, the appropriate energy region for matching meson-nucleon dynamics to diffractive scattering should be around 3 GeV for the helicity flip amplitude. (authors)

Asymmetric H-D exchange reactions of fluorinated aromatic ketones

KAUST Repository

Zhao, Yujun

2012-01-01

Chiral bicyclic guanidine catalyzes the asymmetric H-D exchange reactions. Up to 30% ee was achieved. DFT calculations were employed to elucidate and explain the origin of the reaction\\'s stereoselectivity. © 2012 The Royal Society of Chemistry.

Development and Application of Ligand-Exchange Reaction Method ...

African Journals Online (AJOL)

Purpose: This paper presents an improved kinetic-spectrophotometric procedure for determining clonazepam (CZP) in pharmaceutical formulations and human serum. Methods: The method is based on ligand-exchange reaction. The reaction was followed spectrophotometrically by measuring the rate of change of ...

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

Self-assembled monolayer exchange reactions as a tool for channel interface engineering in low-voltage organic thin-film transistors.

Science.gov (United States)

Lenz, Thomas; Schmaltz, Thomas; Novak, Michael; Halik, Marcus

2012-10-02

In this work, we compared the kinetics of monolayer self-assembly long-chained carboxylic acids and phosphonic acids on thin aluminum oxide surfaces and investigated their dielectric properties in capacitors and low-voltage organic thin-film transistors. Phosphonic acid anchor groups tend to substitute carboxylic acid molecules on aluminum oxide surfaces and thus allow the formation of mixed or fully exchanged monolayers. With different alkyl chain substituents (n-alkyl or fluorinated alkyl chains), the exchange reaction can be monitored as a function of time by static contact angle measurements. The threshold voltage in α,α'-dihexyl-sexithiophene thin-film transistors composed of such mixed layer dielectrics correlates with the exchange progress and can be tuned from negative to positive values or vice versa depending on the dipole moment of the alkyl chain substituents. The change in the dipole moment with increasing exchange time also shifts the capacitance of these devices. The rate constants for exchange reactions determined by the time-dependent shift of static contact angle, threshold voltage, and capacitance exhibit virtually the same value thus proving the exchange kinetics to be highly controllable. In general, the exchange approach is a powerful tool in interface engineering, displaying a great potential for tailoring of device characteristics.

Separation of uranium isotopes by accelerated isotope exchange reactions

International Nuclear Information System (INIS)

Seko, M.; Miyake, T.; Inada, K.; Ochi, K.; Sakamoto, T.

1977-01-01

A novel catalyst for isotope exchange reaction between uranium(IV) and uranium(VI) compounds enables acceleration of the reaction rate as much as 3000 times to make industrial separation of uranium isotopes economically possible

Asymmetric H-D exchange reactions of fluorinated aromatic ketones

KAUST Repository

Zhao, Yujun; Lim, XiaoZhi; Pan, Yuanhang; Zong, Lili; Feng, Wei; Tan, Choonhong; Huang, Kuo-Wei

2012-01-01

Chiral bicyclic guanidine catalyzes the asymmetric H-D exchange reactions. Up to 30% ee was achieved. DFT calculations were employed to elucidate and explain the origin of the reaction's stereoselectivity. © 2012 The Royal Society of Chemistry.

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

International Nuclear Information System (INIS)

Uda, Tatsuhiko

1992-01-01

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

Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

International Nuclear Information System (INIS)

Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-01-01

Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu"3"+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated

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.

Selenocysteine in thiol/disulfide-like exchange reactions.

Science.gov (United States)

Hondal, Robert J; Marino, Stefano M; Gladyshev, Vadim N

2013-05-01

Among trace elements used as cofactors in enzymes, selenium is unique in that it is incorporated into proteins co-translationally in the form of an amino acid, selenocysteine (Sec). Sec differs from cysteine (Cys) by only one atom (selenium versus sulfur), yet this switch dramatically influences important aspects of enzyme reactivity. The main focus of this review is an updated and critical discussion on how Sec might be used to accelerate thiol/disulfide-like exchange reactions in natural selenoenzymes, compared with their Cys-containing homologs. We discuss in detail three major aspects associated with thiol/disulfide exchange reactions: (i) nucleophilicity of the attacking thiolate (or selenolate); (ii) electrophilicity of the center sulfur (or selenium) atom; and (iii) stability of the leaving group (sulfur or selenium). In all these cases, we analyze the benefits that selenium might provide in these types of reactions. It is the biological thiol oxidoreductase-like function that benefits from the use of Sec, since Sec functions to chemically accelerate the rate of these reactions. We review various hypotheses that could help explain why Sec is used in enzymes, particularly with regard to competitive chemical advantages provided by the presence of the selenium atom in enzymes. Ultimately, these chemical advantages must be connected to biological functions of Sec.

Theoretical investigation of exchange and recombination reactions in O(3P)+NO(2Π) collisions

International Nuclear Information System (INIS)

Ivanov, M. V.; Zhu, H.; Schinke, R.

2007-01-01

We present a detailed dynamical study of the kinetics of O( 3 P)+NO( 2 Π) collisions including O atom exchange reactions and the recombination of NO 2 . The classical trajectory calculations are performed on the lowest 2 A ' and 2 A '' potential energy surfaces, which were calculated by ab initio methods. The calculated room temperature exchange reaction rate coefficient, k ex , is in very good agreement with the measured one. The high-pressure recombination rate coefficient, which is given by the formation rate coefficient and to a good approximation equals 2k ex , overestimates the experimental data by merely 20%. The pressure dependence of the recombination rate, k r , is described within the strong-collision model by assigning a stabilization probability to each individual trajectory. The measured falloff curve is well reproduced over five orders of magnitude by a single parameter, i.e., the strong-collision stabilization frequency. The calculations also yield the correct temperature dependence, k r ∝T -1.5 , of the low-pressure recombination rate coefficient. The dependence of the rate coefficients on the oxygen isotopes are investigated by incorporating the difference of the zero-point energies between the reactant and product NO radicals, Δ ZPE , into the potential energy surface. Similar isotope effects as for ozone are predicted for both the exchange reaction and the recombination. Finally, we estimate that the chaperon mechanism is not important for the recombination of NO 2 , which is in accord with the overall T -1.4 dependence of the measured recombination rate even in the low temperature range

Catalytic isotope exchange reaction between deuterium gas and water pre-adsorbed on platinum/alumina

International Nuclear Information System (INIS)

Iida, Itsuo; Kato, Junko; Tamaru, Kenzi.

1976-01-01

The catalytic isotope exchange reaction between deuterium gas and the water pre-adsorbed on Pt/Al 2 O 3 was studied. At reaction temperatures above 273 K, the exchange rate was proportional to the deuterium pressure and independent of the amount of adsorbed water, which suggests that the rate determining step is the supply of deuterium from the gas phase. Its apparent activation energy was 38 kJ mol -1 . Below freezing point of water, the kinetic behaviour was different from that above freezing point. At higher deuterium pressures the rate dropped abruptly at 273 K. Below the temperature the apparent activation energy was 54 kJ mol -1 and the exchange rate depended not on the deuterium pressure but on the amount of the pre-adsorbed water. At lower pressures, however, the kinetic behaviour was the same as the above 273 K, till the rate of the supply of deuterium from the gas phase exceeded the supply of hydrogen from adsorbed water to platinum surface. These results suggest that below 273 K the supply of hydrogen is markedly retarded, the state of the adsorbed water differing from that above 273 K. It was also demonstrated that when the adsorbed water is in the state of capillary condensation, the exchange rate becomes very small. (auth.)

Kinetic study on ligand exchange reaction between EC and 99mTc-GH

International Nuclear Information System (INIS)

Wu Chunying; Luo Shineng; Fang Ping; Huang Heyun; Xie Minhao; Meng Hong

1995-01-01

The ligand exchange reaction between EC and 99m Tc-GH and its influence factors such as concentrations of EC and pH were described. The concentration of EC has no influence on the exchange reaction rate constant, while pH is the most important influence factor. The rate constants of ligand exchange reaction at different pH values were determined. The results showed that in order to make the labelling yield of 99m Tc-EC higher than 90%, pH of the reaction must be higher than 8

Surface- vs Diffusion-Limited Mechanisms of Anion Exchange in CsPbBr3 Nanocrystal Cubes Revealed through Kinetic Studies.

Science.gov (United States)

Koscher, Brent A; Bronstein, Noah D; Olshansky, Jacob H; Bekenstein, Yehonadav; Alivisatos, A Paul

2016-09-21

Ion-exchange transformations allow access to nanocrystalline materials with compositions that are inaccessible via direct synthetic routes. However, additional mechanistic insight into the processes that govern these reactions is needed. We present evidence for the presence of two distinct mechanisms of exchange during anion exchange in CsPbX3 nanocrystals (NCs), ranging in size from 6.5 to 11.5 nm, for transformations from CsPbBr3 to CsPbCl3 or CsPbI3. These NCs exhibit bright luminescence throughout the exchange, allowing their optical properties to be observed in real time, in situ. The iodine exchange presents surface-reaction-limited exchanges allowing all anionic sites within the NC to appear chemically identical, whereas the chlorine exchange presents diffusion-limited exchanges proceeding through a more complicated exchange mechanism. Our results represent the first steps toward developing a microkinetic description of the anion exchange, with implications not only for understanding the lead halide perovskites but also for nanoscale ion exchange in general.

Investor Reaction to Mandatory Offers on the Warsaw Stock Exchange

Directory of Open Access Journals (Sweden)

Szymon Okoń

2012-06-01

Full Text Available The following paper aims to assess investor reaction to mandatory offers on the Warsaw Stock Exchange, which is important because knowledge about these reactions can be used to make better investment decisions. This paper highlights the importance of procedure in making a mandatory offer and its grounds in the Polish legal system. Additionally, it presents empirical research on the reactions of investors to mandatory offers on the Warsaw Stock Exchange. It has been provided that mandatory offers have a significant impact on the price of a company’s shares listed on the Warsaw Stock Exchange. Knowledge about the reactions of investors to a mandatory offer may be used when selecting securities for an investment portfolio. The findings may provide guidance in deciding whether to begin or end investment in the company, both for individual and institutional investors. The event study methodology approach used in the paper is regarded as valuable and can be the basis for further research in other areas of the capital market research, especially in the context of information efficiency.

Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

2017-03-31

Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu{sup 3+} doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface

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

Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

Science.gov (United States)

Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

2016-01-01

Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

Relative mobility of 1-H atoms of carbohydrates in heterogeneous isotope exchange reactions

International Nuclear Information System (INIS)

Akulov, G.P.; Snetkova, E.V.; Kayumov, V.G.; Kaminskii, Yu.L.

1988-01-01

The method of competitive reactions was used to determine the relative mobilities of the 1-H atoms of carbohydrates in reactions of heterogeneous isotope exchange, using various reference standards, catalysts, and buffer systems. On the basis of the results obtained, the investigated carbohydrates are ranged in a series of decreasing mobility of the hydrogen atoms exchanged in heterogeneous isotope exchange reactions. It was demonstrated that the mobility of the 1-H atoms is related to the concentration of the acyclic forms of the carbohydrates

Study of reactions of isotopic exchange of trans-zeatin with tritium

International Nuclear Information System (INIS)

Sidorov, G.V.; Myasoedov, N.F.

2006-01-01

Reactions of isotopic exchange of trans-zeatin with high-radioactive tritium water, with gaseous tritium in solution and solid-phase catalytic hydrogenation are studied to prepare trans-zeatin and dihydrozeatin labelled with tritium. It is shown that reaction of isotopic exchange of trans-zeatin with gaseous tritium both in solutions and without solvents at 160 Deg C and above leads to practically total hydrogenation of initial compound with formation of dihydrozeatin labelled with tritium. Isotopic exchange with tritium water permits to prepare zeatin labelled with tritium with 67 % yield and specific radioactivity 0.68 PBq/mol. It is determined that in the case of solid-phase isotopic exchange within 150-155 Deg C temperature interval both dihydrozeatin and trans-zeatin labelled with tritium are formed [ru

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

Energy Technology Data Exchange (ETDEWEB)

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

1978-05-01

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

Application of tracer isotope in kinetic study of first order ion exchange reaction

International Nuclear Information System (INIS)

Lokhande, R.S.; Singare, P.U.

1998-01-01

Analysis of first order ion exchange reaction rates at different temperatures (27 deg- 48 degC) and particularly at low concentration of potassium iodide solution (electrolyte) ranging from 0.005 M to 0.040 M is carried out by application of radioactive tracer isotope 131 I. With increase in concentration of electrolyte, amount of iodide ion exchanged in millimoles increases. Specific reaction rates of ion exchange reaction are calculated for different temperatures and for different amount of ion exchange resins. It is observed that with increase in temperature, reaction rate increases but the increase is more pronounced for increase in amount of ion exchange resins. For 0.005 M solution of electrolyte, the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min -1 at 48 degC. For 0.005 M solution of electrolyte the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min 1 at 48 degC. For 0.005 M solution of electrolyte at 27 degC the reaction rate increases from 0.121 min -1 for 1.0 g of resin to 0.368 min -1 for 5.0 g of resin. From the reaction rates calculated at different temperatures, energy of activation in kJ/mole is calculated. It is observed that for 0.005 M solution of electrolyte, energy of activation is 4.62 kJ/mole which decreases to 2.87 kJ/mole for increase in concentration of electrolyte to 0.100 M. (author)

Quantum theory of exchange reactions: Use of nonorthogonal bases and coordinates

International Nuclear Information System (INIS)

Stechel, E.B.; Schmalz, T.G.; Light, J.C.

1979-01-01

A general approach to quantum scattering theory of exchange reactions utilizing nonorthogonal (''over-complete'') basis sets and nonorthogonal coordinates is presented. The method is shown to resolve many of the formal and practical difficulties attending earlier theories. Although the inspiration came from the early and accurate work on the collinear H+H 2 reaction by Diestler possible applications include electron transfer processes as well as chemical exchange reactions. The mathematics is formulated in detail and the solution is presented in terms of the R-matrix propagation method preserving all the symmetries of the physical process, i.e., conservation of flux and microscopic reversibility

Studies of nuclear structure in antinucleon charge-exchange reactions

International Nuclear Information System (INIS)

Auerbach, N.

1986-01-01

The antinucleon-nucleus charge exchange reaction is discussed an its use as a probe of isovector excitations in nuclei is described. Attention is drawn to the fact that the (anti p,anti n) reaction will predominantly excite ''pionic'' (i.e., longitudinal spin) modes in nuclei. Comparison between (anti p,anti n) and (n,p) reactions is made. Plans for (anti p,anti n) experiments in the near future are mentioned. 21 refs., 3 figs

Ion exchange equilibrium for some uni-univalent and uni-divalent reaction systems using strongly basic anion exchange resin Duolite A-102 D

Directory of Open Access Journals (Sweden)

R.S. Lokhande

2008-04-01

Full Text Available The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Duolite A-102 D. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems was observed to increase with rise in temperature, indicating the endothermic exchange reactions having enthalpy values of 13.7, 38.0, 23.9, 22.9 kJ/mol, respectively.

Forging Colloidal Nanostructures via Cation Exchange Reactions.

Science.gov (United States)

De Trizio, Luca; Manna, Liberato

2016-09-28

Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

Forging Colloidal Nanostructures via Cation Exchange Reactions

Science.gov (United States)

2016-01-01

Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

Science.gov (United States)

Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-03-01

The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

Radiative heat exchange between surfaces

International Nuclear Information System (INIS)

Yener, Y.; Yuncu, H.

1987-01-01

The geometrical features of radiative heat exchange between surfaces are discussed first by developing various radiation shape factor relations. The governing equations for enclosures with diffusely emitting and diffusely reflecting surfaces, as well as the equations for enclosures with gray surfaces having specular component of reflectivity are introduced next. Finally, a simplified model for enclosures with isothermal surfaces under the assumption of uniform radiosity over the surfaces is discussed, and various working relations for different conditions are presented

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.

Groundwater–Surface Water Exchange

DEFF Research Database (Denmark)

Karan, Sachin

The exchange of groundwater-surface water has been invetigated in the western part of Denmark. Holtum AA provides the framework for all the performed investigations. Several methods are used, primarily eld based measurements ombined with numerical models to achieve insight to the governing...... processes of interaction between groundwater and surface water. By using heat as a tracer it has been possible to use temperature directly as calibrationtargets in a groundwater and heat transport model. Thus, it is possible to use heat investigate the change in groundwater discharge in dynamic conditions...... by using simple temperature devices along a stream to delineate the areas of interest in regard to GW{SW exchange. Thus, at several locations in a stream a temperature data logger was placed in the water column and right at the streambed-water interface. By looking at the correlation of streambed...

EXFOR Basics. A short guide to the neutron reaction data exchange format

International Nuclear Information System (INIS)

McLane, V.; NUCLEAR DATA CENTER NETWORK

2000-01-01

This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969.3 As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: l that is machine-readable (for checking and indicating possible errors); l that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data

Proton exchange in acid–base complexes induced by reaction coordinates with heavy atom motions

International Nuclear Information System (INIS)

Alavi, Saman; Taghikhani, Mahdi

2012-01-01

Highlights: ► Proton exchange in acid–base complexes is studied. ► The structures, binding energies, and normal mode vibrations are calculated. ► Transition state structures of proton exchange mechanism are determined. ► In the complexes studied, the reaction coordinate involves heavy atom rocking. ► The reaction coordinate is not simply localized in the proton movements. - Abstract: We extend previous work on nitric acid–ammonia and nitric acid–alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid–strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are −1 . This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm −1 . Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

On the treatment of exchange effects in direct reactions

International Nuclear Information System (INIS)

Bencze, G.; Chandler, C.; Argonne National Lab., IL; New Mexico Univ., Albuquerque

1985-01-01

Exchange effects in direct reactions are investigated in the framework of the general algebraic theory of identical particle scattering. It is shown that effects due to the permutation symmetry of the system can be separated from the treatment of reaction dynamics. Dynamical aspects of the problem are investigated within the framework of the channel coupling class of N-body theories. (orig.)

The gecko visual pigment: the chromophore dark exchange reaction.

Science.gov (United States)

Crescitelli, F

1988-02-01

This study confirms the occurrence of a dark-exchange reaction in the extracted 521-pigment of the Tokay gecko (G. gekko). The present study involved the exchange, in the dark, of the natural 11-cis-chromophore by the 9-cis-10-F-retinal analog. This analog is able to combine with the 521-opsin to regenerate a photopigment at 492 nm. In addition to this shift in absorbance from 521 to 492 nm, the analog photopigment has a photosensitivity some 2.4% that of the native 521-system in the chloride-sufficient state. These two properties of the regenerated analog pigment have simplified the demonstration of a dark exchange of chromophores. At 15 degrees C the 9-cis-10-F-analog replaces the 11-cis-chromophore by at least 30% (density-wise) in about 15 hr. This exchange occurs with the system in the chloride-deficient state. The presence of chloride during the period in the dark significantly reduces the magnitude of the exchange. Apparently, the protein has a more open structure at the chromophoric binding site, allowing this interchange of chromophores. The addition of chloride induces a conformational change at this site, 'burying' the Schiff base and reducing the exchange reaction. The biological implication of this mobile property of the gecko opsin is that it is similar to the behavior of the cone pigment iodopsin but is unlike that of rhodopsins. This supports the idea that the gecko visual cells, despite their appearance as rods, are phylogenetically related to ancestral photopic receptors.

Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump.

Science.gov (United States)

Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi

2015-04-28

The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products. Copyright © 2015 Elsevier B.V. All rights reserved.

Nucleophilic radioiodination of 6-bromocholesterol via non-isotopic exchange reaction in molten state

International Nuclear Information System (INIS)

El-Shaboury, G.; Farah, K.; El-Tawoosy, M.

2001-01-01

A synthetic method for preparing radioiodinated 6-[ 125 I]iodocholesterol [CL-6- 125 I] for adrenal evaluation is described. The radioiodine atom was incorporated onto the cholesterol molecule via non-isotopic exchange between 6-bromocholesterol [CL-6-Br] and radioiodine as iodide ion [ 125 I - ] in a molten state. The different parameters affecting the yield of exchange were investigated using 125 I (T 1/2 ≅ 60 d) to centralize the different physical and chemical reaction conditions and purification of the final product as pure as 6-[ 125 I]iodocholesterol. The method was suitable to either 131 I (T 1/2 ≅ 8 d) nucleophilic radioiodination which facilitates the scanning of the adrenal for a few days after administration or the use of 124 I (T 1/2 ≅ 4.16 d) nucleophilic radioiodination for PET evaluation of the adrenal. TLC as well as HPLC chromatographic analysis is used to determine the efficiency of the exchange reactions under different chemical reaction conditions and to monitor the stability of the final product as pure as CL-6- 125 I with radiochemical purity of ≅99%. This no-carrier-added method improved the speed of the reaction and affords high radiochemical yield of 90% and suitable specific activity due to the use of CL-6-Br rather than CL-6-I as substrate. Kinetic studies revealed second order iodine-bromine exchange reaction. The activation energy for the exchange reaction in ammonium acetate (m.p. 114 deg C) was calculated to be 4.576 kcal/mole. (author)

Carbonyl-Olefin Exchange Reaction: Present State and Outlook

Science.gov (United States)

Kalinova, Radostina; Jossifov, Christo

The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

International Nuclear Information System (INIS)

Janev, R.K.; Kato, T.; Wang, J.G.

2001-05-01

The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C x H y charge exchange reactions from thermal energies up to several hundreds keV for all C x H y molecules with x=1, 2, 3 and 1 ≤ y ≤ 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

Current status of uranium enrichment by way of chemical exchange reactions

International Nuclear Information System (INIS)

El Basyouny, A.; Bechthold, H.C.; Knoechel, A.; Vollmer, H.J.

1985-04-01

For this report, conference proceedings, patents and other types of literature have been collected to present an account of the current status of uranium enrichment by way of chemical exchange reactions. The report further presents a new concept along with the relevant process strategy developed by the authors. The principal process of the new concept is a chemical exchange process with crown ethers, complexed or free, playing an important part in the reactions. The authors also describe their experiments carried out for establishing suitable chemical systems. (orig./PW) [de

Exchange reactions in the systems of alkali metal, silver and thallium, sulfates, niobates and tantalates

International Nuclear Information System (INIS)

Belyaev, I.N.; Lupejko, T.G.; Nalbandyan, V.B.; Abanina, E.V.

1978-01-01

Investigated are exchange interactions in diagonal cross sections of twenty triple mutual systems with A and A' cations and SO 4 and MO 3 anions where A and A'-Li, Na, K, Ag, Tl, M-Nb, Ta using the methods of X-ray phase, chemical and differential thermal analyses. Exchange reaction between crystal complex oxide and melted salt are effective synthesis method. These reactions in particular permitted to obtain pure AgNbO 3 , AgTaO 3 and their solid solutions at temperatures hundreds degrees lower than in displacement reactions. Equilibrium samples of AMO 3 -A'MO 3 systems, continuous or discontinuous solid solutions, compounds (except NaMO 3 -KMO 3 , and also LiTaO 3 -KTaO 3 ) are formed in exchange reactions when there is sulfate shortage. Thus, exchange reactions can be applied for solid solution synthesis, and also for phase diagram study

Method of relative comparison of the thermohydraulic efficiency of heat exchange intensification in channels of heat-exchange surfaces

International Nuclear Information System (INIS)

Dubrovskij, E.V.; Vasil'ev, V.Ya.

2002-01-01

One introduces a technique to compare relatively thermohydraulic efficiency of heat transfer intensification in channels of heat exchange surfaces of any design types. It is shown that one should compare thermohydraulic efficiency of heat exchange intensification as to the thermal power of heat exchangers and pressure losses in channels with turbulators and in polished channels of heat exchange surfaces on the basis of dimensions of heat exchangers, their heat exchange surfaces and at similar (as to Re numbers) modes of coolant flow [ru

Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump

Energy Technology Data Exchange (ETDEWEB)

Dong, Liang; Xie, Yun [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Du, Liang [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); School of Radiation Medicine and Protection (SRMP), School for Radiological and Interdisciplinary Sciences (RAD-X), Suzhou 215000 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Tan, Zhaoyi, E-mail: zhyitan@126.com [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

2015-04-28

Highlights: • This is the first theoretical investigation about T–H exchange in vacuum oil. • T–H isotope exchange is accomplished through two different change mechanisms. • Isotope exchange is selective, molecules with −OH and −COOH exchange more easily. • The methyl and methylene radicals in waste oil were observed by {sup 1}HNMR. - Abstract: The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium–hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T–H exchange mechanism and the hyrogenation–dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation–dehydrogenation exchange mechanism, the T–H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with −OH and −COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T–H isotope exchange can be determined by the hydrogenation of T{sub 2} or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products.

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.

Exchange reaction of acetylene-d2 with hydrogen chloride

International Nuclear Information System (INIS)

Bopp, A.F.; Kern, R.D.

1975-01-01

A mixture containing 3 percent each of the reactants C 2 D 2 and HCl in an Ne--Ar diluent was studied over the temperature range 1650 to 2600 0 K utilizing a shock tube coupled to a time-of-flight mass spectrometer. Plots of the mole fractions f of the exchange products, DCl and C 2 HD, revealed two distinct regions of growth: (a) an initial low conversion region characterized by an induction period t/sub i/; and (b) a region of accelerated exchange during which exchange products were formed with a quadratic dependence of the reaction time. These two regions labeled a and b were combined using two empirical equations, 1 - f/sub a//f/sub eq,a/ = exp [-k/sub a/[M]t], where t less than or equal to t/sub i/, and 1 - f/sub b//f/sub eq,b/ = exp [-k/sub b/[M](t - t/sub i/) 2 ], in order to represent the entire reaction profile at any given temperature within the interval investigated. The Arrhenius parameters for k/sub a/ and k/sub b/ were determined to be 10 11 . 15+-0 . 30 exp (-19990 +- 2850/RT) and 10 16 . 40+-0 . 41 exp (-31480 +- 4200/RT), respectively, for DCl and 10 11 . 69+-0 . 29 exp (-19150 +- 2740/RT) and 10 15 . 24+-0 . 34 exp (-17620 +- 3480/RT) for C 2 HD. The units for k/sub a/ are cm 3 mol -1 sec -1 and cm 3 mol -1 sec -2 for k/sub b/. Activation energies are reported in cal mol -1 . Comparison with the profiles obtained for acetylene pyrolysis strongly suggests that the mechanism for the exchange is atomic. Furthermore, the exchange experiments indicate that the initial step in the pyrolysis of acetylene is the disproportionation reaction, 2C 2 H 2 → C 2 H + C 2 H 3

Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

Energy Technology Data Exchange (ETDEWEB)

Janev, R.K.; Kato, T. [National Inst. for Fusion Science, Toki, Gifu (Japan); Wang, J.G. [Department of Physics and Astronomy, University of Georgia, Athens (United States)

2001-05-01

The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C{sub x}H{sub y} charge exchange reactions from thermal energies up to several hundreds keV for all C{sub x}H{sub y} molecules with x=1, 2, 3 and 1 {<=} y {<=} 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

1H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase

International Nuclear Information System (INIS)

Esaki, N.; Nakayama, T.; Sawada, S.; Tanaka, H.; Soda, K.

1985-01-01

Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the straight-chain L-amino acids which are not susceptible to elimination. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. For L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically

Effects of pressure, temperature and atomic exchanges on phase separation dynamics in Au/Ni(111) surface alloy: Kinetic Monte Carlo study

Energy Technology Data Exchange (ETDEWEB)

Zvejnieks, G. [Institute for Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Ibenskas, A., E-mail: ibenskas@pfi.lt [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania); Tornau, E.E. [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania)

2015-11-15

Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p, and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R, increases with p), (ii) intermediate regime (weak p–dependence), and (iii) fast homogeneous flow (R decreases with p). We find that only Au–Ni exchange, contrary to both Ni–CO and Au–CO exchanges, significantly reduces the number of screened Ni atoms inside the Au clusters and stimulates the occurrence of Ni-free Au clusters. The size of Au islands depends on both pressure and temperature. At a fixed temperature it decreases with pressure due to an increased step flow rate. In the high temperature limit, despite the step flow rate exponential increase with temperature, the cluster size increases due to an enhanced Au mobility. - Highlights: • Kinetic Monte Carlo study of Au–Ni surface alloy instability to CO pressure and temperature. • Three reaction front propagation regimes. • In channel-like regime, the step flow rate increases with CO pressure as in experiment. • Ni-free Au islands are obtained when Au-Ni adatom exchange mechanism is considered. • The size of Au islands decreases with pressure and increases with temperature.

Effects of pressure, temperature and atomic exchanges on phase separation dynamics in Au/Ni(111) surface alloy: Kinetic Monte Carlo study

International Nuclear Information System (INIS)

Zvejnieks, G.; Ibenskas, A.; Tornau, E.E.

2015-01-01

Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p, and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R, increases with p), (ii) intermediate regime (weak p–dependence), and (iii) fast homogeneous flow (R decreases with p). We find that only Au–Ni exchange, contrary to both Ni–CO and Au–CO exchanges, significantly reduces the number of screened Ni atoms inside the Au clusters and stimulates the occurrence of Ni-free Au clusters. The size of Au islands depends on both pressure and temperature. At a fixed temperature it decreases with pressure due to an increased step flow rate. In the high temperature limit, despite the step flow rate exponential increase with temperature, the cluster size increases due to an enhanced Au mobility. - Highlights: • Kinetic Monte Carlo study of Au–Ni surface alloy instability to CO pressure and temperature. • Three reaction front propagation regimes. • In channel-like regime, the step flow rate increases with CO pressure as in experiment. • Ni-free Au islands are obtained when Au-Ni adatom exchange mechanism is considered. • The size of Au islands decreases with pressure and increases with temperature

Analysis of (3He, t) charge exchange reactions at 140 AMeV

International Nuclear Information System (INIS)

Singh, Pardeep; Zegers, R.G.T.; Danielewicz, Pawel; Noji, S.; Kim, B.T.; Sakai, H.

2014-01-01

The spin-isospin response in nuclei has been studied widely through ( 3 He, t) and (t, 3 He) charge-exchange reactions wherein a proton (neutron) transforms into a neutron (proton), which in turn changes the isospin, ΔT=1, of the nuclei participating in the reaction, either with or without spin transfer. The Gamow-Teller transitions are used to obtain the weak transition strength in the excitation-energy regions inaccessible through β-decay. The strengths deduced using charge exchange experiments provide stringent tests for nuclear structure calculations and serve as inputs for variety of applications in which weak transition strengths play a role. In this context, we explore here the ( 3 He,t) charge-exchange reaction at 140 MeV/u on 18 O, 26 Mg, 58,60,62, 64 Ni, 90 Zr, 118,120 Sn and 208 Pb targets, within the theoretical framework of distorted wave impulse approximation

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

International Nuclear Information System (INIS)

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

1980-01-01

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

Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

Science.gov (United States)

Cooper, Samuel J; Niania, Mathew; Hoffmann, Franca; Kilner, John A

2017-05-17

A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H 2 O and CO 2 ) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO 2 . The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

Kinetics and Mechanisms of Oxygen Surface Exchange on La0.6Sr0.4FeO3-delta Thin Films

DEFF Research Database (Denmark)

Mosleh, Majid; Søgaard, Martin; Hendriksen, Peter Vang

2009-01-01

and oxygen partial pressure [i.e., the incorporation reaction has the same reaction enthalpy (H0=−105 KJ/mol) and entropy (S0=−75.5 J/mol/K) as found for bulk material]. The thin film shows smaller apparent electrical conductivity than reported for bulk. This is due to imperfections in the film, which...... is not totally dense and contains closed porosity. Electrical conductivity relaxation was used to determine the surface exchange coefficient and its dependence on the temperature and oxygen partial pressure. Relaxation curves showed a good fit to a simple exponential decay. The vacancy surface exchange...... coefficient (kV) determined from Kchem shows a slope (log kV vs log PO2) between 0.51 and 0.85. It is further found that kV is proportional to the product of the oxygen partial pressure and the vacancy concentration (kVPO2). Different reaction mechanisms that can account for the observed PO2 and -dependence...

Formation of ZnSe/Bi2Se3 QDs by surface cation exchange and high photothermal conversion

Directory of Open Access Journals (Sweden)

Guozhi Jia

2015-08-01

Full Text Available Water-dispersed core/shell structure ZnSe/Bi2Se3 quantum dots were synthesized by ultrasonicwave-assisted cation exchange reaction. Only surface Zn ion can be replaced by Bi ion in ZnSe quantum dots, which lead to the ultrathin Bi2Se3 shell layer formed. It is significance to find to change the crystal of QDs due to the acting of ultrasonicwave. Cation exchange mechanism and excellent photothermal conversion properties are discussed in detail.

Study on the surface reaction of LaNi{sub 5} alloy during discharge process in KOH solution

Energy Technology Data Exchange (ETDEWEB)

Tan Zuxian [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Yang Yifu [Department of Chemistry, Wuhan University, Wuhan 430072 (China)]. E-mail: yang-y-f1@vip.sina.com; Jiang Fengshan [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Shao Huixia [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

2006-10-05

A new method for studying surface reaction of LaNi{sub 5} absorbing alloy in KOH solution (pH 12) was established. It is based on tip-substrate voltammetry of scanning electrochemical microscopy (SECM) where the tip faradic current is recorded while scanning the substrate potential. The Pt electrode is selected as tip electrode, and the Pt oxide formation-reduction is used as a pH-dependent reaction while the tip potential is held at a constant value. As substrate surface reactions proceed, the pH of solution can be changed, and then the tip faradic current is recorded. The mechanism of discharge process of LaNi{sub 5} alloy was analyzed by comparing the tip current (I {sub tip}) versus substrate potential (E {sub sub}) curve, which reflects the exchange of H{sup +} or OH{sup -} between the alloy surface and the solution, with the substrate current (I {sub sub}) versus substrate potential (E {sub sub}) curve, which reflects the exchange of electron on the LaNi{sub 5} alloy surface. The results showed that the OH{sup -} adsorption process is occurred before the electron transfer process during discharge process, and the adsorptive OH{sup -} helps the oxidation of adsorbed hydrogen atom on the alloy surface. A quantitative assessment for the maximum changes of pH during discharge process is also proposed, and the variation as large as 2.65 pH unit was detected.

Study on the surface reaction of LaNi{sub 5} alloy during discharge process in KOH solution

Energy Technology Data Exchange (ETDEWEB)

Tan, Zuxian; Yang, Yifu; Jiang, Fengshan; Shao, Huixia [Wuhan University, Wuhan (China). Department of Chemistry

2006-10-05

A new method for studying surface reaction of LaNi{sub 5} absorbing alloy in KOH solution (pH 12) was established. It is based on tip-substrate voltammetry of scanning electrochemical microscopy (SECM) where the tip faradic current is recorded while scanning the substrate potential. The Pt electrode is selected as tip electrode, and the Pt oxide formation-reduction is used as a pH-dependent reaction while the tip potential is held at a constant value. As substrate surface reactions proceed, the pH of solution can be changed, and then the tip faradic current is recorded. The mechanism of discharge process of LaNi{sub 5} alloy was analyzed by comparing the tip current (I{sub tip}) versus substrate potential (E{sub sub}) curve, which reflects the exchange of H{sup +} or OH{sup -} between the alloy surface and the solution, with the substrate current (I{sub sub}) versus substrate potential (E{sub sub}) curve, which reflects the exchange of electron on the LaNi{sub 5} alloy surface. The results showed that the OH{sup -} adsorption process is occurred before the electron transfer process during discharge process, and the adsorptive OH{sup -} helps the oxidation of adsorbed hydrogen atom on the alloy surface. A quantitative assessment for the maximum changes of pH during discharge process is also proposed, and the variation as large as 2.65 pH unit was detected. (author)

On the mesonic-exchange currents in the photomesic reactions

International Nuclear Information System (INIS)

Lazard, C.; Maric, Z.; Zivanovic, D.

1979-02-01

The γd→π 0 d reaction is analysed in the framework of the relativistic many-body theory with mesonic degrees of freedom explicitly present. It is shown that the mesonic correlations can be grouped into transition operators containing vertices of some elementary reactions between photon, nucleons and pions. The wave function corrections due to meson exchange currents are included in the transition operators and the S-matrix is obtained with the non relativistic deuteron wave function

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

Science.gov (United States)

Bertulani, C. A.

2018-01-01

Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean ~ 50 MeV/nucleon and higher) are now routinely used to extract information of interest for nuclear astrophysics. This is of extreme relevance as many of the nuclei involved in stellar evolution are short-lived. Therefore, indirect methods became the focus of recent studies carried out in major nuclear physics facilities. Among such methods, heavy ion charge exchange is thought to be a useful tool to infer Gamow-Teller matrix elements needed to describe electron capture rates in stars and also double beta-decay experiments. In this short review, I provide a theoretical guidance based on a simple reaction model for charge exchange reactions.

Determination of the energetics of the UDP-glucose pyrophosphorylase reaction by positional isotope exchange inhibition

International Nuclear Information System (INIS)

Hester, L.S.; Raushel, F.M.

1987-01-01

A method has been developed for obtaining qualitative information about enzyme-catalyzed reactions by measuring the inhibitory effects of added substrates on positional isotope exchange rates. It has been demonstrated for ordered kinetic mechanisms that an increase in the concentration of the second substrate to add to the enzyme will result in a linear increase in the ratio of the chemical and positional isotope exchange rates. The slopes and intercepts from these plots can be used to determine the partitioning ratios of binary and ternary enzyme complexes. The method has been applied to the reaction catalyzed by UDP-glucose pyrophosphorylase. A positional isotope exchange reaction was measured within oxygen-18-labeled UTP as a function of variable glucose 1-phosphate concentration in the forward reaction. In the reverse reaction, a positional isotope exchange reaction was measured within oxygen-18-labeled UDP-glucose as a function of increasing pyrophosphate concentration. The results have been interpreted to indicate that the interconversion of the ternary central complexes is fast relative to product dissociation in either direction. In the forward direction, the release of UDP-glucose is slower than the release of pyrophosphate. The release of glucose 1-phosphate is slower than the release of UTP in the reverse reaction

Moving Towards a State of the Art Charge-Exchange Reaction Code

Science.gov (United States)

Poxon-Pearson, Terri; Nunes, Filomena; Potel, Gregory

2017-09-01

Charge-exchange reactions have a wide range of applications, including late stellar evolution, constraining the matrix elements for neutrinoless double β-decay, and exploring symmetry energy and other aspects of exotic nuclear matter. Still, much of the reaction theory needed to describe these transitions is underdeveloped and relies on assumptions and simplifications that are often extended outside of their region of validity. In this work, we have begun to move towards a state of the art charge-exchange reaction code. As a first step, we focus on Fermi transitions using a Lane potential in a few body, Distorted Wave Born Approximation (DWBA) framework. We have focused on maintaining a modular structure for the code so we can later incorporate complications such as nonlocality, breakup, and microscopic inputs. Results using this new charge-exchange code will be shown compared to the analysis in for the case of 48Ca(p,n)48Sc. This work was supported in part by the National Nuclear Security Administration under the Stewardship Science Academic Alliances program through the U.S. DOE Cooperative Agreement No. DE- FG52-08NA2855.

Surface - atmosphere exchange of ammonia over grazed pasture

NARCIS (Netherlands)

Plantaz, M.A.H.G.

1998-01-01

This thesis deals with the exchange of ammonia between the atmosphere and grazed pasture in an area of intensive livestock breeding. The term exchange is used because gaseous ammonia can be taken up (dry deposition) as well as released (emission) by this type of surface.
Ammonia exchange

Poisoning by carbon monoxide in the hydrogen exchange reaction between deuterium gas and water preadsorbed on a platinum--alumina catalyst

International Nuclear Information System (INIS)

Iida, I.; Tamaru, K.

1979-01-01

Poisoning by carbon monoxide in the exchange reaction between deuterium and the water preadsorbed on a platinum--alumina catalyst was studied, by measuring not only the rate of reaction but also its kinetic behavior and the adsorption of reactants on the catalyst surface. The shape of the poisoning curve is closely associated with the kinetic behavior and exhibited an abrupt change on freezing the adsorbed water below 273 0 K. When the rate is proportional to deuterium pressure and independent of the amount of water adsorbed, the exchange rate dropped sharply by carbon monoxide adsorbed of a few percent coverage without any marked changes in the amount and the rate of hydrogen adsorption on the platinum surface. However, at temperatures lower than 273 0 K and at higher deuterium pressures, the rate depends not on the deuterium pressure but on the amount of water adsorbed. The migration of hydrogen in or through the adsorbed water is seemingly sufficiently suppressed by freezing to control the overall reaction rate. In this case, a small amount of adsorption of carbon monoxide did not show any toxicity, but then a steep poisoning started accompanying a change in the kinetic behavior. It was accordingly demonstrated that the mechanism of the reaction may be better understood by studying poisoning and measuring adsorption, overall rate, and kinetic behavior

Ion exchange and trace element surface complexation reactions associated with applied recharge of low-TDS water in the San Joaquin Valley, California

International Nuclear Information System (INIS)

McNab, Walt W.; Singleton, Michael J.; Moran, Jean E.; Esser, Bradley K.

2009-01-01

Stable isotope data, a dissolved gas tracer study, groundwater age dating, and geochemical modeling were used to identify and characterize the effects of introducing low-TDS recharge water in a shallow aerobic aquifer affected by a managed aquifer recharge project in California's San Joaquin Valley. The data all consistently point to a substantial degree of mixing of recharge water from surface ponds with ambient groundwater in a number of nearby wells screened at depths above 60 m below ground surface. Groundwater age data indicate that the wells near the recharge ponds sample recently recharged water, as delineated by stable O and C isotope data as well as total dissolved solids, in addition to much older groundwater in various mixing proportions. Where the recharge water signature is present, the specific geochemical interactions between the recharge water and the aquifer material appear to include ion exchange reactions (comparative enrichment of affected groundwater with Na and K at the expense of Ca and Mg) and the desorption of oxyanion-forming trace elements (As, V, and Mo), possibly in response to the elevated pH of the recharge water

Theoretical study on platinum-catalyzed isotope exchange reaction mechanism of hydrogen and liquid water

International Nuclear Information System (INIS)

Hu Sheng; Wang Heyi; Luo Shunzhong

2009-04-01

Based on electron and vibration approximate means and the density function theory B3LYP, the ΔG degree and equilibrium pressures of adsorption and dissociation reactions of H 2 and water vapor on Pt surface have been calculated. The adsorption, dissociation and coadsorption actions of H 2 and water were analyzed. According to the ΔG degree, hydrogen molecule combines with metal atoms in single atom, and water vapor molecule has no tendency to dissociate on Pt surface. The dissociation of hydrogen molecule would hold back the direct adsorption of water vapor molecules on Pt surface. The structures of Pt-H (OH 2 ) n + (n=1, 2, 3) hydroniums were optimized. According to the mulliken overlap populations, Pt-H (OH 2 ) + is not stable or produced. Hydrogen isotope exchange occurs between hydration layer and D atoms which adsorb on Pt surface via intermediates (H 2 O) n D + (ads) (n≥2). (authors)

Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach

Science.gov (United States)

Manogaran, Lavaneesvari; Sek, Siok Kun

2017-04-01

Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.

Study of iodine-iodate isotopic exchange reaction in neutral aqueous solutions by radiotracer technique

International Nuclear Information System (INIS)

Tripathi, R.; Ram, K.D.

1993-01-01

The isotopic exchange of iodine atoms in neutral aqueous solutions of iodate ions and iodine (in KI) is found to obey the rate law R = k [IO 3 - ] 0.4 [I 2 ] 1.2 at 175 o C. The addition of neutral ionic salts, e.g. KCl and KNO 3 , in the reaction mixture showed a slight catalytic effect on the exchange rate. Further, the kinetic salt effect indicated the involvement of at least one neutral species on the rate-determining step. The activation energy in neutral aqueous solutions of iodate ions and iodine is found to be 86 ± 3 kJ mol -1 , which decreases in the presence of KCl (79 ± 3 kJ mol -1 and KNO 3 (82 + 3 kJ mol -1 ). The activation parameters, viz. free energy of activation, enthalpy of activation and entropy of activation, were also calculated. Based on these results, an association-dissociation type of reaction mechanism is proposed for this exchange reaction in neutral aqueous medium, similar to that proposed earlier for iodide-iodate isotopic exchange reaction in neutral aqueous solutions, nitrate eutectic melts and iodide-iodate melts. (author)

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.

Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

KAUST Repository

Al-Shareef, Reem A.; Harb, Moussab; Saih, Youssef; Ould-Chikh, Samy; Roldan, Manuel A.; Anjum, Dalaver H.; Guyonnet, Elodie Bile; Candy, Jean-Pierre; Jan, Deng-Yang; Abdo, Suheil F.; Aguilar-Tapia, Antonio; Proux, Olivier; Hazemann, Jean-Louis; Basset, Jean-Marie

2018-01-01

Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

KAUST Repository

Alshareef, Reem Abdul aziz Hamed

2018-04-25

Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

Multiscale simulations of ligand adsorption and exchange on gold nanoparticles.

Science.gov (United States)

Gao, Hui-Min; Liu, Hong; Qian, Hu-Jun; Jiao, Gui-Sheng; Lu, Zhong-Yuan

2018-01-17

We have developed a multiscale model that combines first-principles methods with atomistic and mesoscopic simulations to explore the molecular structures and packing density of the ligands present on the gold nanoparticle (AuNP) surface, as well as the adsorption/exchange reaction kinetics of cetyltrimethylammonium bromide (CTAB)/PEG-SH ligands on different facets of gold, namely, Au(111), Au(100), and Au(110). Our model predicts that on clean gold surfaces, CTAB adsorption is diffusion limited. Specifically, CTAB has the preferentially higher adsorption rate and coverage density on Au(100) and Au(110) surfaces, forming a more compact layer with respect to that on the Au(111) surface, which could result in greater growth of gold nanoparticles along the (111) direction. As opposed to CTAB adsorption, the exchange reaction between PEG-SH with CTAB shows no selectivity to different crystal faces, and the reaction process follows Langmuir diffusion kinetics. Kinetic analysis reveals that, in water, the exchange reaction is zeroth order with respect to the concentration of an incoming PEG-SH, indicative of a dissociative exchange mechanism. The observed rate constant decreases exponentially with the PEG-SH chain length, consistent with a diffusion process for the free PEG-SH in water. In particular, we show that the exchange efficiency increases as the chain rigidness and size of the incoming ligand and/or steric bulk of the initial protecting ligand shell are decreased. Our objectives are to provide a model to assess the kinetics and thermodynamics of the adsorption/exchange reaction process, and we expect that these findings will have important implications for routine surface characterization of AuNPs.

The 10B (7Li, 7Be)10Be charge-exchange reaction

International Nuclear Information System (INIS)

Etchegoyen, A.

1987-01-01

It is analysed the mechanisms: direct charge-exchange through the two-body residual force (Q opt ∼ 0.2 MeV, which is close to the reaction Q-value of - 1,42 MeV); and single-Nucleon Knock-on exchange (SNKE) due to the intereacting nucleons being undistinguishable. These mechanisms are analysed in detail for producing 10 B ( 7 Li, 7 Be) 10 Be reaction. The experience was carried out at the Tandar Laboratory using conventional electronics. The elastic scattering was simultaneously measured in order to obtain an optical model parameter set. (M.C.K.) [pt

On the treatment of exchange effects in direct reactions

International Nuclear Information System (INIS)

Bencze, Gy.

1984-11-01

In the theoretical description of direct nuclear reactions the dynamic effects are combined with 'kinematical' effects due to the quantum mechanical exchange interaction caused by the Pauli principle governing the mechanics of identical particles. In the present paper it is shown that in the frame of general algebraic theory of identical particle scattering the effects of the permutational symmetry of nucleons can be separated on an exact way from the treatment of reaction dynamics. Dynamical approximations may be used only after the separation of permutational effects. (D.Gy.)

EXFOR Systems Manual Nuclear reaction Data Exchange Format

International Nuclear Information System (INIS)

McLane, V.

2000-01-01

EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format

EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

Energy Technology Data Exchange (ETDEWEB)

MCLANE,V.; NUCLEAR DATA CENTER NETWORK

2000-05-19

EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

Kinetics of H-D exchange in olefins with complicating reactions

International Nuclear Information System (INIS)

Trokhimets, A.I.

1979-01-01

The kinetics of H-D-exchange is considered for olefins under conditions when simple and complicated exchange occur together with hydrogenation. If hydrogenation takes place in the system, it is theoretically impossible to derive the integrated rate equation for the accumulation of deuterium in the olefin. The variation of the concentration of different deuteroolefins during the process can be calculated numerically. A method is proposed for evaluating the contribution of individual steps to the overall process and determining the rate constants of the most important reactions. (author)

Synthesis of layered sodium lanthanum selenide through ion exchange reactions

International Nuclear Information System (INIS)

Butts, Laura J.; Strickland, Nicholas; Martin, Benjamin R.

2009-01-01

Layered hexagonal KLaSe2 (α-NaFeO 2 -type) was synthesized using the reactive flux method and analyzed by powder XRD to determine its lattice constants (space group R-3m, a = 4.40508(5) A, c = 22.7838(5) A). NaLaSe 2 , which normally crystallizes as a disordered rock salt structure with mixed Na+/La + 3 sites, was synthesized through a solid state ion exchange reaction at 585 deg. C from a 1:3 molar ratio mixture of KLaSe 2 :NaI. The product of this reaction was hexagonally layered NaLaSe 2 (space group R-3m, a = 4.3497(3) A, c = 20.808(2) A) isostructural to KLaSe 2 . This product was analyzed by comparison with members of the set of solid solutions Na (1-x) K (x) LaSe 2 to confirm that the extent ion exchange in this reaction was complete. Cubic (disordered) NaLaSe 2 was also reacted with KI to yield the poorly crystalline hexagonally layered product with the approximate formula Na 0.79 K 0.21 LaSe 2

EXFOR basics: A short guide to the nuclear reaction data exchange format

International Nuclear Information System (INIS)

McLane, V.

1996-07-01

This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear data compilation centers. This format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The exchange format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine). The data presently included in the EXFOR exchange include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle induced reaction data, a selected compilation of photon-induced reaction data

Fabrication of Cationic Exchange Polystyrene Nanofibers for Drug ...

African Journals Online (AJOL)

Purpose: To prepare polystyrene nanofiber ion exchangers (PSNIE) with surface cation exchange functionality using a new method based on electrospinning and also to optimize crosslinking and sulfonation reactions to obtain PSNIE with maximum ion exchange capacity (IEC). Method: The nanofibers were prepared from ...

Hydrogen-deuterium exchange reaction of 2-methylpyridine catalyzed by several fatty acids

International Nuclear Information System (INIS)

Hirata, Hirohumi; Fukuzumi, Kazuo.

1976-01-01

Hydrogen-deuterium exchange reaction of 2-methylpyridine has been studied by using several fatty acids as catalysts. The reaction was carried out in a sealed pyrex tube at 120 0 C, and the contents of the products were determined by mass spectrometry. Reaction of 2-methylpyridine with monodeuteroacetic acid (1 : 1, mol/mol) arrived at a equilibrium (d 0 reversible d 1 reversible d 2 reversible d 3 ) in 2 hr (d 0 41%, d 1 42%, d 2 15%, d 3 2%). No exchange was observed for the reaction of pyridine with monodeuteroacetic acid. The conversion-time curves of typical series reactions (d 0 → d 1 → d 2 → d 3 ) were obtained for the fatty acid catalyzed exchange in deuterium oxide. The effect of the fatty acid RCO 2 H (substrate : fatty acid : D 2 O=1 : 0.86 : 27.6, mol/mol/mol) on the conversion was in the order of R; C 1 --C 3 4 --C 10 , where the reaction mixtures were homogeneous in the case of C 1 --C 3 and were heterogeneous in the case of C 4 --C 10 . The effects of the initial concentration of the substrates and the catalysts (RCO 2 H) on the total conversion were studied by using some fatty acids (R; C 2 , C 4 and C 9 ) in deuterium oxide (for 2 hr). The total conversion of the substrate increases with increasing the concentration of the acids. The total conversion decreases in the case of R=C 9 , but, increases in the case of R=C 2 with increasing the concentration of the substrate. In the case of reactions with low concentrations of the substrate, the reactivity was in the order of C 9 >C 4 >C 2 , while with high concentrations, the reactivity was in the order of C 4 >C 2 >C 9 and C 9 >C 4 >C 2 with high and low concentrations of the acids, respectively. A possible reaction mechanism was proposed and discussed. (auth.)

Why Seemingly Trivial Events Sometimes Evoke Strong Emotional Reactions: The Role of Social Exchange Rule Violations.

Science.gov (United States)

Leary, Mark R; Diebels, Kate J; Jongman-Sereno, Katrina P; Fernandez, Xuan Duong

2015-01-01

People sometimes display strong emotional reactions to events that appear disproportionate to the tangible magnitude of the event. Although previous work has addressed the role that perceived disrespect and unfairness have on such reactions, this study examined the role of perceived social exchange rule violations more broadly. Participants (N = 179) rated the effects of another person's behavior on important personal outcomes, the degree to which the other person had violated fundamental rules of social exchange, and their reactions to the event. Results showed that perceptions of social exchange rule violations accounted for more variance in participants' reactions than the tangible consequences of the event. The findings support the hypothesis that responses that appear disproportionate to the seriousness of the eliciting event are often fueled by perceived rule violations that may not be obvious to others.

EXFOR systems manual: Nuclear reaction data exchange format

International Nuclear Information System (INIS)

McLane, V.

1996-07-01

This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. In addition to storing the data and its bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine)

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

On quark model relations for hypercharge-exchange reactions

International Nuclear Information System (INIS)

Kluyver, J.C.; Blokzijl, R.; Massaro, G.G.G.; Wolters, G.F.; Grossmann, P.; Lamb, P.R.; Wells, J.

1978-01-01

Peripheral two-body reactions of the type K - p → M 0 + Λ, Σ 0 or Σ 0 (1385) are considered. Predictions based on the additive quark model and SU(6) baryon wave functions are tested against data on cross sections and polarisations for given momentum transfer. Data obtained in a high statistics experiment at 4.2 GeV/c K - momentum, as well as data from a large variety of other experiments are used. Highly significant violations of these predictions are observed in the data. These violations are shown to occur in a systematic fashion, according to which SU(6) must be relaxed, but the amplitude structure implied by additivity would remain valid. As an application an amplitude analysis for natural parity exchange reactions with M 0 = π, phi and rho respectively is performed, which determines a relative phase, which cannot be obtained in model-independent analysis. Also reactions with M 0 = delta or B are considered, and some implications for coupling constants are discussed. (Auth.)

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

Science.gov (United States)

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

2018-04-19

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

Reaction mechanism and nuclear correlations study by low energy pion double charge exchange

International Nuclear Information System (INIS)

Weinfeld, Z.

1993-06-01

In pion double-charge-exchange (DCX) reactions, a positive (negative) pion is incident on a nucleus and a negative (positive) pion emerges. These reactions are of fundamental interest since the process must involve at least two nucleons in order to conserve charge. Although two nucleon processes are present in many reactions they are usually masked by the dominant single nucleon processes. DCX is unique in that respect since it is a two nucleon process in lowest order and thus may be sensitive to two-nucleon correlations. Measurements of low energy pion double-charge-exchange reactions to the double-isobaric-analog-state (DIAS) and ground-state (GS) of the residual nucleus provide new means for studying nucleon-nucleon correlations in nuclei. At low energies (T π 7/2 shell at energies ranging from 25 to 65 MeV. Cross sections were measured on 42,44,48 Ca, 46,50 Ti and 54 Fe. The calcium isotopes make a good set of nuclei on which to study the effects of correlations in DCX reactions

Experimental evaluation of improved dual temperature hydrogen isotopic exchange reaction system

International Nuclear Information System (INIS)

Asakura, Yamato; Uchida, Shunsuke

1984-01-01

A proposed dual temperature hydrogen isotopic exchange reaction system between water and hydrogen gas is evaluated experimentally. The proposed system is composed of low temperature co-current reactors for reaction between water mists and hydrogen gas and high temperature co-current reactors for reaction between water vapor and hydrogen gas. Thus, operation is possible under atmospheric pressure with high reaction efficiency. Using the pilot test system which is composed of ten low temperature (30 0 C) reaction units and ten high temperature (200 0 C) reaction units, an experimental separation of deuterium from light water is carried out. The enrichment factor under steady state conditions, its dependency on operating time, and the reaction period necessary to obtain the steady state enrichment factor are determined experimentally and compared with calculations. It is shown that separation ability in a multistage reaction system can be estimated by numerical calculation using actual reaction efficiency in a unit reactor. (author)

Catalytic activity in reactions of isotopic exchange of carbon monoxide and adsorption properties of catalysts on zinc oxide base

International Nuclear Information System (INIS)

Mikheeva, T.M.; Kasatkina, L.A.; Volynkina, A.Ya.

1987-01-01

Activity of different zinc oxide samples in reaction of CO homomolecular isotopic exchnge (HMIE) ( 13 C 18 O+ 12 C 16 O= 13 C 16 O+ 12 C 18 O), CO adsorption on ZnO and isotopic exchange between adsorbed and gaseous CO are investigated. The most active is ZnO sample prepared from ZnCO 3 . Quantitative ratio between different with respect to surface strength molecules of adsorbed CO are experimentally determined. It is shown that by increase of ZnO time contact with CO the quantity of adsorbed CO(N σ/0 ), capable of fast exchange with a gaseous phase, is reduced and the quantity of slowly exchanged adsorbed CO is increased. Correlation between decrease of N σ/0 and decrease of CO HMIE with the catalyst holding time in CO medium is stated

Charge exchange reactions and the efficiency of solar neutrino detectors

International Nuclear Information System (INIS)

Austin, S.M.; Anantaraman, N.; Love, W.G.

1994-01-01

The efficiencies of solar neutrino detectors are often based in part on weak interaction strengths determined by (p,n) and other charge exchange reactions. Although the (p,n) determinations are surprisingly good, it is shown that they may be inaccurate for important Gamow-Teller transitions whose strengths are a small fraction of the sum rule limit. This emphasizes the importance of direct calibration with ν sources for detectors such as 127 I and 115 In where direct β-decay information cannot be obtained. It may also bear on recent attempts to compare charge exchange and beta decay in the mass-37 system

Ligand Exchange Kinetics of Environmentally Relevant Metals

Energy Technology Data Exchange (ETDEWEB)

Panasci, Adele Frances [Univ. of California, Davis, CA (United States)

2014-07-15

The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as ²³⁷Np is a radioactive transuranic element with a half-life of 2 million years.

13C(α,n)16O reaction as the knock-out exchange process

International Nuclear Information System (INIS)

Kim, G.; Khajdarov, R.R.; Zaparov, Eh.A.

2000-01-01

S-factor for the 13 C(α,n) 16 O reaction is studied. In the framework of the simple phenomenological model this reaction is analysed as neutron knocked-out by α-particle exchange process. The analysis demonstrates the importance of taking into account 2p-state in 13 C. The 13 C(α,n) 16 O cross section is considered both as the knock-out exchange process and as it's combination with process through a compound nucleus. It was shown that for E α s value extrapolated to low energies is found to be noticeably larger that of R-matrix analysis. Different ways of improving the proposed model are discussed. (author)

Quasiclassical trajectory study of the molecular beam kinetics of the deuterium atom--hydrogen halide exchange reactions

International Nuclear Information System (INIS)

Raff, L.M.; Suzukawa, H.H. Jr.; Thompson, D.L.

1975-01-01

Unadjusted quasiclassical trajectory computations have been carried out to simulate the molecular beam scattering of thermal D atom beams at 2800 degreeK crossed with beams of HCl and HI at 250 degreeK. Total reaction cross sections, energy partitioning distributions, and differential scattering cross sections have been computed for the exchange reactions D+HCl → DCl+H and D+HI → DI+H while total reaction cross sections are reported for the corresponding abstractions, i.e., D+HCl → HD+Cl and D+HI → HD+I. For the exchange reactions, the computed reaction cross sections are within the range estimated from the crossed beam experiments. The calculated average energy partitioned into relative translational motion of products is in near quantitative agreement with the beam results, and the predicted differential scattering cross sections appear to be in qualitative accord with the beam experiments. The over-all agreement between theory and experiment indicates that previously computed values for the thermal rate coefficients for the exchange reactions are of the right order and that a systematic error exists in the interpretation of photolysis data in the hydrogen--hydrogen halide systems

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

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.

Preparation of radioactive acetyl-l-carnitine by an enzymatic exchange reaction

International Nuclear Information System (INIS)

Emaus, R.; Bieber, L.L.

1982-01-01

A rapid method for the preparation of [1- 14 C]acetyl-L-carnitine is described. The method involves exchange of [1- 14 C]acetic acid into a pool of unlabeled acetyl-L-carnitine using the enzymes acetyl-CoA synthetase and carnitine acetyltransferase. After isotopic equilibrium is attained, radioactive acetylcarnitine is separated from the other reaction components by chromatography on Dowex 1 (C1 - ) anion exchange resin. One of the procedures used to verify the product [1- 14 C]acetyl-L-carnitine can be used to synthesize (3S)-[5- 14 C]citric acid

Tensor exchange amplitudes in K +- N charge exchange reactions

International Nuclear Information System (INIS)

Svec, M.

1979-01-01

Tensor (A 2 ) exchange amplitudes in K +- N charge exchange (CEX) are constructed from the K +- N CEX data supplemented by information on the vector (rho) exchange amplitudes from πN sca tering. We observed new features in the t-structure of A 2 exchange amplitudes which contradict the t-de pendence anticipated by most of the Regge models. The results also provide evidence for violation of weak exchange degeneracy

EXFOR systems manual: Nuclear reaction data exchange format. Revision 97/1

International Nuclear Information System (INIS)

McLane, V.

1997-07-01

This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Center Network. In addition to storing the data and its' bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility rather than optimization of data processing in order to meet the diverse needs of the nuclear reaction data centers. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine)

Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons.

Science.gov (United States)

Greene, Samuel M; Shan, Xiao; Clary, David C

2015-12-17

Quantum mechanical methods for calculating rate constants are often intractable for reactions involving many atoms. Semiclassical transition state theory (SCTST) offers computational advantages over these methods but nonetheless scales exponentially with the number of degrees of freedom (DOFs) of the system. Here we present a method with more favorable scaling, reduced-dimensionality SCTST (RD SCTST), that treats only a subset of DOFs of the system explicitly. We apply it to three H abstraction and exchange reactions for which two-dimensional potential energy surfaces (PESs) have previously been constructed and evaluated using RD quantum scattering calculations. We differentiated these PESs to calculate harmonic frequencies and anharmonic constants, which were then used to calculate cumulative reaction probabilities and rate constants by RD SCTST. This method yielded rate constants in good agreement with quantum scattering results. Notably, it performed well for a heavy-light-heavy reaction, even though it does not explicitly account for corner-cutting effects. Recent extensions to SCTST that improve its treatment of deep tunneling were also evaluated within the reduced-dimensionality framework. The success of RD SCTST in this study suggests its potential applicability to larger systems.

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)

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

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

International Nuclear Information System (INIS)

Gober, J.R.

1988-01-01

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

A phenomenological study of the π- p → π0 n charge exchange reaction at high energy

International Nuclear Information System (INIS)

Michaud, Y.

1995-01-01

The aim of the study was to examine the behaviour of the proton-proton elastic scattering, for mass center energies around 10 GeV, and more especially to study the charge exchange reaction π - p → π 0 n for mass center energies between 3 and 20 GeV. A formalism based on the Glauber model has been used, and a Regge trajectory exchange term was introduced in the model in order to enable the description of the lower energy domain (inferior to 10 GeV) that is characterized by a large contribution of meson exchanges at the scattering amplitude. The Glauber model is then applied to the charge exchange reaction and the differential cross section is analyzed for a center mass energy comprised between 3 and 20 GeV, together with the polarization at 40 GeV/c. The approach is then validated through the study of the π - p → η n reaction. The size of the kernel of proton and pion components implied in the π - p → π 0 n reaction, is also investigated. 90 refs., 48 figs., 4 tabs., 5 appends

Strong Metal Support Interaction of Pt and Ru Nanoparticles Deposited on HOPG Probed by the H-D Exchange Reaction

DEFF Research Database (Denmark)

Fiordaliso, Elisabetta M.; Dahl, Søren; Chorkendorff, Ib

2012-01-01

The interaction between metals and support is investigated in the case of 50 Å Pt and 50 Å Ru films deposited on a HOPG substrate. The films are prepared by electron beam physical vapor deposition and annealed in UHV to temperatures up to 700 °C. The equilibrium hydrogen exchange rate between...... adsorbed and gas phase at 1 bar is measured before and after annealing. The rate is measured in the temperature range of 40–200 °C at 1 bar, by utilization of the H-D exchange reaction. Experiments are performed on fresh cleaved and sputtered HOPG, which give similar results. We find that annealing...... the films from 150 up to 700 °C increases the amount of carbon present in the films up to 95%, as derived by surface analysis, indicating the formation of a carbon layer on top of the metal films. The exchange rate decreases dramatically with increasing carbon content on the films for both metals, pointing...

Kinetics of the radiation-induced exchange reactions of H2, D2, and T2: a review

International Nuclear Information System (INIS)

Pyper, J.W.; Briggs, C.K.

1978-01-01

Mixtures of H 2 --T 2 or D 2 --T 2 will exchange to produce HT or DT due to catalysis by the tritium β particle. The kinetics of the reaction D 2 + T 2 = 2DT may play an important role in designing liquid or solid targets of D 2 --DT--T 2 for implosion fusion, and distillation schemes for tritium cleanup systems in fusion reactors. Accordingly, we have critically reviewed the literature for information on the kinetics and mechanism of radiation-induced self-exchange reactions among the hydrogens. We found data for the reaction H 2 + T 2 = 2HT in the gas phase and developed a scheme based on these data to predict the halftime to equilibrium for any gaseous H 2 + T 2 mixture at ambient temperature with an accuracy of +-10 percent. The overall order of the H 2 + T 2 = 2HT reaction is 1.6 based on an initial rate treatment of the data. The most probable mechanism for radiation-induced self-exchange reaction is an ion-molecule chain mechanism

Use of deuterium n. m. r. spectroscopy in mechanistic studies of exchange reactions of ethers on supported metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Campbell, J.A.; Kemball, Charles; McDougall, G.S.

1987-10-01

Exchange reactions of diethyl ether (DEE) and tetrahydrofuran (THF) with deuterium have been studied over supported nickel, palladium, platinum, and rhodium catalysts. Products from most of the systems were analysed by deuterium n.m.r. spectroscopy (55.28 MHz) which gave quantitative results about the distribution of deuterium in the exchanged ethers. The results confirm earlier conclusions about the mechanism of the exchange of DEE and provide new evidence about the reactions of THF. Some hydrogenolysis occurred simultaneously with exchange of THF over both nickel and platinum.

Ion exchange kinetics of alkaline earths on Zr(IV) arsenosilicate cation exchanger

International Nuclear Information System (INIS)

Varshney, K.G.; Agrawal, S.; Varshney, K.

1984-01-01

A new approach based on the Nernst-Planck equations was applied to study the ion exchange kinetics for the exchange reactions of Mg(II), Ca(II), Sr(II) and Ba(II) with H + -ions at various temperatures on the zirconium(IV) arsenosilicate phase. Under the conditions of particle diffusion, the rate of exchange was found to be independent of the metal ion concentration at and above 0.1 M in aqueous medium. Energy and entropy of activation were determined and found to vary linearly with the ionic radii and mobilities of alkaline earths, a unique feature observed for an inorganic ion exchanger. The results are useful for predicting the ion exchange processes occurring on the surface of an inorganic material of the type studied. (author)

Gaseous anion chemistry. Hydrogen-deuterium exchange in mono- and dialcohol alkoxide ions: ionization reactions in dialcohols

International Nuclear Information System (INIS)

Lloyd, J.R.; Agosta, W.C.; Field, F.H.

1980-01-01

The subject of this work is H-D exchange in certain gaseous anions using D 2 as the exchanging agent. The anions involved are produced from ethylene glycol, 1,3-propanediol, 1,4-butanediol, ethanol, 1-propanol, and 1-butanol. Spectra and postulated ionization reactions for these mono- and dialcohols are given. Hydrogen-deuterium exchange occurs in the (M - 1) - and (2M - 1) - ions of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The amount of exchange occurring is 3-8 times greater in (2M - 1) - than in (M - 1) - . The amount of H-D exchange occurring in ethanol, 1-propanol, and 1-butanol is small or zero in the (2M - 1) - ions and in the (M - 1) - ion for 1-butanol [the only (M - 1) - ion which could be examined experimentally]. The amount of exchange occurring in the (2M - 1) - and (M - 1) - ions from ethylene glycol is not affected by the total pressure or composition of the reaction mixture in the ionization chamber of the mass spectrometer. A novel hydrogen-bridging mechanism is suggested to account for the observed exchange occurring in the dialcohols

Acetone and Water on TiO(110): H/D Exchange

International Nuclear Information System (INIS)

Henderson, Michael A.

2005-01-01

Isotopic H/D exchange between coadsorbed acetone and water on the TiO(110) surface was examined using temperature programmed desorption (TPD) as a function of coverage and two surface pretreatments (oxidation and reduction). Coadsorbed acetone and water interact repulsively on reduced TiO(110) based on results from the companion paper to this study, with water exerting a greater influence in destabilizing acetone and acetone having only a nominal influence on water. Despite the repulsive interaction between these coadsorbates, about 0.02 ML of a 1 ML d6-acetone on the reduced surface exhibits H/D exchange with coadsorbed water, with the exchange occurring exclusively in the high temperature region of the d?-acetone TPD spectrum at ∼340 K. The effect was confirmed with combinations of d?-acetone and D?O. The extent of exchange decreased on the reduced surface with water coverages above ∼0.3 ML due to the ability of water to displace coadsorbed acetone from first layer sites to the multilayer. In contrast, the extent of exchange increased by a factor of 3 when the surface was pre-oxidized prior to coadsorption. In this case, there was no evidence for the negative influence of high water coverages on the extent of H/D exchange. Comparison of the TPD spectra from the exchange products (either d?- or d?-acetone depending on the coadsorption pairing) suggests that, in addition to the 340 K exchange process seen on the reduced surface, a second exchange process was observed on the oxidized surface at ∼390 K. In both cases (oxidized and reduced), desorption of the H/D exchange products appeared to be reaction limited and to involve the influence of OH/OD groups (or water formed during recombinative desorption of OH/OD groups) instead of molecularly adsorbed water. The 340 K exchange process is assigned to reaction at step sites and the 390 K exchange process is attributed to the influence of oxygen adatoms deposited during surface oxidation. The H/D exchange

Oxygen exchange at gas/oxide interfaces: how the apparent activation energy of the surface exchange coefficient depends on the kinetic regime.

Science.gov (United States)

Fielitz, Peter; Borchardt, Günter

2016-08-10

In the dedicated literature the oxygen surface exchange coefficient KO and the equilibrium oxygen exchange rate [Fraktur R] are considered to be directly proportional to each other regardless of the experimental circumstances. Recent experimental observations, however, contradict the consequences of this assumption. Most surprising is the finding that the apparent activation energy of KO depends dramatically on the kinetic regime in which it has been determined, i.e. surface exchange controlled vs. mixed or diffusion controlled. This work demonstrates how the diffusion boundary condition at the gas/solid interface inevitably entails a correlation between the oxygen surface exchange coefficient KO and the oxygen self-diffusion coefficient DO in the bulk ("on top" of the correlation between KO and [Fraktur R] for the pure surface exchange regime). The model can thus quantitatively explain the range of apparent activation energies measured in the different regimes: in the surface exchange regime the apparent activation energy only contains the contribution of the equilibrium exchange rate, whereas in the mixed or in the diffusion controlled regime the contribution of the oxygen self-diffusivity has also to be taken into account, which may yield significantly higher apparent activation energies and simultaneously quantifies the correlation KO ∝ DO(1/2) observed for a large number of oxides in the mixed or diffusion controlled regime, respectively.

Momentum transfer in relativistic heavy ion charge-exchange reactions

Science.gov (United States)

Townsend, L. W.; Wilson, J. W.; Khan, F.; Khandelwal, G. S.

1991-01-01

Relativistic heavy ion charge-exchange reactions yield fragments (Delta-Z = + 1) whose longitudinal momentum distributions are downshifted by larger values than those associated with the remaining fragments (Delta-Z = 1, -2,...). Kinematics alone cannot account for the observed downshifts; therefore, an additional contribution from collision dynamics must be included. In this work, an optical model description of collision momentum transfer is used to estimate the additional dynamical momentum downshift. Good agreement between theoretical estimates and experimental data is obtained.

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

Science.gov (United States)

Ji, Y.; Shen, C.

2014-03-01

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

Isotopic Exchange in Porous and Dense Magnesium Borohydride.

Science.gov (United States)

Zavorotynska, Olena; Deledda, Stefano; Li, Guanqiao; Matsuo, Motoaki; Orimo, Shin-ichi; Hauback, Bjørn C

2015-09-01

Magnesium borohydride (Mg(BH4)2) is one of the most promising complex hydrides presently studied for energy-related applications. Many of its properties depend on the stability of the BH4(-) anion. The BH4(-) stability was investigated with respect to H→D exchange. In situ Raman measurements on high-surface-area porous Mg(BH4 )2 in 0.3 MPa D2 have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas-solid isotopic exchange follows the BH4(-) +D˙ →BH3D(-) +H˙ mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH4)2 and its dense-phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid-state H(D) diffusion is considerably slower than the gas-solid H→D exchange reaction at the surface and it is a rate-limiting steps for hydrogen desorption and absorption in Mg(BH4)2. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

Science.gov (United States)

Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

2015-01-01

The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

Charge exchange reactions and solar neutrino detection in 81Br

International Nuclear Information System (INIS)

Liu, K.F.; Gabbard, F.

1983-01-01

The feasibility of 81 Br as the detector of the solar neutrino flux hinges upon the knowledge of the Gamow-Teller matrix element from the ground state of 81 Br to the (5/2) - state at 0.457 MeV in 81 Kr. The possibility of obtaining this matrix element is discussed in terms of the (p,n) and ( 3 He, t) charge exchange reactions. .ID CR2009 .PG 98 112

A mathematical analysis of Prx2-STAT3 disulfide exchange rate constants for a bimolecular reaction mechanism.

Science.gov (United States)

Langford, Troy F; Deen, William M; Sikes, Hadley D

2018-03-22

Appreciation of peroxiredoxins as the major regulators of H 2 O 2 concentrations in human cells has led to a new understanding of redox signaling. In addition to their status as the primary reducers of H 2 O 2 to water, the oxidized peroxiredoxin byproduct of this reaction has recently been shown capable of participation in H 2 O 2 -mediated signaling pathways through disulfide exchange reactions with the transcription factor STAT3. The dynamics of peroxidase-transcription factor disulfide exchange reactions have not yet been considered in detail with respect to how these reactions fit into the larger network of competing reactions in human cells. In this study, we used a kinetic model of oxidation and reduction reactions related to H 2 O 2 metabolism in the cytosol of human cells to study the dynamics of peroxiredoxin-2 mediated oxidation of the redox-regulated transcription factor STAT3. In combination with previously reported experimental data, the model was used to estimate the rate coefficient of a biomolecular reaction between Prx2 and STAT3 for two sets of assumptions that constitute lower and upper bound cases. Using these estimates, we calculated the relative rates of the reaction of oxidized peroxiredoxin-2 and STAT3 and other competing reactions in the cytosol. These calculations revealed that peroxiredoxin-2-mediated oxidation of STAT3 likely occurs at a much slower rate than competing reactions in the cytosol. This analysis suggests the existence of more complex mechanisms, potentially involving currently unknown protein-protein recognition partners, which facilitate disulfide exchange reactions between peroxiredoxin-2 and STAT3. Copyright © 2018 Elsevier Inc. All rights reserved.

Exchanged cations and water during reactions in polypyrrole macroions from artificial muscles.

Science.gov (United States)

Valero, Laura; Otero, Toribio F; Martínez, José G

2014-02-03

The movement of the bilayer (polypyrrole-dodecylbenzenesulfonate/tape) during artificial muscle bending under flow of current square waves was studied in aqueous solutions of chloride salts. During current flow, polypyrrole redox reactions result in variations in the volumes of the films and macroscopic bending: swelling by reduction with expulsion of cations and shrinking by oxidation with the insertion of cations. The described angles follow a linear function, different in each of the studied salts, of the consumed charge: they are faradaic polymeric muscles. The linearity indicates that cations are the only exchanged ions in the studied potential range. By flow of the same specific charge in every electrolyte, different angles were described by the muscle. The charge and the angle allow the number and volume of both the exchanged cations and the water molecules (related to a reference) between the film to be determined, in addition to the electrolyte per unit of charge during the driving reaction. The attained apparent solvation numbers for the exchanged cations were: 0.8, 0.7, 0.6, 0.5, 0.5, 0.4, 0.25, and 0.0 for Na(+), Mg(2+), La(3+), Li(+), Ca(2+), K(+), Rb(+), and Cs(+), respectively. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Air/surface exchange processes of mercury and their linkage to atmospheric pools

International Nuclear Information System (INIS)

Bahlmann, Enno; Ebinghaus, Ralf

2001-01-01

The atmospheric mercury cycle is strongly linked to the terrestrial, aquatic and biologic cycle of mercury via air/surface exchange processes. In order to quantify mercury fluxes from and to the atmosphere to predict local and regional source contributions the methods for flux measurements as well as the physicochemical factors controlling air/surface exchange processes must be assessed. We will describe methods for the determination of mercury and mercury species in ambient air which are basic for investigation of air/surface exchange processes. Further on we will describe approaches for studying the physicochemical factors controlling this processes by using a new laboratory flux measurement system. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-03-15

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

A computational study of a recreated G protein-GEF reaction intermediate competent for nucleotide exchange: fate of the Mg ion.

Directory of Open Access Journals (Sweden)

Mériam Ben Hamida-Rebaï

Full Text Available Small G-proteins of the superfamily Ras function as molecular switches, interacting with different cellular partners according to their activation state. G-protein activation involves the dissociation of bound GDP and its replacement by GTP, in an exchange reaction that is accelerated and regulated in the cell by guanine-nucleotide exchange factors (GEFs. Large conformational changes accompany the exchange reaction, and our understanding of the mechanism is correspondingly incomplete. However, much knowledge has been derived from structural studies of blocked or inactive mutant GEFs, which presumably closely represent intermediates in the exchange reaction and yet which are by design incompetent for carrying out the nucleotide exchange reaction. In this study we have used comparative modelling to recreate an exchange-competent form of a late, pre-GDP-ejection intermediate species in Arf1, a well-characterized small G-protein. We extensively characterized three distinct models of this intermediate using molecular dynamics simulations, allowing us to address ambiguities related to the mutant structural studies. We observed in particular the unfavorable nature of Mg2+ associated forms of the complex and the establishment of closer Arf1-GEF contacts in its absence. The results of this study shed light on GEF-mediated activation of this small G protein and on predicting the fate of the Mg ion at a critical point in the exchange reaction. The structural models themselves furnish additional targets for interfacial inhibitor design, a promising direction for exploring potentially druggable targets with high biological specificity.

Thermal-hydraulic performance of the finned surface of a compact heat exchanger

International Nuclear Information System (INIS)

Errasti Cabrera, Michel

2015-01-01

In this work the thermal-hydraulic behavior of the finned surface of a compact heat exchanger is obtained in tube-fin configuration corrugated (wavy). Through numerical simulation are determined average values ​​of intensification of heat transfer and pressure loss in the inter-channel finned. The objective is to characterize the surface to use as a reference, to make comparisons with other heat exchange surfaces enhanced using traditional techniques combined with more current, such as vortex generators. The study is conducted in laminar flow, with Reynolds numbers below 1000. In the working model compact exchanger tubes and corrugated fins (wavy) heat is described, and the results of the coefficient of overall heat transfer and the pressure drop are explained from the local characteristics of the velocity field and temperature inside the heat exchanger. (Full text)

Kinetic analysis of the reactivity of aromatic amino acids in the T-for-H exchange reaction

International Nuclear Information System (INIS)

Yoshida, Akira; Imaizumi, Hiroshi; Sato, Takayuki; Kano, Naoki

2009-01-01

To quantitatively evaluate the influence of tritium ( 3 H or T) on ecosystem, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between each aromatic amino acid (L-tyrosine, L-phenylalanine, or L-2-phenylglycine) and HTO vapor was observed at 50-70degC in the gas-solid system. Applying the A''-McKay plot method to data (obtained in the exchange reaction), the rate constants (k) of functional groups of each aromatic amino acid in this reaction was obtained. Comparing the rate constants, following six matters have been found in the T-for-H exchange reaction. (1) The reactivity of the functional groups in each amino acid increases with increasing temperature. (2) The reactivity of the functional groups of the amino acids (used) increases in the order of L-tyrosine, L-phenylalanine, and L-2-phenylglycine. (3) As to l-tyrosine, 1) the temperature dependence of each functional group increases in the order of COOH group, OH one, and NH 2 one, 2) the reactivity of OH group is 3.8 times greater than that of NH 2 one, and 3) the reactivity of COOH group is 2.0 times greater than NH 2 one. (4) As to the influence of the substituent, the reactivity of NH 2 group is larger than that of the COOH one. (5) Using the A''-McKay plot method, the reactivity of each functional group in an amino acid can be nondestructively and simultaneously clarified without using masking reagent. (6) The results obtained in this work is useful for preventing T contamination and for evaluating the influence of T on environment. (author)

Thermodynamics of calcium-isotope-exchange reactions. 1. Exchange between isotopic calcium carbonates and aqueous calcium ions

International Nuclear Information System (INIS)

Zhang, R.S.; Nash, C.P.; Rock, P.A.

1988-01-01

This paper reports the authors results for the direct experimental determination of the equilibrium constant for the calcium-isotope-exchange reaction 40 CaCO 3 (s) + 44 CaCl 2 (aq) reversible 44 CaCO 2 (s) + 40 CaCl 2 (aq). The reaction was studied in electrochemical double cells without liquid junction of the type shown in eq 2. The experimental value of the equilibrium constant at 295 +/- 2 K is K = 1.08 +/- 0.02. The experimental value for K is compared with the values of K calculated for various model reactions according to the statistical thermodynamic theory of isotope effects. The isotopic solid carbonates were modeled according to both the Debye and Kieffer theories. No structured models of solvated isotopic aqueous calcium ions yield calculated equilibrium constants in agreement with their experimental results. This conclusion is in agreement with published molecular dynamics calculations which show that the aqueous solvation of Ca 2 =(aq) is essentially unstructured

Experimental Investigation of Gaseous Reaction Products from Na-CO{sub 2} Reaction in Na/CO{sub 2} Heat Exchanger leakage scenario

Energy Technology Data Exchange (ETDEWEB)

Go, A-Reum; Jung, Hwa-Young; Kim, Min Seok; Lee, Jeong Ik [KAIST, Daejeon (Korea, Republic of); Min, Jaehong; Wi, Myung-Hwan [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2015-10-15

The SFRs have operated with the steam Rankine cycle as a power conversion system. However, the potential sodium-water reaction (SWR) whose chemical reactivity is vigorous and instantaneous has been one of the major issues concerning the safety and integrity of the SFRs. In order to avoid SWR, supercritical CO{sub 2}(S-CO{sub 2}) Brayton cycles have been investigated recently. Compared to conventional steam Rankine cycles, S-CO{sub 2} Brayton cycle features higher thermal efficiency and potential compactness of its required equipment. In spite of the superiority of S-CO{sub 2} Brayton cycle, there is a potential reactive process between sodium and CO{sub 2} if the pressure boundary fails in the sodium-CO{sub 2} heat exchanger. The leakage scenario which could lead to mechanical and thermal problems should be evaluated. Previous studies have reported the following major reaction formulas. Each reaction occurs competitively. In this paper, the experimental setup to observe the pressure variation and CO concentration in Na-CO{sub 2} heat exchanger during the CO{sub 2} leak is explained. Before the experiment is carried out, water-CO{sub 2} mock-up test will be performed. In order to evaluate the leakage scenario in Na-CO{sub 2} heat exchanger more accurately, this study will be important for guaranteeing the system of SFR coupled with S-CO{sub 2} cycle.

Basic reactions of osteoblasts on structured material surfaces

Directory of Open Access Journals (Sweden)

U. Meyer

2005-04-01

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

The use of deuterium n.m.r. spectroscopy in mechanistic studies of exchange reactions of ethers on supported metal catalysts

International Nuclear Information System (INIS)

Campbell, J.A.; Kemball, Charles; McDougall, G.S.

1987-01-01

Exchange reactions of diethyl ether (DEE) and tetrahydrofuran (THF) with deuterium have been studied over supported nickel, palladium, platinum, and rhodium catalysts. Products from most of the systems were analysed by deuterium n.m.r. spectroscopy (55.28 MHz) which gave quantitative results about the distribution of deuterium in the exchanged ethers. The results confirm earlier conclusions about the mechanism of the exchange of DEE and provide new evidence about the reactions of THF. Some hydrogenolysis occurred simultaneously with exchange of THF over both nickel and platinum. (author)

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

Novel exchange mechanisms in the surface diffusion of oxides

International Nuclear Information System (INIS)

Harris, Duncan J; Lavrentiev, Mikhail Yu; Harding, John H; Allan, Neil L; Purton, John A

2004-01-01

We use temperature-accelerated dynamics to show the importance of exchange mechanisms in surface diffusion and growth of simple oxides. Such mechanisms can dominate transport processes both on terraces and steps for both homoepitaxial and heteroepitaxial growth. We suggest that the mixing inevitable when an exchange mechanism is present must be considered when attempts are made to grow sharp interfaces in oxide nanostructures. (letter to the editor)

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

Nucleon charge exchange reaction and antiproton elastic scattering at intermediate energies

International Nuclear Information System (INIS)

Kronenfeld, J.

1985-02-01

This work treats the medium energy nuclear (p,n) charge exchange reaction to analog states and the low energy elastic scattering of antiprotons and investigates the central aspects of a microscopic theory based on multiple-scattering series which are pertinent to these reactions. A two-step term of the Distorted Wave Impulse Approximation (DWIA) in treating the (p,n) reaction, was included. For the very absorptive p-bar interaction with nuclei we conjecture that a partial infinite summation, constituing a renormalization of the single scattering term of the optical potential series provides the dominant feature of this interaction. In this work the excitation of analog states is calculated and it was found that the (p,n) reaction is described fairly well by the DWIA. In the first part of the work the (p,n) reaction in the energy range 100-200 MeV was treated. The DWIA calculations were based on eikonalization. In the second part of the work the p-barA interaction with the selfconsistent scheme mentioned above, for scattering energies 30-120 MeV, was examined. (author)

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

International Nuclear Information System (INIS)

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

1976-01-01

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

Exchange energy of inhomogenous electron gas near a metal surface

International Nuclear Information System (INIS)

Miglio, L.; Tosi, M.P.; March, N.H.

1980-12-01

Using the first-order density matrix of an infinite-barrier model of a metal surface, the exchange energy density can be evaluated exactly as a function of distance z from the barrier. This result is compared with the local approximation -3/4e 2 (3/π)sup(1/3) rhosup(4/3)(z) where rho is the electron density in the model. The local approximation is demonstrated to be quantitatively accurate at all z. The integrated surface exchange energy is given to within 3% by the local theory. (author)

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.

Bidirectional exchange of biogenic volatiles with vegetation: emission sources, reactions, breakdown and deposition

Science.gov (United States)

Niinemets, Ülo; Fares, Silvano; Harley, Peter; Jardine, Kolby J.

2014-01-01

Biogenic volatile organic compound (BVOC) emissions are widely modeled as inputs to atmospheric chemistry simulations. However, BVOC may interact with cellular structures and neighboring leaves in a complex manner during volatile diffusion from the sites of release to leaf boundary layer and during turbulent transport to the atmospheric boundary layer. Furthermore, recent observations demonstrate that the BVOC emissions are bidirectional, and uptake and deposition of BVOC and their oxidation products are the rule rather than the exception. This review summarizes current knowledge of within-leaf reactions of synthesized volatiles with reactive oxygen species (ROS), uptake, deposition and storage of volatiles and their oxidation products as driven by adsorption on leaf surface and solubilization and enzymatic detoxification inside leaves. The available evidence indicates that due to reactions with ROS and enzymatic metabolism, the BVOC gross production rates are much larger than previously thought. The degree to which volatiles react within leaves and can be potentially taken up by vegetation depends on compound reactivity, physicochemical characteristics, as well as their participation in leaf metabolism. We argue that future models should be based on the concept of bidirectional BVOC exchange and consider modification of BVOC sink/source strengths by within-leaf metabolism and storage. PMID:24635661

Uranium isotope exchange between gaseous UF6 and solid UF5

International Nuclear Information System (INIS)

Yato, Yumio; Kishimoto, Yoichiro; Sasao, Nobuyuki; Suto, Osamu; Funasaka, Hideyuki

1996-01-01

Based on a collision model, a new rate equation is derived for uranium isotope exchange between gaseous UF 6 and solid UF 5 by considering the number of UF 5 molecules on the solid surface to be dependent on time. The reaction parameters included in the equation are determined from the experimental data and compared with the previous ones. A remarkable agreement is found between the particle sizes of UF 5 estimated from the reaction parameter and from the direct observation with an electron microscope. The rate equation given in this work fully satisfies the related mass conservation and furthermore includes explicitly the terms related to the UF 6 density and the mean size of UF 5 particles, both of which are considered to cause an important effect on the reaction. This remarkable feature facilitates the simulation studies on this reaction under various conditions. The long term behavior of a simulated exchange reaction is studied under the condition considered to be close to that in a recovery zone of the MLIS process. The result indicates that the reaction is virtually limited to the solid surface under this conditions and thus the depletion of 235 UF 5 concentration averaged over the whole UF 5 particles is not significant even after 200 h of the exchange reaction

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)

Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

Science.gov (United States)

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

2018-01-09

Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

Double Charge Exchange Reactions and Double Beta Decay

Science.gov (United States)

Auerbach, N.

2018-05-01

The subject of this presentation is at the forefront of nuclear physics, namely double beta decay. In particular one is most interested in the neutrinoless process of double beta decay, when the decay proceeds without the emission of two neutrinos. The observation of such decay would mean that the lepton conservation symmetry is violated and that the neutrinos are of Majorana type, meaning that they are their own anti-particles. The life time of this process has two unknowns, the mass of the neutrino and the nuclear matrix element. Determining the nuclear matrix element and knowing the cross-section well will set limits on the neutrino mass. There is a concentrated effort among the nuclear physics community to calculate this matrix element. Usually these matrix elements are a very small part of the total strength of the transition operators involved in the process. There is no simple way to “calibrate” the nuclear double beta decay matrix element. The double beta decay is a double charge exchange process, therefore it is proposed that double charge exchange reactions using ion projectiles on nuclei that are candidates for double beta decay, will provide additional necessary information about the nuclear matrix elements.

A paradox: The thermal rate coefficient for the H+DCl → HCl+D exchange reaction

International Nuclear Information System (INIS)

Thompson, D.L.; Suzukawa, H.H. Jr.; Raff, L.M.

1975-01-01

Previously reported photolysis experiments indicate that the frequency factors associated with the hydrogen-exchange reactions H+DCl → HCl+D and D+HCl → DCl+H are on the order of 10 10 cm 3 /molcenter-dotsec. A series of unadjusted, quasiclassical trajectory calculations were been carried out to compute the thermal rate coefficients and activation parameters for a series of 13 thermal processes of the type A+BC → AB+C, where A=H, D, or Cl and BC=H 2 , D 2 , HCl, DCl, or Cl 2 . In addition, hot-atom yield ratios have been computed from the IRP equation for the reactions D*+DCl → D 2 +Cl, D*+Cl 2 → DCl + Cl as a function of the initial D* laboratory energy. The computations yield (1) hot-atom DCl/D 2 yield ratios within a factor of 2 of the experimental values; (2) thermal activation energies in satisfactory agreement with experiment for all processes investigated; and (3) frequency factors in reasonable accord with experiment for all the reactions except the hydrogen exchange reactions

Addition and spin exchange rate constants by longitudinal field μSR: the Mu + NO reaction

International Nuclear Information System (INIS)

Senba, Masayoshi; Gonzalez, A.C.; Kempton, J.R.; Arseneau, D.J.; Pan, J.J.; Tempelmann, A.; Fleming, D.G.

1991-01-01

The addition reaction Mu + NO + M → MuNO + M and the spin exchange reaction Mu(↑) + NO(↓)→Mu(↓)+NO(↑) have been measured by longitudinal field μSR at room temperature in the presence of up to 58 atm of N 2 as inert collider. The pressure dependence of the longitudinal relaxation rate due to the addition reaction (λ c ) demonstrates that the system is still in the low pressure regime in this pressure range. The corresponding termolecular rate constant has been determined as k 0.Mu =(1.10±0.25)x10 -32 cm 6 molecules -2 s -1 , almost 4 times smaller than the corresponding H atom reaction k 0,H =3.90x10 -32 cm 6 molecules -2 s -1 . The average value of the spin exchange rate constants in the 2.5-58 atm pressure range, k SE = (3.16±0.06)x10 -10 cm 3 molecule -1 s -1 , is in good agreement with previous values obtained by transverse field μSR. (orig.)

A meson-exchange isobar model for the {pi}{sup +}d {r_reversible} pp reaction

Energy Technology Data Exchange (ETDEWEB)

Canton, L.; Cattapan, G.; Dortmans, P.J.; Pisent, G. [Istituto Nazionale di Fisica Nucleare, Padua (Italy); Svenne, J.P. [Manitoba Univ., Winnipeg, MB (Canada). Dept. of Physics]|[Winnipeg Inst. for Theoretical Physics, Winnipeg, MB (Canada)

1994-10-10

A broad set of observables are calculated for the {pi}{sup +} d {r_reversible} pp reaction with a relatively simple meson-exchange isobar model. The comparison between the calculated results and experimental data (including spin observables), shows that the model gives an overall phenomenologically acceptable description of the reaction around the {Delta} resonance. The effects due to the inclusion of Galilei invariant (pseudovector) recoil term in the {pi}NN vertex, of relativistic corrections to the {rho}-exchange component of the {Delta}N transition potential, and of NN final state interaction in the {pi}{sup +}d {yields} p+p process are also discussed. It is estimated that the model is sufficiently simple to be extended to the case of pion absorption on other light nuclei, in particular {sup 3}He (or tritium). 32 refs., 13 figs.

Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

Science.gov (United States)

Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

2016-08-01

The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

New method for the hydrogen isotope exchange reaction in a hydrophobic catalyst bed

International Nuclear Information System (INIS)

Asakura, Y.; Kikuchi, M.; Yusa, H.

1982-01-01

To improve the isotope exchange reaction efficiency between water and hydrogen, a new reactor in which water mists and hydrogen gas react cocurrently was studied. To apply this to the enrichment of tritium in heavy water, a dual temperature isotope exchange reactor which is composed of cocurrent low temperature reactors and the usual countercurrent high temperature reactor was proposed and analyzed using a McCabe-Thiele diagram. By utilizing cocurrent reactors, in combination, the necessary catalyst volume can be reduced to one-tenth as compared with the usual countercurrent low temperature reactor. 17 refs

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)

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

Preparation of Two-Layer Anion-Exchange Poly(ethersulfone Based Membrane: Effect of Surface Modification

Directory of Open Access Journals (Sweden)

Lucie Zarybnicka

2016-01-01

Full Text Available The present work deals with the surface modification of a commercial microfiltration poly(ethersulfone membrane by graft polymerization technique. Poly(styrene-co-divinylbenzene-co-4-vinylbenzylchloride surface layer was covalently attached onto the poly(ethersulfone support layer to improve the membrane electrochemical properties. Followed by amination, a two-layer anion-exchange membrane was prepared. The effect of surface layer treatment using the extraction in various solvents on membrane morphological and electrochemical characteristics was studied. The membranes were tested from the point of view of water content, ion-exchange capacity, specific resistance, permselectivity, FT-IR spectroscopy, and SEM analysis. It was found that the two-layer anion-exchange membranes after the extraction using tetrahydrofuran or toluene exhibited smooth and porous surface layer, which resulted in improved ion-exchange capacity, electrical resistance, and permselectivity of the membranes.

Swi5-Sfr1 protein stimulates Rad51-mediated DNA strand exchange reaction through organization of DNA bases in the presynaptic filament.

KAUST Repository

Fornander, Louise H; Renodon-Corniè re, Axelle; Kuwabara, Naoyuki; Ito, Kentaro; Tsutsui, Yasuhiro; Shimizu, Toshiyuki; Iwasaki, Hiroshi; Nordé n, Bengt; Takahashi, Masayuki

2013-01-01

The Swi5-Sfr1 heterodimer protein stimulates the Rad51-promoted DNA strand exchange reaction, a crucial step in homologous recombination. To clarify how this accessory protein acts on the strand exchange reaction, we have analyzed how the structure

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.

Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

Science.gov (United States)

Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

2018-06-01

Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

Chemistry of sustainability-Part I: Carbon dioxide as an organic synthon and Part II: Study of thermodynamics of cation exchange reactions in semiconductor nanocrystals

Science.gov (United States)

Sathe, Ajay A.

chapter introduces the role of nanomaterials in sustainable solar energy conversion and storage. The use of cation exchange reactions in nanocrystals to access novel materials is highlighted. Despite having shown tremendous promise in the synthetic applications, the fundamental measurements of the thermodynamic and kinetic parameters of a cation exchange reaction are largely non-existent. This impedes the future growth of this powerful methodology. The technique of isothermal titration calorimetry is introduced, and its importance to studying the thermochemical changes occurring during cation exchange is outlined. The final chapter presents results obtained from the isothermal titration calorimetry on the prototypical cation exchange reaction between cadmium selenide and silver ions. The role of nanoparticle size, identity of the silver salt, solvent, surface ligands and temperature is studied. Recommendations for future investigations using ITC as well as other characterization techniques for discerning the kinetics of cation exchange are presented. I believe that a more unified mechanistic understanding of the cation exchange process in nanomaterials will aid the development of more efficient and robust materials for applications in a wide variety of fields.

Relationship Between Equilibrium Hydrogen Pressure and Exchange Current for the Hydrogen Electrode-Reaction at Mmni(3.9-X)Mn(0.4)A1(X)Co(0.7) Alloy Electrodes

NARCIS (Netherlands)

Senoh, H.; Morimoto, K.; Inoue, H.; Iwakura, C.; Notten, P.H.L.

2000-01-01

We present a theoretical relationship between equilibrium hydrogen pressure and exchange current for the hydrogen electrode reaction which considers the degree of hydrogen coverage at the electrode surface. Electrochemical measurements at MmNi3.9–xMn0.4AlxCo0.7 (0 x 0.8) electrodes were performed to

EXFOR basics. A short guide to the nuclear reaction data exchange format

International Nuclear Information System (INIS)

McLane, Victoria

2000-01-01

EXFOR is the agreed exchange format for the transmission of experimental nuclear reaction data between national and international nuclear data centers for the benefit of nuclear data users in all countries. This report is intended as a guide to data users. For a complete guide to the EXFOR system see: EXFOR Systems Manual, IAEA-NDS-207 (BNL-NCS-63330-00/04-Rev.) (author)

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

Absorption of carbon dioxide and isotope exchange rate of carbon in a reaction system between carbon dioxide and carbamic acid

International Nuclear Information System (INIS)

Takeshita, Kenji; Kitamoto, Asashi

1985-01-01

The performance of isotope separation of carbon-13 by chemical exchange between carbon dioxide and carbamic acid was studied. The working fluid used in the study was a solution of DNBA, (C 4 H 9 ) 2 NH and n-octane mixture. Factors related to the isotope exchange rate were measured, such as the absorption rate of carbon dioxide into the solution of DNBA and n-octane, the isotope exchange rate and the separation factor in the reaction between CO 2 and carbamic acid. The absorption of CO 2 into the working fluid was the sum of chemical absorption by DNBA and physical absorption by n-octane. The absorption of carbon dioxide into the working fluid was negligible at temperatures over 90 0 C, but increased gradually at lower temperatures. Carbon dioxide was absorbed into DNBA by chemical absorption, and DNBA was converted to carbamic acid by the reaction. The reaction for synthesis and decomposition of carbamic acid was reversible. The separation factor in equilibrium reached a large value at lower temperatures. The isotope exchange rate between gas and liquid was proportional to the product of the concentration of carbamic acid and the concentration of CO 2 by physical absorption. The isotope separation of carbon by chemical exchange reaction is better operated under the conditions of lower temperature and higher pressure. (author)

Positional isotope exchange analysis of the uridine-diphosphoglucose pyrophosphorylase reaction

International Nuclear Information System (INIS)

Hester, L.; Hilscher, L.; Raushel, F.M.

1986-01-01

The enzyme uridine-diphosphoglucose pyrophosphorylase catalyzes the reversible formation of pyrophosphate and UDP-glucose from UTP and glc-1P. The positional isotope exchange reaction was measured using oxygen-18 labelled UTP. The synthesis of [β- 18 O 2 , βγ- 18 O, γ- 18 O 3 ]UTP was accomplished by the coupled activities of carbamate kinase, nucleoside diphosphate kinase, and nucleoside monophosphate kinase. The exchange of an oxygen-18 from a β-nonbridge position of the labelled UTP to the αβ-bridge position was measured with 31 P NMR. The ratio of the rate of net substrate turnover and the positional isotope exchange rate was measured as a function of the initial glc-1P concentration. This ratio was found to increase with an increasing concentration of glc-1P. The intercept at low glc-1P was found to be 1.2 and the slope was 4.5 mM -1 . These results have been interpreted to mean that this enzyme has an ordered addition of substrates. The lower limit for the release of pyrophosphate from E-UDPG-PP/sub i/ relative to V 2 is 1.2. The rate constant for the release of UTP from E-UTP relative to V 1 is 9

A Generalizable Top-Down Nanostructuring Method of Bulk Oxides: Sequential Oxygen-Nitrogen Exchange Reaction.

Science.gov (United States)

Lee, Lanlee; Kang, Byungwuk; Han, Suyoung; Kim, Hee-Eun; Lee, Moo Dong; Bang, Jin Ho

2018-05-27

A thermal reaction route that induces grain fracture instead of grain growth is devised and developed as a top-down approach to prepare nanostructured oxides from bulk solids. This novel synthesis approach, referred to as the sequential oxygen-nitrogen exchange (SONE) reaction, exploits the reversible anion exchange between oxygen and nitrogen in oxides that is driven by a simple two-step thermal treatment in ammonia and air. Internal stress developed by significant structural rearrangement via the formation of (oxy)nitride and the creation of oxygen vacancies and their subsequent combination into nanopores transforms bulk solid oxides into nanostructured oxides. The SONE reaction can be applicable to most transition metal oxides, and when utilized in a lithium-ion battery, the produced nanostructured materials are superior to their bulk counterparts and even comparable to those produced by conventional bottom-up approaches. Given its simplicity and scalability, this synthesis method could open a new avenue to the development of high-performance nanostructured electrode materials that can meet the industrial demand of cost-effectiveness for mass production. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden-Popper phases?

Science.gov (United States)

Tomkiewicz, Alex C; Tamimi, Mazin A; Huq, Ashfia; McIntosh, Steven

2015-01-01

The possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A(n-1)A(2)'B(n)O(3n+1), A(n-1)A(2)'B(n)X(3n+1); LaSrCo(0.5)Fe(0.5)O(4-δ) (n = 1), La(0.3)Sr(2.7)CoFeO(7-δ) (n = 2) and LaSr3Co(1.5)Fe(1.5)O(10-δ) (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. This is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. We conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.

Kinetics and mechanism of ligand-exchange reactions of Cd(II) chelates

Energy Technology Data Exchange (ETDEWEB)

Nivorozhkin, L.E.; Kalabin, G.A.; Nivorozhkin, A.L.; Valeev, R.B.; Minkin, V.I.

1987-03-01

Tetrahedral Cd(II) bis(5-thio(or seleno)pyrazole-4-carboxaldiminates) of types II and III have been synthesized for the first time. The kinetics of the degenerate ligand exchange and enantiomerization of the complexes obtained have been studied by dynamic /sup 111/Cd, /sup 77/Se, and /sup 1/H (s = 1/2) NMR. The rate of intramolecular enantiomerization (k = 1/tau) is more than an order of magnitude greater than the corresponding values for processes of degenerate ligand exchange (a second-order reaction) determined from the dynamics of the averaging of the /sup 111/Cd-/sup 77/Se and /sup 111/Cd-N=CH spin-spin coupling constants. The cleavage and formation processes of the Cd-Se and Cd-N bonds are isoenergetic (..delta.. G/sub 298//sup not equal to/ = 14.4 kcal/mole for chelate II with X = Se and R = CH/sub 2/C/sub 6/H/sub 5/). The free energies of activation of degenerate ligand exchange determined form the dynamics of the averaging of the /sup 111/Cd N=CH spin-spin coupling constant increase from 12.7 to 17.9 kcal/mole along the following series for R: C/sub 2/H/sub 5/ < Ar < CH/sub 2/C/sub 6/H/sub 5/ < t-C/sub 4/H/sub 9/ < cyclo-C/sub 6/H/sub 11/. Replacement of the sulfur atom in the chelate ring by selenium results in increases in the rates of ligand exchange. A mechanism of degenerate ligand exchange has been proposed.

General Tritium Labelling of Gentamicin C by catalytic hydrogen exchange Reaction with Tritiated Water

International Nuclear Information System (INIS)

Suarez, C.; Diaz, D.; Paz, D.

1991-01-01

Gentamicin C was labelled with tritium by means of a PtO2 catalyzed hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H2O-3H, and 50 mg of prereduced PtO2) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 degree celsius, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accomplished with a cellulose column eluted with the lower phase of chloroform-methanol 17 % ammonium hydroxide (2:1:1, v/v) . Chemical purity, determined by HPLC, was 96,5 % and radiochemical one was 95. Main exchange degradation products show biological activity. (Author) 12 refs

General Tritium labelling of gentamicin C by catalytic hydrogen exchange reaction with tritiated water

International Nuclear Information System (INIS)

Suarez, C.; Diaz, D.

1991-01-01

Gentamicin C was labelled with tritium by means of a PtO 2 catalized hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H 2 O- 3 H, and 50 mg of prereduced PtO 2 ) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 o C, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accoumplished with a cellulose column eluted with the lower phase of chloroform-methanol 17 % ammonium hydroxide (2:1:1, v/v). Chemical purity, determined by HPLC, was 96,5 % and radiochemical one was 95 % . Main exchange degradation products show biological activity. (Author). 12 refs

Surface-ionization field mass-spectrometry studies of nonequilibrium surface ionization

International Nuclear Information System (INIS)

Blashenkov, Nikolai M; Lavrent'ev, Gennadii Ya

2007-01-01

The ionization of polyatomic molecules on tungsten and tungsten oxide surfaces is considered for quasiequilibrium or essentially nonequilibrium conditions (in the latter case, the term nonequilibrium surface ionization is used for adsorbate ionization). Heterogeneous reactions are supposed to proceed through monomolecular decay of polyatomic molecules or fragments of multimolecular complexes. The nonequilibrium nature of these reactions is established. The dependences of the current density of disordered ions on the surface temperature, electric field strength, and ionized particle energy distribution are obtained in analytical form. Heterogeneous dissociation energies, the ionization potentials of radicals, and the magnitude of reaction departure from equilibrium are determined from experimental data, as are energy exchange times between reaction products and surfaces, the number of molecules in molecular complexes, and the number of effective degrees of freedom in molecules and complexes. In collecting the data a new technique relying on surface-ionization field mass-spectrometry was applied. (instruments and methods of investigation)

Measurement of exclusive hypercharge-exchange reactions at 35 to 140 GeV/c

International Nuclear Information System (INIS)

Arenton, M. W.; Ayres, D.S.; Cohen, D.

1978-07-01

Data on the reactions π + p → K + Σ + and π + p → K + Y* + were obtained using the Fermilab Single Arm Spectrometer Facility at incident π + momenta of 35, 70, and 140 GeV/c for momentum transfers vertical bar t vertical bar less than or approximately equal to 1 GeV 2 . The line-reversed reactions K - p → π - Σ + and K - p → π - Y* + were also studied at 70 GeV/c with the same apparatus in order to test exchange degeneracy of the K*(890) and K**(1420) trajectories. Preliminary results on the first set of reactions at 70 GeV/c are presented and found to be in qualitative agreement with the model of Navelet and Stevens

Adsorption behaviour and kinetics of exchange of Zn2+ and Eu3+ ions on a composite ion exchanger

International Nuclear Information System (INIS)

Morcos, T.N.

2007-01-01

Equilibria and kinetics of exchange of both Zn2+ and Eu3+ ions on a composite ion-exchanger, cobalt hexacyanocobaltate (III) (CoHCC) incorporated in polyacrylonitrile (PAN), has been studied. The apparent capacity of CoHCC-PAN for Zn2+ and Eu3+ was determined and found to be 0.353 and 0.69 meq/g, respectively. The higher capacity for Eu3+ ions than that for Zn2+ ions is due to the higher electrostatic interaction strength of the higher charge ion with the surface. Freundlich and Langmiur adsorption isotherms were used to investigate solute (Zn2+ or Eu3+) exchange phenomenon at the liquid/solid interface. The results indicated that both Langmuir and Freundlich isotherms fit well for both Zn2+ and Eu3+. Sorption data have been also treated with the Dubinin-Radushkevich equation. The kinetics of Zn2+ or Eu3+ sorption on the composite seems to show that the reaction was proceed via two steps. The first one was fast and probably due to adsorption followed by a slow exchange reaction. In view of the data obtained on the effect of particle size and metal ion concentrations on the rate of exchange reaction, it is concluded that the mechanism for both ions was chemical control. Generally, it seems that there are two exchange sites chemically equivalent but present in pores of different sizes which lead to different degrees of dehydration of the ions sorbed on the two sites

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

Gallium sorption on montmorillonite and illite colloids: Experimental study and modelling by ionic exchange and surface complexation

International Nuclear Information System (INIS)

Benedicto, Ana; Degueldre, Claude; Missana, Tiziana

2014-01-01

Highlights: • Ga sorption onto illite and montmorillonite was studied and modelled for the first time. • The developed sorption model was able to well explain Ga sorption in both clays. • Number of free parameters was reduced applying the linear free energy relationship. • Cationic exchange dominate sorption at pH < 4.5; surface complexation at higher pH. - Abstract: The migration of metals as gallium (Ga) in the environment is highly influenced by their sorption on clay minerals, as montmorillonite and illite. Given the increased usage of gallium in the industry and the medicine, the Ga-associated waste may result in environmental problems. Ga sorption experiments were carried out on montmorillonite and illite colloids in a wide range of pH, ionic strength and Ga concentration. A Ga sorption model was developed combining ionic exchange and surface complexation on the edge sites (silanol and aluminol-like) of the clay sheets. The complexation constants were estimated as far as possible from the Ga hydrolysis constants applying the linear free energy relationship (LFER), which allowed to reduce the number of free parameters in the model. The Ga sorption behaviour was very similar on illite and montmorillonite: decreasing tendency with pH and dependency on ionic strength at very acidic conditions. The experimental data modelling suggests that the Ga sorption reactions avoid the Ga precipitation, which is predicted in absence of clay colloids between pH 3.5 and 5.5. Assuming this hypothesis, clay colloids would affect Ga aqueous speciation, preventing precipitation in favour of sorption. Ga sorption on montmorillonite and illite can be explained on the basis of three main reactions: Ga 3+ exchange at very acidic conditions (pH < ∼3.8); Ga(OH) 4 - complexation on protonated weak sites in acidic-neutral conditions (between pH ∼5.2 and pH ∼7.9); and Ga(OH) 3 complexation on strong sites at basic conditions (pH > ∼7.9)

Photochemical exchange reactions of thymine, uracil and their nucleosides with selected amino acids

International Nuclear Information System (INIS)

Shetlar, M.D.; Taylor, J.A.; Hom, K.

1984-01-01

The photoinduced exchange reactions of thymine with lysine at basic pH, using 254 nm light, have been studied. Three products have been isolated, namely, 6-amino-2-(1-thyminyl)hexanoic acid (Ia), 2-amino-6-(1-thyminyl)hexanoic acid (IIa) and 1-amino-5-(1-thyminyl)pentane (IIIa). Compound IIIa was shown to be a secondary product, produced by photochemical decarboxylation of Ia. Photochemical reaction of thymine with glycine and alanine at basic pH led, respectively, to formation of 2-(1-thyminyl)acetic acid (Ic) and 2-(1-thyminyl)propionic acid (Id). Compounds Ic and Id underwent photolysis to produce the decarboxylated secondary products 1-methylthymine and 1-ethylthymine, respectively. Thymidine reacts photochemically with glycine and alanine to produce the same products. Irradiation of DNA in the presence of lysine at basic pH led to the formation of the same products formed in the thymine-lysine system, namely Ia, IIa and IIIa. Uracil was found to undergo analogous photochemical exchange reactions with lysine to form 6-amino-2-(1-uracilyl)hexanoic acid (Ib), and 2-amino-6-(1-uracilyl)hexanoic acid (IIb). Compound Ib was found to undergo photodecarboxylation to form 1-amino-5-(1-uracilyl)pentane (IIIb), analogous to the secondary photoreaction of Ia. Photoreaction of uracil with 1,5-diaminopentane (cadaverine) likewise led to formation of IIIb. (author)

Reactions of modulated molecular beams with pyrolytic graphite IV. Water vapor

International Nuclear Information System (INIS)

Olander, D.R.; Acharya, T.R.; Ullman, A.Z.

1977-01-01

The reaction of water vapor with the prism plane face of anneal pyrolytic graphite was investigated by modulated molecular beam--mass spectrometry methods. The equivalent water vapor pressure of the beam was approx.2 x 10 -5 Torr and the graphite temperature was varied from 300 to 2500 0 K. The mechanism was deduced from three types of experiments: isotope exchange utilizing modulated H 2 O and steady D 2 O beams; measurements of the phase difference between H 2 O and neon reflected from the surface from a mixed primary beam of these species; and reaction of a modulated H 2 O beam to produce CO and H 2 . Based upon the isotope exchange experiments chemisorption of water on graphite was found to be dissociative and reversible. Incident water molecules chemisorbed with a sticking probability of 0.15 +- 0.02 to form the complexes C--OH and C--H. Recombination of the surface complexes reverses the adsorption step and is responsible for the isotope exchange properties of the graphite surface. This process is unactivated. Reaction to produce CO and H 2 also results from collisions of the primary surface complexes, but this step has an activation energy of 170 kJ/mole. This reaction yields bound complexes tentatively identified as C--O and H--C--H, which then decompose to produce the stable reaction products. All of the above steps exhibit characteristic times on the order of milliseconds, and are therefore detectable by the modulated beam method. All surface intermediates are strongly affected by solution and diffusion in the bulk of the solid

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)

Surface composition of magnetron sputtered Pt-Co thin film catalyst for proton exchange membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Vorokhta, Mykhailo, E-mail: vorohtam@gmail.com [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Khalakhan, Ivan; Václavů, Michal [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Kovács, Gábor; Kozlov, Sergey M. [Departament de Química Física and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, c/ Martí i Franquès 1, 08028 Barcelona (Spain); Kúš, Peter; Skála, Tomáš; Tsud, Natalia; Lavková, Jaroslava [Charles University in Prague, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague (Czech Republic); Potin, Valerie [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université Bourgogne, 9 Av. A. Savary, BP 47870, F-21078 Dijon Cedex (France); and others

2016-03-01

Graphical abstract: - Highlights: • Nanostructured Pt-Co thin catalyst films were grown on carbon by magnetron sputtering. • The surface composition of the nanostructured Pt-Co films was investigated by surface analysis techniques. • We carried out modeling of Pt-Co nanoalloys by computational methods. • Both experiment and modeling based on density functional theory showed that the surface of Pt-Co nanoparticles is almost exclusively composed of Pt atoms. - Abstract: Recently we have tested a magnetron sputtered Pt-Co catalyst in a hydrogen-fed proton exchange membrane fuel cell and showed its high catalytic activity for the oxygen reduction reaction. Here we present further investigation of the magnetron sputtered Pt-Co thin film catalyst by both experimental and theoretical methods. Scanning electron microscopy and transmission electron microscopy experiments confirmed the nanostructured character of the catalyst. The surface composition of as-deposited and annealed at 773 K Pt-Co films was investigated by surface analysis techniques, such as synchrotron radiation photoelectron spectroscopy and X-ray photoelectron spectroscopy. Modeling based on density functional theory showed that the surface of 6 nm large 1:1 Pt-Co nanoparticles is almost exclusively composed of Pt atoms (>90%) at typical operation conditions and the Co content does not exceed 20% at 773 K, in agreement with the experimental characterization of such films annealed in vacuum. According to experiment, the density of valence states of surface atoms in Pt-Co nanostructures is shifted by 0.3 eV to higher energies, which can be associated with their higher activity in the oxygen reduction reaction. The changes in electronic structure caused by alloying are also reflected in the measured Pt 4f, Co 3p and Co 2p photoelectron peak binding energies.

Fundamental characteristics study of anion-exchange PVDF-SiO(2) membranes.

Science.gov (United States)

Zuo, Xingtao; Shi, Wenxin; Yu, Shuili; He, Jiajie

2012-01-01

A new type of poly(vinylidene fluoride)(PVDF)-SiO(2) hybrid anion-exchange membrane was prepared by blending method. The anion-exchange groups were introduced by the reaction of epoxy groups with trimethylamine (TMA). Contact angle between water and the membrane surface was measured to characterize the hydrophilicity change of the membrane surface. The effects of nano-sized SiO(2) particles in the membrane-forming materials on the membrane mechanical properties and conductivity were also investigated. The experimental results indicated that PVDF-SiO(2) anion-exchange membranes exhibited better water content, ion-exchange capacity, conductivity and mechanic properties, and so may find potential applications in alkaline membrane fuel cells and water treatment processes.

Neutrino nuclear responses for double beta decays and astro neutrinos by charge exchange reactions

Science.gov (United States)

Ejiri, Hiroyasu

2014-09-01

Neutrino nuclear responses are crucial for neutrino studies in nuclei. Charge exchange reactions (CER) are shown to be used to study charged current neutrino nuclear responses associated with double beta decays(DBD)and astro neutrino interactions. CERs to be used are high energy-resolution (He3 ,t) reactions at RCNP, photonuclear reactions via IAR at NewSUBARU and muon capture reactions at MUSIC RCNP and MLF J-PARC. The Gamow Teller (GT) strengths studied by CERs reproduce the observed 2 neutrino DBD matrix elements. The GT and spin dipole (SD) matrix elements are found to be reduced much due to the nucleon spin isospin correlations and the non-nucleonic (delta isobar) nuclear medium effects. Impacts of the reductions on the DBD matrix elements and astro neutrino interactions are discussed.

Surface modification of a proton exchange membrane and hydrogen storage in a metal hydride for fuel cells

Science.gov (United States)

Andrews, Lisa

Interest in fuel cell technology is rising as a result of the need for more affordable and available fuel sources. Proton exchange membrane fuel cells involve the catalysis of a fuel to release protons and electrons. It requires the use of a polymer electrolyte membrane to transfer protons through the cell, while the electrons pass through an external circuit, producing electricity. The surface modification of the polymer, NafionRTM, commonly researched as a proton exchange membrane, may improve efficiency of a fuel cell. Surface modification can change the chemistry of the surface of a polymer while maintaining bulk properties. Plasma modification techniques such as microwave discharge of an argon and oxygen gas mixture as well as vacuum-ultraviolet (VUV) photolysis may cause favorable chemical and physical changes on the surface of Nafion for improved fuel cell function. A possible increase in hydrophilicity as a result of microwave discharge experiments may increase proton conductivity. Grafting of acrylic acid from the surface of modified Nafion may decrease the permeation of methanol in a direct methanol fuel cell, a process which can decrease efficiency. Modification of the surface of Nafion samples were carried out using: 1) An indirect Ar/O2 gas mixture plasma investigating the reaction of oxygen radicals with the surface, 2) A direct Ar/O2 gas mixture plasma investigating the reaction of oxygen radicals and VUV radiation with the surface and, 3) VUV photolysis investigating exclusively the interaction of VUV radiation with the surface and any possible oxidation upon exposure to air. Acrylic acid was grafted from the VUV photolysed Nafion samples. All treated surfaces were analyzed using X-ray photoelectron spectroscopy (XPS). Fourier transform infrared spectroscopy (FTIR) was used to analyze the grafted Nafion samples. Scanning electron microscopy (SEM) and contact angle measurements were used to analyze experiments 2 and 3. Using hydrogen as fuel is a

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.

Using a Spectral Method to Evaluate Hyporheic Exchange and its Effect on Reach Scale Nitrate Removal.

Science.gov (United States)

Moren, I.; Worman, A. L. E.; Riml, J.

2017-12-01

Previous studies have shown that hyporheic exchange processes can be of great importance for the transport, retention and mass removal of nutrients in streams. Specifically, the flow of surface water through the hyporheic zone enhances redox-sensitive reactions such as coupled nitrification-denitrification. This self-cleaning capacity of streams can be utilized in stream restoration projects aiming to improve water quality by reconstructing the geomorphology of the streams. To optimize the effect of restoration actions we need quantitative understanding of the linkage between stream geomorphology, hyporheic exchange processes and the desired water quality targets. Here we propose an analytical, spectral methodology to evaluate how different stream geomorphologies induce hyporheic exchange on a wide range of spatial and temporal scales. Measurements of streambed topographies and surface water profiles from agricultural streams were used to calculate the average hyporheic exchange velocity and residence times and the result was compared with in-stream tracer test. Furthermore, the hyporheic exchange induced by steps in the surface water profile was derived as a comparison of the theoretical capacity of the system. Based on differences in hyporheic exchange, the mass removal of nitrate could be derived for the different geomorphologies. The maximum nitrate mass removal was found to be related to a specific Damkhöler number, which reflects that the mass removal can be either reaction or transport controlled. Therefore, although hyporheic exchange induced by steps in the surface water profile was generally larger than the hyporheic exchange in the observed natural reaches, this would not necessarily lead a larger nitrate mass removal provided that the hyporheic residence times are not long enough to facilitate denitrification processes. The study illustrates the importance to investigate a stream thoroughly before any remediation actions are implemented, specifically

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

Energy Technology Data Exchange (ETDEWEB)

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

1978-09-01

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

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.

Surface area of antimony oxide by isotope exchange and other methods

Energy Technology Data Exchange (ETDEWEB)

Rao, Y.K.; Acharya, B.V.; Rangamannar, B.

1985-06-17

Specific surface areas of antimony oxide samples, one commercial, the other prepared from antimony trichloride were measured by heterogeneous isotope exchange, gas adsorption, air permeability and microscopic methods. Specific surface areas obtained by these four methods for the two samples were compared and the observed differences are explained.

Surface Modification and Surface - Subsurface Exchange Processes on Europa

Science.gov (United States)

Phillips, C. B.; Molaro, J.; Hand, K. P.

2017-12-01

The surface of Jupiter's moon Europa is modified by exogenic processes such as sputtering, gardening, radiolysis, sulfur ion implantation, and thermal processing, as well as endogenic processes including tidal shaking, mass wasting, and the effects of subsurface tectonic and perhaps cryovolcanic activity. New materials are created or deposited on the surface (radiolysis, micrometeorite impacts, sulfur ion implantation, cryovolcanic plume deposits), modified in place (thermal segregation, sintering), transported either vertically or horizontally (sputtering, gardening, mass wasting, tectonic and cryovolcanic activity), or lost from Europa completely (sputtering, plumes, larger impacts). Some of these processes vary spatially, as visible in Europa's leading-trailing hemisphere brightness asymmetry. Endogenic geologic processes also vary spatially, depending on terrain type. The surface can be classified into general landform categories that include tectonic features (ridges, bands, cracks); disrupted "chaos-type" terrain (chaos blocks, matrix, domes, pits, spots); and impact craters (simple, complex, multi-ring). The spatial distribution of these terrain types is relatively random, with some differences in apex-antiapex cratering rates and latitudinal variation in chaos vs. tectonic features. In this work, we extrapolate surface processes and rates from the top meter of the surface in conjunction with global estimates of transport and resurfacing rates. We combine near-surface modification with an estimate of surface-subsurface (and vice versa) transport rates for various geologic terrains based on an average of proposed formation mechanisms, and a spatial distribution of each landform type over Europa's surface area. Understanding the rates and mass balance for each of these processes, as well as their spatial and temporal variability, allows us to estimate surface - subsurface exchange rates over the average surface age ( 50myr) of Europa. Quantifying the timescale

Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

International Nuclear Information System (INIS)

Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Juergen

2011-01-01

Highlights: → Oxygen exchange kinetics of Pt on YSZ investigated by means of Pt model electrodes. → Two different geometry dependencies of the polarization resistance identified. → At higher temperatures the oxygen exchange reaction proceeds via a Pt surface path. → At lower temperatures a bulk path through the Pt thin film electrode is discussed. - Abstract: The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 deg. C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 deg. C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

Scaling properties of fracture surfaces on glass strengthened by ionic exchange

International Nuclear Information System (INIS)

Garza-Mendez, F.J.; Hinojosa-Rivera, M.; Gomez, I.; Sanchez, E.M.

2007-01-01

In this work the results of the statistical topometric analysis of fracture surfaces of soda-lime-silica glass with and without ionic exchange treatment are reported. In this case, the mechanism of substitution is K + -Na + . atomic force microscopy (AFM) was employed to record the topometric data from the fracture surface. The roughness exponent (ζ) and the correlation length (ξ) were calculated by the variable bandwidth method. The analysis for both glasses (subjected and non-subjected to ionic exchange) for ζ shows a value ∼0.8, this value agrees well with that reported in the literature for rapid crack propagation in a variety of materials. The correlation length shows different values for each condition. These results, along with those of microhardness indentations suggest that the self-affine correlation length is influenced by the complex interactions of the stress field of microcracks with that resulting from the collective behavior of the point defects introduced by the strengthening mechanism of ionic exchange

Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange : an RPSCB Peer Exchange

Science.gov (United States)

2014-08-01

This report summarizes the Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange, held in Birmingham, Alabama, sponsored by the Federal Highway Administration (FHWA) Office of Safetys Roadway Safety Professi...

Aprotic solvent systems provide mechanistic windows for biomolecular reactions: nucleic acid proton exchange

International Nuclear Information System (INIS)

McConnell, B.; Tan, A.

1986-01-01

Detection of general acid-base catalysis of proton transfer reactions in aqueous cytidine (or adenosine) is completely obscured by the highly reactive endocyclic protonated species of the nucleobase, whose amino proton lifetime is much shorter than that of the neutral form. In aqueous solution, protonation of the nucleobase always accompanies protonation of the buffer catalyzing exchange. However, in DMSO/water mixtures this is not the case; aqueous protonated acetate or chloroacetate can be added to cytidine in DMSO solutions without further dissociation of the buffer or significant protonation of cytidine N-3. Under these conditions general acid catalysis is observed, which involves an H-bonded complex between cytidine (N-3) and the buffer acid. Increased amino proton exchange in response to H-bond donation to C(N-3) is further suggested by increased 1 H NMR saturation-recovery rates with the formation of G-C base-pairs in DMSO and by the inverse dependence of amino proton exchange on nucleoside concentration

An Active Alkali-Exchanged Faujasite Catalyst for p-Xylene Production via the One-Pot Diels-Alder Cycloaddition/Dehydration Reaction of 2,5-Dimethylfuran with Ethylene.

Science.gov (United States)

Rohling, Roderigh Y; Uslamin, Evgeny; Zijlstra, Bart; Tranca, Ionut C; Filot, Ivo A W; Hensen, Emiel J M; Pidko, Evgeny A

2018-02-02

The one-pot Diels-Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p -xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents.

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.

Novel support effects on the mechanism of propene-deuterium: Addition and exchange reactions over dispersed ZrO2

International Nuclear Information System (INIS)

Naito, Shuichi; Tanimoto, Mitsutoshi

1995-01-01

The effect on the rate and mechanisms of propene-deuterium reactions of dispersing ZrO 2 on various supports such as silica, alumina, and titanium dioxide has been studied by microwave spectroscopic analysis of monodeuteropropene as well as by kinetic investigation. By dispersal of ZrO 2 on these supports, the rate of the C 3 H 6 -D 2 reactions is increased considerbly compared to that over unsupported ZrO 2 , with the decrease of activation energy. Hydrogen exchange in propene proceeds simultaneously with addition via the associative mechanism through n-propyl and s-propyl intermediates. Through XPS analysis of ZrO 2 /SiO 2 , it was found that a monolayer of ZrO 2 is formed over the silica support. The monolayer catalyst exhibits catalytic behavior quite different from that of unsupported ZrO 2 . On the other hand, alumina surfaces modified by ZrO 2 layers may be the main active sites in the case of ZrO 2 /Al 2 O 3 . The marked enhancement of the reaction rate in the lower loading region of ZrO 2 /TiO 2 may be explained by the strong interaction of atomically dispersed zirconium ions with active centers on TiO 2 . 28 refs., 10 figs., 1 tab

Analysis of ping-pong reaction mechanisms by positional isotope exchange. Application to galactose-1-phosphate uridyltransferase

International Nuclear Information System (INIS)

Hester, L.S.; Raushel, F.M.

1987-01-01

A new positional isotope exchange method has been developed that can be used for the analysis of enzyme-catalyzed reactions which have ping-pong kinetic mechanisms. The technique can be used to measure the relative rates of ligand dissociation from enzyme-product complexes. Enzyme is incubated with the labeled substrate and an excess of the corresponding unlabeled product. The partitioning of the enzyme-product complex back toward free enzyme is determined from the rate of positional isotope exchange within the original labeled substrate. The partitioning of the enzyme-product complex forward toward free enzyme is determined from the rate of formation of totally unlabeled substrate. It has been shown that the ratio of the two rates provides a lower limit for the release of product from the enzyme-product complex. The technique has been applied to the reaction catalyzed by galactose-1-phosphate uridyltransferase. The lower limit for the release of glucose 1-phosphate from the uridyl-enzyme relative to the maximal velocity of the reverse reaction was determined to be 3.4 +/- 0.5

Adaptable liquid crystal elastomers with transesterification-based bond exchange reactions.

Science.gov (United States)

Hanzon, Drew W; Traugutt, Nicholas A; McBride, Matthew K; Bowman, Christopher N; Yakacki, Christopher M; Yu, Kai

2018-02-14

Adaptable liquid crystal elastomers (LCEs) have recently emerged to provide a new and robust method to program monodomain LCE samples. When a constant stress is applied with active bond exchange reactions (BERs), polymer chains and mesogens gradually align in the strain direction. Mesogen alignment is maintained after removing the BER stimulus (e.g. by lowering the temperature) and the programmed LCE samples exhibit free-standing two-way shape switching behavior. Here, a new adaptable main-chain LCE system was developed with thermally induced transesterification BERs. The network combines the conventional properties of LCEs, such as an isotropic phase transition and soft elasticity, with the dynamic features of adaptable network polymers, which are malleable to stress relaxation due to the BERs. Polarized Fourier transform infrared measurements confirmed the alignment of polymer chains and mesogens after strain-induced programming. The influence of the creep stress, temperature, and time on the strain amplitude of two-way shape switching was examined. The LCE network demonstrates an innovative feature of reprogrammability, where the reversible shape-switching memory of programmed LCEs is readily deleted by free-standing heating as random BERs disrupt the mesogen alignment, so LCEs are reprogrammed after returning to the polydomain state. Due to the dynamic nature of the LCE network, it also exhibits a surface welding effect and can be fully dissolved in the organic solvent, which might be utilized for green and sustainable recycling of LCEs.

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....

Performance evaluation of anion exchange resins Purolite NRW-5050 and Duolite A-611 by application of radioisotopic techniques

International Nuclear Information System (INIS)

Singare, P.U.

2014-01-01

Radioanalytical techniques using 131 I and 82 Br as tracer isotopes were applied to study the kinetics of iodide and bromide ion-isotopic exchange reactions taking place between the external labeled ionic solution and the resin surface. The results indicate low values of specific reaction rate (min -1 ), amount of ion exchanged (mmol) and initial rate of ion exchange (mmol/min) for bromide ion-isotopic exchange reaction as compared to that obtained for iodide ion-isotopic exchange reaction. It was observed that for iodide ion-isotopic exchange reaction performed at 35.0 C, 1 000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution, the values of specific reaction rate (min -1 ), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and log K d were 0.340, 0.394, 0.134 and 20.2 respectively for Purolite NRW-5050 resin, which was higher than the respective values of 0.216, 0.290, 0.063 and 18.2 as that obtained by using Duolite A-611. The results of present investigation indicate that during the two ion-isotopic exchange reactions, for both the resins, there exists a strong positive linear correlation between amount of ions exchanged and concentration of ionic solution; and strong negative correlation between amount of ions exchanged and temperature of exchanging medium. From the results it appears that as compared to Duolite A-611 resins, Purolite NRW-5050 resins shows superior performance under identical experimental conditions.

Controlled growth of gold nanoparticles in zeolite L via ion-exchange reactions and thermal reduction processes

KAUST Repository

Zeng, Shangjing; Ding, Shuang; Li, Shangyu; Wang, Runwei; Zhang, Zongtao

2014-01-01

The growth of gold nanoparticles in zeolite can be controlled using ion-exchange reactions and thermal reduction processes. We produce a number of different sizes of the gold nanoparticles with the particle size increasing with increased temperature

Microscopic theory of cation exchange in CdSe nanocrystals.

Science.gov (United States)

Ott, Florian D; Spiegel, Leo L; Norris, David J; Erwin, Steven C

2014-10-10

Although poorly understood, cation-exchange reactions are increasingly used to dope or transform colloidal semiconductor nanocrystals (quantum dots). We use density-functional theory and kinetic Monte Carlo simulations to develop a microscopic theory that explains structural, optical, and electronic changes observed experimentally in Ag-cation-exchanged CdSe nanocrystals. We find that Coulomb interactions, both between ionized impurities and with the polarized nanocrystal surface, play a key role in cation exchange. Our theory also resolves several experimental puzzles related to photoluminescence and electrical behavior in CdSe nanocrystals doped with Ag.

Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

Energy Technology Data Exchange (ETDEWEB)

Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H. [KAERI, Taejon (Korea, Republic of)

2005-11-15

Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities.

Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

International Nuclear Information System (INIS)

Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H.

2005-01-01

Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities

New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

Science.gov (United States)

Ferreira-Aparicio, Paloma

2009-09-01

The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

Swi5-Sfr1 protein stimulates Rad51-mediated DNA strand exchange reaction through organization of DNA bases in the presynaptic filament.

KAUST Repository

Fornander, Louise H

2013-12-03

The Swi5-Sfr1 heterodimer protein stimulates the Rad51-promoted DNA strand exchange reaction, a crucial step in homologous recombination. To clarify how this accessory protein acts on the strand exchange reaction, we have analyzed how the structure of the primary reaction intermediate, the Rad51/single-stranded DNA (ssDNA) complex filament formed in the presence of ATP, is affected by Swi5-Sfr1. Using flow linear dichroism spectroscopy, we observe that the nucleobases of the ssDNA are more perpendicularly aligned to the filament axis in the presence of Swi5-Sfr1, whereas the bases are more randomly oriented in the absence of Swi5-Sfr1. When using a modified version of the natural protein where the N-terminal part of Sfr1 is deleted, which has no affinity for DNA but maintained ability to stimulate the strand exchange reaction, we still observe the improved perpendicular DNA base orientation. This indicates that Swi5-Sfr1 exerts its activating effect through interaction with the Rad51 filament mainly and not with the DNA. We propose that the role of a coplanar alignment of nucleobases induced by Swi5-Sfr1 in the presynaptic Rad51/ssDNA complex is to facilitate the critical matching with an invading double-stranded DNA, hence stimulating the strand exchange reaction.

Studies in the reaction dynamics of beam-gas chemiluminescent reactions

International Nuclear Information System (INIS)

Prisant, M.G.

1984-01-01

This thesis develops techniques for the analysis and interpretation of data obtained from beam-gas chemiluminescence experiments. These techniques are applied to experimental studies of atom transfer reactions of the type A + BC → AB + C. A procedure is developed for determining the product rotational alignment in the center-of-mass frame from polarization measurements of chemiluminescent atom-diatom exchange reactions under beam-gas conditions. Knowledge of a vector property of a reaction, such as product alignment, provides information on the disposition of angular momentum by a chemical reaction. Fluorescence polarization and hence product alignment are measured for two prototype reactions. The reaction of metastable calcium atoms with hydrogen-chloride gas yields highly aligned calcium-chloride product which exhibits little variation of alignment with vibrational state. The reaction of ground-state calcium with fluorine gas yields moderately aligned product which shows strong variation of alignment with vibration. A multi-surface direct-interaction model is developed to interpret product alignment and population data. The predictions of this model for the reaction of calcium with fluorine show reasonable agreement with experiment

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...

Radiation exchange factors between specular inner surfaces of a rectangular enclosure such as transplant production unit

International Nuclear Information System (INIS)

Abdel-Ghany, Ahmed M.; Kozai, Toyoki

2006-01-01

General mathematical relations are presented for the specular exchange factors, F S , of diffuse radiation exchange between the inner surfaces of a rectangular enclosure. Three of these surfaces are specular reflectors, diffuse emitters and the fourth surface is a diffuse reflector, diffuse emitter. This enclosure can be used as a transplant production unit with artificial lighting for electric energy saving purposes. An image system and the crossed string method are used to derive these relations. The resulting expressions are conceptually simple and similar to the commonly known expressions of the exchange factors between diffuse surfaces, F. The accuracy of the presented F S relations was examined for different numbers of multiple reflections, N, on the specular surfaces and for different aspect ratios (ratio of the width, w to the height, h). The results proved that the relations are accurate and strongly satisfy the well-known relation of the radiation exchange between enclosure surfaces and satisfy the reciprocity relation. For any aspect ratio, considering N of 150 between highly reflective surfaces (ρ = 0.99) is sufficient to estimate the F S factors without any possible error. Using specular reflecting surfaces in such cases significantly reduces the electric energy consumption used for lighting

Studies on ligand exchange reaction of functionalized mercaptothiadiazole compounds onto citrate capped gold nanoparticles

International Nuclear Information System (INIS)

Kalimuthu, Palraj; John, S. Abraham

2010-01-01

Mercaptothiadiazole ligands functionalized with thiol (2,5-dimercapto-1,3,4-thiadiazole (DMT)) and methyl (5-methyl-2-mercapto-1,3,4-thiadiazole (MMT)) groups capped onto citrate capped gold nanoparticles (C-AuNPs) by ligand exchange reaction was investigated by UV-vis spectroscopy, FT-IR spectroscopy and transmission electron microscopy (TEM) techniques. The surface plasmon resonance band at 522 nm for C-AuNPs was shifted to 530 nm after capping with DMT whereas an additional band was observed at 630 nm due to aggregation in addition to a shift in the band at 522 nm after capping of MMT onto C-AuNPs. Thus, capping of DMT onto C-AuNPs leads to the formation of stable AuNPs while capping of MMT leads to the formation of unstable AuNPs. FT-IR studies show that the citrate ions were completely replaced by both DMT and MMT ligands from the AuNPs. TEM images indicate that the size and shape of the AuNPs remain same after capping of these ligands.

Solvent effects on the kinetics of the chlorine isotopic exchange reaction between chloride ion and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorchloridothioate

International Nuclear Information System (INIS)

Mikolajczyk, M.; Slebocka-Tilk, H.; Reimschussel, W.

1982-01-01

The effect of solvent on the kinetics of the chlorine isotopic exchange reaction between 36 Cl- ions and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorochloridothioate has been investigated in nitromethane, acetonitrile, propylene carbonate, benzonitrile, nitrobenzene, and hexamethyl-phosphoric triamide. The rate constants decrease with increasing electrophilicity of the solvent. A good correlation between the logarithm of the rate constants and acceptor number (AN) of the solvent was obtained with identical slopes for reactions with phosphoryl and thiophosporyl compounds. The slopes for the dependence of ΔH or TΔS vs. AN for chlorine isotopic exchange in (PHO) 2 pace are opposite those for the exchange reaction in (PHO) 2 PSCl, so a constant ratio of k/sub p=O//k/sub p=s/ is observed, resulting from compensation of ΔH by ΔS. The effect of solvent on the initial state (from solubility measurements) and the transition state of the reaction between (PhO) 2 PSCl and the Cl- ion was evaluated. Changes of solvation of (PHO) 2 PSCE have practically no effect on the kinetics of the reactions. Changes of solvation of the chloride ion and of the transition state primarily influence the rate constants and activation parameters of the investigated isotopic-exchange reaction

Global observations and modeling of atmosphere-surface exchange of elemental mercury: a critical review

Science.gov (United States)

Zhu, Wei; Lin, Che-Jen; Wang, Xun; Sommar, Jonas; Fu, Xuewu; Feng, Xinbin

2016-04-01

Reliable quantification of air-surface fluxes of elemental Hg vapor (Hg0) is crucial for understanding mercury (Hg) global biogeochemical cycles. There have been extensive measurements and modeling efforts devoted to estimating the exchange fluxes between the atmosphere and various surfaces (e.g., soil, canopies, water, snow, etc.) in the past three decades. However, large uncertainties remain due to the complexity of Hg0 bidirectional exchange, limitations of flux quantification techniques and challenges in model parameterization. In this study, we provide a critical review on the state of science in the atmosphere-surface exchange of Hg0. Specifically, the advancement of flux quantification techniques, mechanisms in driving the air-surface Hg exchange and modeling efforts are presented. Due to the semi-volatile nature of Hg0 and redox transformation of Hg in environmental media, Hg deposition and evasion are influenced by multiple environmental variables including seasonality, vegetative coverage and its life cycle, temperature, light, moisture, atmospheric turbulence and the presence of reactants (e.g., O3, radicals, etc.). However, the effects of these processes on flux have not been fundamentally and quantitatively determined, which limits the accuracy of flux modeling. We compile an up-to-date global observational flux database and discuss the implication of flux data on the global Hg budget. Mean Hg0 fluxes obtained by micrometeorological measurements do not appear to be significantly greater than the fluxes measured by dynamic flux chamber methods over unpolluted surfaces (p = 0.16, one-tailed, Mann-Whitney U test). The spatiotemporal coverage of existing Hg0 flux measurements is highly heterogeneous with large data gaps existing in multiple continents (Africa, South Asia, Middle East, South America and Australia). The magnitude of the evasion flux is strongly enhanced by human activities, particularly at contaminated sites. Hg0 flux observations in East

Ion exchange and hydrolysis reactions in zeolites

International Nuclear Information System (INIS)

Harjula, Risto.

1993-09-01

Among other uses, zeolites are efficient cation exchangers for aquatic pollution control. At present they they are mainly used in nuclear waste effluent treatment and in detergency. In the thesis, several ion exchange equilibria, important in these main fields of zeolite applications, were studied, with special emphasis on the formulation and calculation of the equilibria. The main interest was the development of thermodynamic formulations for the calculation of zeolite ion exchange equilibria in solutions of low or very low (trace) ion concentration, which are relevant for the removal of trace pollutants, such as radionuclides, from waste waters. Two groups of zeolite-cation systems were studied. First, binary Ca 2+ /Na + exchange in zeolites X and Y, which are of interest for detergency applications. Second, binary Cs + /Na + and Cs + /K + exchanges, and ternary Cs + /Na + /K + exchange in mordenite, which are important in nuclear waste effluent treatment. The thesis is based on five previous publications by author. (100 refs., 7 figs.)

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).

Hydrogen/deuterium exchange in mass spectrometry.

Science.gov (United States)

Kostyukevich, Yury; Acter, Thamina; Zherebker, Alexander; Ahmed, Arif; Kim, Sunghwan; Nikolaev, Eugene

2018-03-30

The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies. © 2018 Wiley Periodicals, Inc.

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.

Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

Science.gov (United States)

Epov, Vladimir N

2011-08-07

A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

Thermochemical study of deuterium exchange reactions in water-alcohol and alcohol-alcohol systems

International Nuclear Information System (INIS)

Khurma, J.R.; Fenby, D.V.

1979-01-01

Molar excess enthalpies of water-alcohol systems have been analyzed to give equilibrium constants and enthalpies of the reactions 2ROH + D 2 O = 2ROD + H 2 O (R = CH 3 , C 2 H 5 , n-C 3 H 7 ). The equilibrium constants are significantly greater than the ''random'' value. Molar excess enthalpies of alcohol-alcohol systems have been analyzed to give enthalpies of reactions ROH + R'OD = ROD + R'OH. The enthalpies of water-alcohol and alcohol-alcohol exchange reactions form a self-consistent set and are in good agreement with values from earlier studies. Molar excess enthalpies at 298.15 K are reported for n-C 3 H 7 OH and n-C 3 H 7 OD with H 2 O, D 2 O, CH 3 OH, CH 3 OD, C 2 H 5 OH, and C 2 H 5 OD

Mineral carbonation of gaseous carbon dioxide using a clay-hosted cation exchange reaction.

Science.gov (United States)

Kang, Il-Mo; Roh, Ki-Min

2013-01-01

The mineral carbonation method is still a challenge in practical application owing to: (1) slow reaction kinetics, (2) high reaction temperature, and (3) continuous mineral consumption. These constraints stem from the mode of supplying alkaline earth metals through mineral acidification and dissolution. Here, we attempt to mineralize gaseous carbon dioxide into calcium carbonate, using a cation exchange reaction of vermiculite (a species of expandable clay minerals). The mineralization is operated by draining NaCI solution through vermiculite powders and continuously dropping into the pool of NaOH solution with CO2 gas injected. The mineralization temperature is regulated here at 293 and 333 K for 15 min. As a result of characterization, using an X-ray powder diffractometer and a scanning electron microscopy, two types of pure CaCO3 polymorphs (vaterite and calcite) are identified as main reaction products. Their abundance and morphology are heavily dependent on the mineralization temperature. Noticeably, spindle-shaped vaterite, which is quite different from a typical vaterite morphology (polycrystalline spherulite), forms predominantly at 333 K (approximately 98 wt%).

Implied and Local Volatility Surfaces for South African Index and Foreign Exchange Options

Directory of Open Access Journals (Sweden)

Antonie Kotzé

2015-01-01

Full Text Available Certain exotic options cannot be valued using closed-form solutions or even by numerical methods assuming constant volatility. Many exotics are priced in a local volatility framework. Pricing under local volatility has become a field of extensive research in finance, and various models are proposed in order to overcome the shortcomings of the Black-Scholes model that assumes a constant volatility. The Johannesburg Stock Exchange (JSE lists exotic options on its Can-Do platform. Most exotic options listed on the JSE’s derivative exchanges are valued by local volatility models. These models needs a local volatility surface. Dupire derived a mapping from implied volatilities to local volatilities. The JSE uses this mapping in generating the relevant local volatility surfaces and further uses Monte Carlo and Finite Difference methods when pricing exotic options. In this document we discuss various practical issues that influence the successful construction of implied and local volatility surfaces such that pricing engines can be implemented successfully. We focus on arbitrage-free conditions and the choice of calibrating functionals. We illustrate our methodologies by studying the implied and local volatility surfaces of South African equity index and foreign exchange options.

On line determination of deuterium in hydrogen water exchange reaction by mass spectrometry. IRP-10

International Nuclear Information System (INIS)

Sharma, J.D.; Alphonse, K.P.; Mishra, Sushama; Prabhu, S.A.; Mohan, Sadhana; Tangri, V.K.

2007-01-01

The Deuterium (D)/Hydrogen (H) analysis at low Concentration is generally carried out by Mass Spectrometry. Mass Spectrometer is specially designed for the measurement of Mass 2 and 3 ratio. The Deuterium analysis of water and hydrogen in concentration range of a few ppm to about 1% plays an important role in the Heavy Water Production Plants. For the enrichment of the Deuterium concentration in H 2 O by H 2 - H 2 O exchange a catalyst is essential as reaction is relatively slow. Heavy Water Division has developed in house Platinum based catalyst for the isotopic exchange of Hydrogen and Water

Tritons for the study of the charge-exchange reactions with the LHE streamer chamber: status and some possibilities

International Nuclear Information System (INIS)

Avramenko, S.A.; Belikov, Yu.A.; Golokhvastov, A.I.; Kirillov, A.D.; Khorozov, S.A.; Komolov, L.N.; Lukstin'sh, Yu.; Rukoyatkin, P.A.

1997-01-01

The 6 and 9 GeV/c secondary tritons, produced in the 4 He+A→ 3 H+X reaction, were used to study the charge-exchange reactions using a streamer chamber in magnetic field. The triton formation schemes, the beam parameters achieved as well as a way to reduce the beam momentum spread are given in the paper

Oxygen exchange between C18O2 and ''acidic'' oxide and zeolite catalysts

International Nuclear Information System (INIS)

Peri, J.B.

1975-01-01

The exchange of oxygen between C 18 O 2 and several high-area oxides, including silica, γ-alumina, silica--alumina, and zeolite catalysts, was studied. Infrared spectra of adsorbed CO 2 and of surface ''carbonates'' were used to follow the rate of oxygen exchange and investigate the nature of unusually exchangeable surface oxide ions, present at low concentrations. Interaction of CO 2 with the surface typically produced initial exchange of one oxygen atom, as expected from interaction with a single oxide ion (CO 2 + O 2- reversible CO 3 2- ), and the number of exchangeable ions increased with increasing temperature. The rate of oxygen exchange did not correlate with chemisorption to form stable surface carbonates or with the extent of strong physical adsorption of CO 2 . With dry silica, exchange was insignificant below 600 0 ; with catalytically active zeolites and dry γ-alumina, it was detectable at 200 0 and fairly rapid at 300--400 0 . Silica--alumina required 100--150 0 higher temperature for exchange than did an active zeolite. Activity for cracking and other hydrocarbon reactions may be related to the ease of exchange of some surface oxide ions with CO 2 . Active zeolites have reactive oxide sites resembling those on dry γ-alumina, but such sites on zeolites are probably less-readily eliminated by chemisorption of H 2 O or other compounds. (U.S.)

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.

Isotope exchange reactions in hydrogen mixtures

International Nuclear Information System (INIS)

Czaplinski, W.; Gula, A.; Kravtsov, A.; Mikhailov, A.; Popov, N.

1990-12-01

The rates of isotopic exchange for the excited states of muonic hydrogen are calculated as functions of collision energy. Ground state population q 1s for different collision energies, target densities and isotope concentrations is obtained. It is shown that for principal quantum numbers n > 5 the isotopic exchange still considerably influences the value of q 1s . (author)

Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

Science.gov (United States)

Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

2012-04-28

The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction. This journal is © the Owner Societies 2012

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.

An investigation of one- versus two-dimensional semiclassical transition state theory for H atom abstraction and exchange reactions.

Science.gov (United States)

Greene, Samuel M; Shan, Xiao; Clary, David C

2016-02-28

We investigate which terms in Reduced-Dimensionality Semiclassical Transition State Theory (RD SCTST) contribute most significantly in rate constant calculations of hydrogen extraction and exchange reactions of hydrocarbons. We also investigate the importance of deep tunneling corrections to the theory. In addition, we introduce a novel formulation of the theory in Jacobi coordinates. For the reactions of H atoms with methane, ethane, and cyclopropane, we find that a one-dimensional (1-D) version of the theory without deep tunneling corrections compares well with 2-D SCTST results and accurate quantum scattering results. For the "heavy-light-heavy" H atom exchange reaction between CH3 and CH4, deep tunneling corrections are needed to yield 1-D results that compare well with 2-D results. The finding that accurate rate constants can be obtained from derivatives of the potential along only one dimension further validates RD SCTST as a computationally efficient yet accurate rate constant theory.

Complex ion kinetics. Reaction rates on ion-exchange resins compared to those in water

International Nuclear Information System (INIS)

Liss, I.B.; Murmann, R.K.

1975-01-01

A comparison has been made between the rates in water and on an ion-exchange resin for the aquation of [(NH 3 ) 5 CoOReO 3 ] 2+ and [(H 2 O) 5 CrCl] 2+ and for the 18 O isotopic exchange of water with [(NH 3 ) 5 Co(OH 2 )] 3+ and ReO 4 - . The rate of water exchange on [(NH 3 ) 5 Co(OH 2 )] 3+ was not changed by association with Dowex 50W resins. Aquation of [(NH 3 ) 5 CoOReO 3 ] 2+ and water exchange on ReO 4 - had modified pH dependencies when associated with a resin. With the cobalt complex the rates were faster on the resin in the acidic region and slower on the resin in the basic region. A new term in the rate equation was observed when ReO 4 - was on the resin, first order in H + , while the other terms appear to be unchanged. Aquation of [(H 2 O) 5 CrCl] 2+ was much slower when it was absorbed on the resin. This was related to the known ionic strength effect of the reaction. (auth)

Morphing of the Dissipative Reaction Mechanism

International Nuclear Information System (INIS)

Schroeder, W.U.; Toke, J.; Gawlikowicz, W.; Houck, M.A.; Lu, J.; Pienkowski, L.

2003-01-01

Important trends in the evolution of heavy-ion reaction mechanisms with bombarding energy and impact parameter are reviewed. Essential features of dissipative reactions appear preserved at E/A = 50-62 MeV, such as dissipative orbiting and multi-nucleon exchange. The relaxation of the A/Z asymmetry with impact parameter is slow. Non-equilibrium emission of light particles and clusters is an important process accompanying the evolution of the mechanism. Evidence is presented for a new mechanism of statistical cluster emission from hot, metastable primary reaction products, driven by surface entropy. These results suggest a plausible reinterpretation of multi-fragmentation. (authors)

Morphing of the Dissipative Reaction Mechanism

Energy Technology Data Exchange (ETDEWEB)

Schroeder, W.U.; Toke, J.; Gawlikowicz, W.; Houck, M.A.; Lu, J.; Pienkowski, L. [Rochester Univ., Dept. of Chemistry, Rochester, NY (United States)

2003-07-01

Important trends in the evolution of heavy-ion reaction mechanisms with bombarding energy and impact parameter are reviewed. Essential features of dissipative reactions appear preserved at E/A = 50-62 MeV, such as dissipative orbiting and multi-nucleon exchange. The relaxation of the A/Z asymmetry with impact parameter is slow. Non-equilibrium emission of light particles and clusters is an important process accompanying the evolution of the mechanism. Evidence is presented for a new mechanism of statistical cluster emission from hot, metastable primary reaction products, driven by surface entropy. These results suggest a plausible reinterpretation of multi-fragmentation. (authors)

Global observations and modeling of atmosphere–surface exchange of elemental mercury: a critical review

Directory of Open Access Journals (Sweden)

W. Zhu

2016-04-01

Full Text Available Reliable quantification of air–surface fluxes of elemental Hg vapor (Hg0 is crucial for understanding mercury (Hg global biogeochemical cycles. There have been extensive measurements and modeling efforts devoted to estimating the exchange fluxes between the atmosphere and various surfaces (e.g., soil, canopies, water, snow, etc. in the past three decades. However, large uncertainties remain due to the complexity of Hg0 bidirectional exchange, limitations of flux quantification techniques and challenges in model parameterization. In this study, we provide a critical review on the state of science in the atmosphere–surface exchange of Hg0. Specifically, the advancement of flux quantification techniques, mechanisms in driving the air–surface Hg exchange and modeling efforts are presented. Due to the semi-volatile nature of Hg0 and redox transformation of Hg in environmental media, Hg deposition and evasion are influenced by multiple environmental variables including seasonality, vegetative coverage and its life cycle, temperature, light, moisture, atmospheric turbulence and the presence of reactants (e.g., O3, radicals, etc.. However, the effects of these processes on flux have not been fundamentally and quantitatively determined, which limits the accuracy of flux modeling. We compile an up-to-date global observational flux database and discuss the implication of flux data on the global Hg budget. Mean Hg0 fluxes obtained by micrometeorological measurements do not appear to be significantly greater than the fluxes measured by dynamic flux chamber methods over unpolluted surfaces (p = 0.16, one-tailed, Mann–Whitney U test. The spatiotemporal coverage of existing Hg0 flux measurements is highly heterogeneous with large data gaps existing in multiple continents (Africa, South Asia, Middle East, South America and Australia. The magnitude of the evasion flux is strongly enhanced by human activities, particularly at contaminated sites. Hg0

Energy exchange in thermal energy atom-surface scattering: impulsive models

International Nuclear Information System (INIS)

Barker, J.A.; Auerbach, D.J.

1979-01-01

Energy exchange in thermal energy atom surface collisions is studied using impulsive ('hard cube' and 'hard sphere') models. Both models reproduce the observed nearly linear relation between outgoing and incoming energies. In addition, the hard-sphere model accounts for the widths of the outcoming energy distributions. (Auth.)

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

Energy Technology Data Exchange (ETDEWEB)

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

1961-07-01

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

Deuterium exchange reaction between hydrogen and water in a trickle-bed column packed with novel catalysts

International Nuclear Information System (INIS)

Ahn, D. H.; Baek, S. W.; Lee, H. S.; Kim, K. R.; Kang, H. S.; Lee, S. H.; Jeong, H. S.

1998-01-01

The activity of a novel catalyst (Pt/SDBC) for deuterium exchange reaction between water and hydrogen streams in a trickle bed was measured. The performance of the catalyst was compared with a commercial catalyst with same metal content. The catalytic activity for the bed of wet-proofed catalyst diluted with hydrophillic packing material also measured. The Pt/SDBC catalyst shows higher activity in the liquid phase reaction than the commercial catalyst as measured in the vapor phase reaction. The performance for 50% dilution of the Pt/SDBC catalyst bed with hydrophillic packing material is better than that of the 100% bed due to more liquid holdup and better water distribution

Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

Science.gov (United States)

Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

2018-04-25

The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

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)

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.

Controlled growth of gold nanoparticles in zeolite L via ion-exchange reactions and thermal reduction processes

KAUST Repository

Zeng, Shangjing

2014-09-01

The growth of gold nanoparticles in zeolite can be controlled using ion-exchange reactions and thermal reduction processes. We produce a number of different sizes of the gold nanoparticles with the particle size increasing with increased temperature of the final heat treatment. © 2014 Elsevier B.V.

Effect of fluoride on ion exchange, remineralization and acid resistance of surface enamel

Energy Technology Data Exchange (ETDEWEB)

Aponte-Merced, L A; Feagin, F F [Alabama Univ., Birmingham (USA)

1979-01-01

In a system of constant ion activities the rates of F/sup -/ exchange in enamel, under conditions of exchange alone and remineralization, depended on the concentration of F/sup -/ in solutions. Acid resistance of surface minerals resulted from exchange of F/sup -/ for OH/sup -/ in the enamel at pH 7.0 and 4.5. The level of 0.5 mM NaF, compared to 0.05 and 5.0 mM, caused maximum rates of isotopic exchange of /sup 45/Ca and maximum acid resistance of enamel. Similarly low levels of F/sup -/ may be feasible for use in caries prevention in the absence and presence of remineralization.

Investigation and optimization of the depth of flue gas heat recovery in surface heat exchangers

Science.gov (United States)

Bespalov, V. V.; Bespalov, V. I.; Melnikov, D. V.

2017-09-01

Economic issues associated with designing deep flue gas heat recovery units for natural gas-fired boilers are examined. The governing parameter affecting the performance and cost of surface-type condensing heat recovery heat exchangers is the heat transfer surface area. When firing natural gas, the heat recovery depth depends on the flue gas temperature at the condenser outlet and determines the amount of condensed water vapor. The effect of the outlet flue gas temperature in a heat recovery heat exchanger on the additionally recovered heat power is studied. A correlation has been derived enabling one to determine the best heat recovery depth (or the final cooling temperature) maximizing the anticipated reduced annual profit of a power enterprise from implementation of energy-saving measures. Results of optimization are presented for a surface-type condensing gas-air plate heat recovery heat exchanger for the climatic conditions and the economic situation in Tomsk. The predictions demonstrate that it is economically feasible to design similar heat recovery heat exchangers for a flue gas outlet temperature of 10°C. In this case, the payback period for the investment in the heat recovery heat exchanger will be 1.5 years. The effect of various factors on the optimal outlet flue gas temperature was analyzed. Most climatic, economical, or technological factors have a minor effect on the best outlet temperature, which remains between 5 and 20°C when varying the affecting factors. The derived correlation enables us to preliminary estimate the outlet (final) flue gas temperature that should be used in designing the heat transfer surface of a heat recovery heat exchanger for a gas-fired boiler as applied to the specific climatic conditions.

Implementation of a vibrationally linked chemical reaction model for DSMC

Science.gov (United States)

Carlson, A. B.; Bird, Graeme A.

1994-01-01

A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.

Theoretical Study of Sodium-Water Surface Reaction Mechanism

Science.gov (United States)

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

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

Theoretical study of sodium-water surface reaction mechanism

International Nuclear Information System (INIS)

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

2012-01-01

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

GROUNDWATER-SURFACE WATER EXCHANGE AND IMPLICATIONS FOR LARGE RIVER RESTORATION

Science.gov (United States)

Movement of river water into and out of high-porosity alluvial deposits can have an important influence on surface water quality and aquatic habitat. In our study of a 60-km reach of the Willamette River in Oregon, USA, we: 1) used tracers to estimate the rate of exchange betw...

$\\beta$- decay of $^{58}$Zn. A critical test for the charge-exchange reaction as a probe for the $\\beta$- decay strength distribution

CERN Multimedia

2002-01-01

% IS353 \\\\ \\\\ Due to its importance in fundamental physics and astrophysics, a great effort both theoretically and experimentally is devoted to study Gamow Teller (GT)-strength. The GT-strength and its distribution play a key role in late stellar evolution. During the pre-supernova core-collapse of massive stars, the electron capture and nuclear $\\beta$ -decay determine the electron-to-baryon ratio, which influences the infall dynamics and the mass of the final core. The cross-section of the charge-exchange reaction at forward angles with energies above 100~MeV is expected to be proportional to the squares of Fermi and GT matrix elements. This proportionality should provide a Q-value free method to probe the weak interaction strength and renormalization effects in nuclei. Thus charge-exchange reactions are often used to determine the experimental GT-strength. However, the connection between the GT-strength and the cross-section of the charge-exchange reaction is partially model-dependent and the question aris...

Two-body hypercharge-exchange reactions in K-p and π+p interactions at 10 and 16 GeV/c

International Nuclear Information System (INIS)

Girtler, P.; Otter, G.; Sliwa, K.; Barnham, K.W.J.; Eason, R.M.; Newham, P.; Pollock, B.; Wells, J.; Mandl, F.; Markytan, M.

1979-01-01

Cross section values or upper limits are presented for twenty-five two-body hypercharge-exchange reactions in K - p and π + p interactions at 10 and 16 GeV/c. The 16 GeV/c results are compared with some predictions of line-reversal plus exchange-degenerate Regge poles, of SU(3) and of the additive quark model. Agreement is found in all cases. (author)

Mass-independent isotope effects in chemical exchange reaction

International Nuclear Information System (INIS)

Nishizawa, Kazushige

2000-01-01

Isotope effects of some elements in chemical exchange reaction were investigated by use of liquid-liquid extraction, liquid membrane or chromatographic separation. Cyclic polyether was used for every method. All polyethers used in a series of the studies were made clear that they distinguished the isotopes not only by their nuclear masses but also by their nuclear sizes and shapes. Chromium isotopes, for example, were recognized to have enrichment factors being proportional to δ 2 > which is a parameter to show field shift or the nuclear size and shape of the isotope. It follows that the chromium isotopes are separated not by their masses but by their field shift effects. Nuclear spin also played a great role to separate odd mass number isotopes from even mass number isotopes in even atomic number elements. Contribution of the nuclear spin (I=3/2) of 53 Cr to total enrichment factor, ε 53/52 = -0.00028, for 53 Cr to 52 Cr was observed to be, ε spin = -0.0025. (author)

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

Energy Technology Data Exchange (ETDEWEB)

Jia, Hanzhong, E-mail: jiahz@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Li, Li [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Chen, Hongxia; Zhao, Yue [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); School of Geology and Mining Engineering, Xinjiang University, Urumqi 830046 (China); Li, Xiyou [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China)

2015-04-28

Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe{sup 3+} > Al{sup 3+} > Cu{sup 2+} >> Ca{sup 2+} > K{sup +} > Na{sup +}, which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na{sup +}-smectite and K{sup +}-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe{sup 3+}, Al{sup 3+}, and Cu{sup 2+} are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O{sub 2}{sup −}· , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation.

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

International Nuclear Information System (INIS)

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-01-01

Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe 3+ > Al 3+ > Cu 2+ >> Ca 2+ > K + > Na + , which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na + -smectite and K + -smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe 3+ , Al 3+ , and Cu 2+ are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O 2 − · , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation

Neutrino and antineutrino charge-exchange reactions on 12C

International Nuclear Information System (INIS)

Samana, A. R.; Krmpotic, F.; Paar, N.; Bertulani, C. A.

2011-01-01

We extend the formalism of weak interaction processes, obtaining new expressions for the transition rates, which greatly facilitate numerical calculations, for both neutrino-nucleus reactions and muon capture. Explicit violation of the conserved vector current hypothesis by the Coulomb field, as well as development of a sum-rule approach for inclusive cross sections, has been worked out. We have done a thorough study of exclusive (ground-state) properties of 12 B and 12 N within the projected quasiparticle random phase approximation (PQRPA). Good agreement with experimental data achieved in this way put into evidence the limitations of the standard RPA and QRPA models, which come from the inability of the RPA to open the p 3/2 shell and from the nonconservation of the number of particles in the QRPA. The inclusive neutrino/antineutrino (ν/ν-tilde) reactions 12 C(ν,e - ) 12 N and 12 C(ν-tilde,e + ) 12 B are calculated within both the PQRPA and the relativistic QRPA. It is found that (i) the magnitudes of the resulting cross sections are close to the sum-rule limit at low energy, but significantly smaller than this limit at high energies, for both ν and ν-tilde; (ii) they increase steadily when the size of the configuration space is augmented, particularly for ν/ν-tilde energies >200 MeV; and (iii) they converge for sufficiently large configuration space and final-state spin. The quasi-elastic 12 C(ν,μ - ) 12 N cross section recently measured in the MiniBooNE experiment is briefly discussed. We study the decomposition of the inclusive cross section based on the degree of forbiddenness of different multipoles. A few words are dedicated to the ν/ν-tilde- 12 C charge-exchange reactions related to astrophysical applications.

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.

Spin-wave resonance frequency in ferromagnetic thin film with interlayer exchange coupling and surface anisotropy

Science.gov (United States)

Zhang, Shuhui; Rong, Jianhong; Wang, Huan; Wang, Dong; Zhang, Lei

2018-01-01

We have investigated the dependence of spin-wave resonance(SWR) frequency on the surface anisotropy, the interlayer exchange coupling, the ferromagnetic layer thickness, the mode number and the external magnetic field in a ferromagnetic superlattice film by means of the linear spin-wave approximation and Green's function technique. The SWR frequency of the ferromagnetic thin film is shifted to higher values corresponding to those of above factors, respectively. It is found that the linear behavior of SWR frequency curves of all modes in the system is observed as the external magnetic field is increasing, however, SWR frequency curves are nonlinear with the lower and the higher modes for different surface anisotropy and interlayer exchange coupling in the system. In addition, the SWR frequency of the lowest (highest) mode is shifted to higher (lower) values when the film thickness is thinner. The interlayer exchange coupling is more important for the energetically higher modes than for the energetically lower modes. The surface anisotropy has a little effect on the SWR frequency of the highest mode, when the surface anisotropy field is further increased.

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.

The determination of specific surface of sodium polyuranates

International Nuclear Information System (INIS)

Bilgin, B.; Atun, G.

2002-01-01

Three different sodium polyuranates were prepared by titration of uranyl nitrate with a sodium hydroxide solution labeled with 22 Na as the radiotracer. Polyuranates whose composition was *Na 2 O.7,5UO 3 .11H 2 O (sample A), *Na 2 O.4,3 UO 3 .4,7H 2 O (sample B), and *Na 2 O.2UO 3 .4H 2 O (sample C) were precipitated at pH 5.6, 8.5 and 11.2, respectively. The specific surface areas of these samples were determined by the BET method using methylene blue (MB) as the adsorbate. The sodium polyuranate surfaces were saturated by sequential adsorption of MB. The adsorption data gave an S-shaped isotherm and were fitted to the BET equation. The specific surface areas calculated from the BET isotherm decreased in order A > B > C. The isotope and ion exchange reactions between the sodium polyuranates and Li + , Na + , K + , Rb + , Cs + , Ca 2+ , Sr 2+ , and Ba 2+ ions were compared before and after MB coverage. The results showed that the isotope and ion exchange fractions decrease on the covered surfaces indicating particle diffusion mechanism dominated exchange reactions

The fractal geometry of nutrient exchange surfaces does not provide an explanation for 3/4-power metabolic scaling

Directory of Open Access Journals (Sweden)

Painter Page R

2005-08-01

Full Text Available Abstract Background A prominent theoretical explanation for 3/4-power allometric scaling of metabolism proposes that the nutrient exchange surface of capillaries has properties of a space-filling fractal. The theory assumes that nutrient exchange surface area has a fractal dimension equal to or greater than 2 and less than or equal to 3 and that the volume filled by the exchange surface area has a fractal dimension equal to or greater than 3 and less than or equal to 4. Results It is shown that contradicting predictions can be derived from the assumptions of the model. When errors in the model are corrected, it is shown to predict that metabolic rate is proportional to body mass (proportional scaling. Conclusion The presence of space-filling fractal nutrient exchange surfaces does not provide a satisfactory explanation for 3/4-power metabolic rate scaling.

Independent control of the shape and composition of ionic nanocrystals through sequential cation exchange reactions

Energy Technology Data Exchange (ETDEWEB)

Luther, Joseph Matthew; Zheng, Haimei; Sadtler, Bryce; Alivisatos, A. Paul

2009-07-06

Size- and shape-controlled nanocrystal growth is intensely researched for applications including electro-optic, catalytic, and medical devices. Chemical transformations such as cation exchange overcome the limitation of traditional colloidal synthesis, where the nanocrystal shape often reflects the inherent symmetry of the underlying lattice. Here we show that nanocrystals, with established synthetic protocols for high monodispersity, can be templates for independent composition control. Specifically, controlled interconversion between wurtzite CdS, chalcocite Cu2S, and rock salt PbS occurs while preserving the anisotropic dimensions unique to the as-synthesized materials. Sequential exchange reactions between the three sulfide compositions are driven by the disparate solubilites of the metal ion exchange pair in specific coordinating molecules. Starting with CdS, highly anisotropic PbS nanorods are created, which serve as an important material for studying strong 2-dimensional quantum confinement, as well as for optoelectronic applications. Furthermore, interesting nanoheterostructures of CdS|PbS are obtained by precise control over ion insertion and removal.

Enhanced bimolecular exchange reaction through programmed coordination of a five-coordinate oxovanadium complex for efficient redox mediation in dye-sensitized solar cells.

Science.gov (United States)

Oyaizu, Kenichi; Hayo, Noriko; Sasada, Yoshito; Kato, Fumiaki; Nishide, Hiroyuki

2013-12-07

Electrochemical reversibility and fast bimolecular exchange reaction found for VO(salen) gave rise to a highly efficient redox mediation to enhance the photocurrent of a dye-sensitized solar cell, leading to an excellent photovoltaic performance with a conversion efficiency of 5.4%. A heterogeneous electron-transfer rate constant at an electrode (k0) and a second-order rate constant for an electron self-exchange reaction (k(ex)) were proposed as key parameters that dominate the charge transport property, which afforded a novel design concept for the mediators based on their kinetic aspects.

First-order exchange coefficient coupling for simulating surface water-groundwater interactions: Parameter sensitivity and consistency with a physics-based approach

Science.gov (United States)

Ebel, B.A.; Mirus, B.B.; Heppner, C.S.; VanderKwaak, J.E.; Loague, K.

2009-01-01

Distributed hydrologic models capable of simulating fully-coupled surface water and groundwater flow are increasingly used to examine problems in the hydrologic sciences. Several techniques are currently available to couple the surface and subsurface; the two most frequently employed approaches are first-order exchange coefficients (a.k.a., the surface conductance method) and enforced continuity of pressure and flux at the surface-subsurface boundary condition. The effort reported here examines the parameter sensitivity of simulated hydrologic response for the first-order exchange coefficients at a well-characterized field site using the fully coupled Integrated Hydrology Model (InHM). This investigation demonstrates that the first-order exchange coefficients can be selected such that the simulated hydrologic response is insensitive to the parameter choice, while simulation time is considerably reduced. Alternatively, the ability to choose a first-order exchange coefficient that intentionally decouples the surface and subsurface facilitates concept-development simulations to examine real-world situations where the surface-subsurface exchange is impaired. While the parameters comprising the first-order exchange coefficient cannot be directly estimated or measured, the insensitivity of the simulated flow system to these parameters (when chosen appropriately) combined with the ability to mimic actual physical processes suggests that the first-order exchange coefficient approach can be consistent with a physics-based framework. Copyright ?? 2009 John Wiley & Sons, Ltd.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-06-15

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

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

International Nuclear Information System (INIS)

Nguyen, Luan; Tao, Franklin

2016-01-01

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

Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

Directory of Open Access Journals (Sweden)

Lukasz JOZWIAK

2017-02-01

Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14406

Enolate Stabilization by Anion-π Interactions: Deuterium Exchange in Malonate Dilactones on π-Acidic Surfaces.

Science.gov (United States)

Miros, François N; Zhao, Yingjie; Sargsyan, Gevorg; Pupier, Marion; Besnard, Céline; Beuchat, César; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

2016-02-18

Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion-π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π-acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π-acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α-protons in the (1) H NMR spectra. The reactivity of these protons on π-acidic surfaces is measured by hydrogen-deuterium (H-D) exchange for 11 different examples, excluding controls. The velocity of H-D exchange increases with π acidity (NDI core substituents: SO2 R>SOR>H>OR>OR/NR2 >SR>NR2 ). The H-D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11-13 atoms). Most importantly, H-D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)-macrocycle is reported). For maximal π acidity, transition-state stabilizations up to -18.8 kJ mol(-1) are obtained for H-D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pKa =10.9 calculates to a ΔpKa =-5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as "impossible" in biology, the found enolate-π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven-component π-acidity gradient over almost 1 eV demonstrates quantitatively that such important anion-π activities can be expected only from

H/D exchange in the reaction of D2 with Bis(triphenyl phosphite)(acetylacetonato)rhodium(I), Rh(P(OPh)3)2(acac)

International Nuclear Information System (INIS)

Whitmore, B.C.; Eisenberg, R.

1984-01-01

The reaction of Rh(P)OPh) 3 ) 2 (acac) (1) with D 2 benzene has been studied by 1 H NMR spectroscopy, and complex 1 has been found to undergo H/D exchange at the ortho positions of the coordinated phosphite ligands and at the central methine position of the acetylacetonate ligand. At 75 0 C, the exchange reaction proceeds with the extent of deuterium incorporation into P(OPh) 3 being the same as that into acac at all stages of the H/D exchange process. At 60 0 C, deuterium incorporation into P(OPh) 3 is initially more rapid than that into the acac ligand. The initial rate of deuterium incorporation into P(OPh) 3 by 1 in benzene-d 6 under D 2 at 60 0 C proceeds with a first-order rate constant of 9.6 x 10 -5 s -1 . A mechanism for this exchange process is proposed. 13 references, 3 figures, 2 tables

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.

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.

OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

Energy Technology Data Exchange (ETDEWEB)

Byrn, Marianne; Calvin, Melvin

1965-12-01

Using infra-red spectroscopy, the equilibrium exchange times have been determined for a series of ketones, aromatic aldehydes, and {beta}-ketoesters reacting with oxygen 18 enriched water. These exchange times have been evaluated in terms of steric and electronic considerations, and applied to a discussion of the exchange times of chlorophylls a and b and chlorophyll derivatives.

Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering

Science.gov (United States)

Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig

The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.

Isotope exchange of molecular oxygen with oxygen of La0,7Sr0,3CoO3-δ

International Nuclear Information System (INIS)

Vdovin, G.K.; Kuzin, B.L.; Kurumchin, Eh.Kh.

1991-01-01

The exchange rate of the oxygen in La 0,7 Sr 0,3 CoO 3-δ has been measured by an isotopic exchange method at temperatures 620-1250 K and pressures 1.6-10 torr. The activation energy and the dependence of the exchange rate on pressures in gas have been defined. It is suggested that the knees on the temperature dependences of the exchange rate are attributed to the appearance of Co 2+ ions on the surface of the sample at elevated temperature as new centres of the exchange reaction. The activation energies of the adsorption and desorption processes on the La 0,7 Sr 0,3 CoO 3-δ surface have been estimated

Molecular beam scattering experiments on the abstraction and exchange reactions of deuterium atoms with the hydrogen halides HCl, HBr, and HI

International Nuclear Information System (INIS)

Bauer, W.; Rusin, L.Y.; Toennies, J.P.

1978-01-01

Molecular beam scattering experiments have been carried out on the abstraction and exchange reactions of deuterium atoms (T=2600 K) with the hydrogen halides HX(T=300 K) in the range of scattering angles: 0 0 0 (theta/sub cm/=0 0 is the direction of the incident D-atom beam). The apparatus employed a very sensitive electron bombardment detector with a sufficiently low H 2 background to make possible the measurement of differential cross sections of about 0.1 A 2 /sr for reactively scattered HD and H and nonreactively scattered D-atoms. The measured HD signal can be largely attributed to various background sources and only serves to establish a rough upper limit on the abstraction cross section in the angular range investigated. The H-atom signal was more intense. The observed angular distribution was forward peaked, and is attributed to the exchange reaction. The nonreactively scattered D-atom signal was used in conjunction with a recently reported effective spherically symmetric potential to provide an absolute calibration of the detector sensitivity. The measured integral cross sections for the exchange reactions are 2.3 A 2 (D+HCl), 1.3 A 2 (D+HBr) and 1.6 A 2 (D+HI) with an estimated error of about +- 30%. The absolute cross sections and the H-atom angular distributions are consistent with the DX distributions measured by McDonald and Herschbach. Both experimental angular distributions are considerably narrower than those predicted by the recent classical trajectory calculations of Raff, Suzukawa, and Thompson. The implications of the new data for the activation energies for the exchange reactions are discussed

Cumulative Significance of Hyporheic Exchange and Biogeochemical Processing in River Networks

Science.gov (United States)

Harvey, J. W.; Gomez-Velez, J. D.

2014-12-01

Biogeochemical reactions in rivers that decrease excessive loads of nutrients, metals, organic compounds, etc. are enhanced by hydrologic interactions with microbially and geochemically active sediments of the hyporheic zone. The significance of reactions in individual hyporheic flow paths has been shown to be controlled by the contact time between river water and sediment and the intrinsic reaction rate in the sediment. However, little is known about how the cumulative effects of hyporheic processing in large river basins. We used the river network model NEXSS (Gomez-Velez and Harvey, submitted) to simulate hyporheic exchange through synthetic river networks based on the best available models of network topology, hydraulic geometry and scaling of geomorphic features, grain size, hydraulic conductivity, and intrinsic reaction rates of nutrients and metals in river sediment. The dimensionless reaction significance factor, RSF (Harvey et al., 2013) was used to quantify the cumulative removal fraction of a reactive solute by hyporheic processing. SF scales reaction progress in a single pass through the hyporheic zone with the proportion of stream discharge passing through the hyporheic zone for a specified distance. Reaction progress is optimal where the intrinsic reaction timescale in sediment matches the residence time of hyporheic flow and is less efficient in longer residence time hyporheic flow as a result of the decreasing proportion of river flow that is processed by longer residence time hyporheic flow paths. In contrast, higher fluxes through short residence time hyporheic flow paths may be inefficient because of the repeated surface-subsurface exchanges required to complete the reaction. Using NEXSS we found that reaction efficiency may be high in both small streams and large rivers, although for different reasons. In small streams reaction progress generally is dominated by faster pathways of vertical exchange beneath submerged bedforms. Slower exchange

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.

Nucleon exchange properties of the E/A=8.5 MeV 74Ge+165Ho reaction

International Nuclear Information System (INIS)

Planeta, R.; Kwiatkowski, K.; Zhou, S.H.; Viola, V.E.; Breuer, H.; McMahan, M.A.; Kehoe, W.; Mignerey, A.C.

1990-01-01

Mass and charge distributions have been measured for damped projectile-like fragments in the reaction 74 Ge+ 165 Ho at 8.5 MeV per nucleon bombarding energy. Coincidences were measured between Z- and A-identified projectile-like fragments and angle-correlated heavy reaction partners in order to derive the primary mass distribution for projectile-like fragments. Centroids and variances of the primary and post-evaporative Z, N, and A distributions are presented. The evolution of the primary N and Z distributions as a function of energy loss is found to deviate from predictions of the nucleon exchange transport model

Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

Science.gov (United States)

Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

2017-08-22

Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

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.

Ion-Exchange Processes and Mechanisms in Glasses

International Nuclear Information System (INIS)

McGrail, B.P.; Icenhower, J.P.; Darab, J.G.; Shuh, D.K.; Baer, D.R.; Shutthanandan, V.; Thevuthasan, S.; Engelhard, M.H.; Steele, J.L.; Rodriguez, E.A.; Liu, P.; Ivanov, K.E.; Booth, C.H.; Nachimuthu, P.

2001-01-01

Leaching of alkalis from glass is widely recognized as an important mechanism in the initial stages of glass-water interactions. Pioneering experimental studies [1-3] nearly thirty-five years ago established that alkali (designated as M + ) are lost to solution more rapidly than network-forming cations. The overall chemical reaction describing the process can be written as: (triple b ond)Si-O-M + H + → (triple b ond)Si-OH + M + (1) or (triple b ond)Si-O-M + H 3 O + → (triple b ond)Si-OH + M + + H 2 O. (2) Doremus and coworkers [4-7] fashioned a quantitative model where M + ions in the glass are exchanged for counter-diffusing H 3 O + or H + . Subsequent investigations [8], which have relied heavily on reaction layer analysis, recognized the role of H 2 O molecules in the alkali-exchange process, without minimizing the importance of charged hydrogen species. Beginning in the 1980s, however, interest in M + -H + exchange reactions in silicate glasses diminished considerably because important experimental observations showed that network hydrolysis and dissolution rates were principally controlled by the chemical potential difference between the glass and solution (chemical affinity) [9]. For nuclear waste glasses, formation of alteration products or secondary phases that remove important elements from solution, particularly Si, was found to have very large impacts on glass dissolution rates [10,11]. Consequently, recent work on glass/water interactions has focused on understanding this process and incorporating it into models [12]. The ion-exchange process has been largely ignored because it has been thought to be a short duration, secondary or tertiary process that had little or no bearing on long-term corrosion or radionuclide release rates from glasses [13]. The only significant effect identified in the literature that is attributed to alkali ion exchange is an increase in solution pH in static laboratory tests conducted at high surface area-to-volume ratios

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

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.

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.

A phenomenological study of the {pi}{sup -} p {yields} {pi}{sup 0} n charge exchange reaction at high energy; Etude phenomenologique de la reaction d`echange de charge {pi}{sup -} p {yields} {pi}{sup 0} n a haute energie

Energy Technology Data Exchange (ETDEWEB)

Michaud, Y

1995-09-21

The aim of the study was to examine the behaviour of the proton-proton elastic scattering, for mass center energies around 10 GeV, and more especially to study the charge exchange reaction {pi}{sup -} p {yields} {pi}{sup 0} n for mass center energies between 3 and 20 GeV. A formalism based on the Glauber model has been used, and a Regge trajectory exchange term was introduced in the model in order to enable the description of the lower energy domain (inferior to 10 GeV) that is characterized by a large contribution of meson exchanges at the scattering amplitude. The Glauber model is then applied to the charge exchange reaction and the differential cross section is analyzed for a center mass energy comprised between 3 and 20 GeV, together with the polarization at 40 GeV/c. The approach is then validated through the study of the {pi}{sup -} p {yields} {eta} n reaction. The size of the kernel of proton and pion components implied in the {pi}{sup -} p {yields} {pi}{sup 0} n reaction, is also investigated. 90 refs., 48 figs., 4 tabs., 5 appends.

Gas exchange measurements in natural systems

International Nuclear Information System (INIS)

Broecker, W.S.; Peng, T.H.

1983-01-01

Direct knowledge of the rates of gas exchange in lakes and the ocean is based almost entirely on measurements of the isotopes 14 C, 222 Rn and 3 He. The distribution of natural radiocarbon has yielded the average rate of CO 2 exchange for the ocean and for several closed basin lakes. That of bomb produced radiocarbon has been used in the same systems. The 222 Rn to 226 Ra ratio in open ocean surface water has been used to give local short term gas exchange rates. The radon method generally cannot be used in lakes, rivers, estuaries or shelf areas because of the input of radon from sediments. A few attempts have been made to use the excess 3 He produced by decay of bomb produced tritium in lakes to give gas transfer rates. The uncertainty in the molecular diffusivity of helium and in the diffusivity dependence of the rate of gas transfer holds back the application of this method. A few attempts have been made to enrich the surface waters of small lakes with 226 Ra and 3 H in order to allow the use of the 222 Rn and 3 He methods. While these studies give broadly concordant results, many questions remain unanswered. The wind velocity dependence of gas exchange rate has yet to be established in field studies. The dependence of gas exchange rate on molecular diffusivity also remains in limbo. Finally, the degree of enhancement of CO 2 exchange through chemical reactions has been only partially explored. 49 references, 2 figures, 2 tables

Ion exchange equilibrium constants

CERN Document Server

Marcus, Y

2013-01-01

Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and

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

The deuterium-exchange reaction between water and hydrogen with the thin-film hydrophobic catalyst

International Nuclear Information System (INIS)

Yamashita, Hisao; Mizumoto, Mamoru; Matsuda, Shimpei

1985-01-01

The deuterium-exchange reaction between water and hydrogen with a hydrophobic catalyst was studied. The hydrophobic catalyst was composed of platinum as an active component and porous poly(tetrafluoroethylene) (PTFE) as a support. The PTFE support was in two forms, i.e., (a) a pellet and (b) a thin-film with the thickness of 50 μm. The primary purpose of the thin film hydrophobic catalyst was to reduce the platinum usage in the reactor. The activity of the catalyst was measured in a trickle bed reactor at atmospheric pressure and temperature of 20 ∼ 70 deg C. It has been found that the employment of the thin-film catalyst reduced the platinum usage to 1/5 of the reactor in the case of using a conventional catalyst. Platinum particles on the thin-film catalyst work efficiently because the reactants were easily diffused to the active sites. It has also been found that the isotopic exchange rate with the thin-film catalyst increased with the increase in the ratio of liquid/gas and increased with the rise of the reaction temperature. It was found from an endurance test that the activity of the thin-film catalyst decreased gradually due to the condensation of water vapor in the catalyst, but was regenarated by heating the catalyst to remove the condensed water. (author)

Kinetic study on ligand exchange reaction between ethylenedicysteine and 99mTc- glucoheptonate (99mTc-GH)

International Nuclear Information System (INIS)

Wu, C.Y.; Ji, S.R.; Lu, C.X.; Ding, S.Y.; Chen, Z.P.; Lin, X.T.

2002-01-01

Aim: 99m Tc-L,L-ethylenedicysteine( 99m Tc-EC)is a new type of renal imaging agent. It can be labeled very easily and efficiently at room temperature through direct labeling at pH 12. The need for direct labeling at pH 12 does not compromise the simplicity and ease of preparation of 99m Tc-EC and its practical usefulness in daily routine. On the basis of the labeling experiments, we developed a ligand exchange labeling method, in which the labeling EC with 99m Tc can be performed at pH 8. In order to provide a theoretic basis, a detailed kinetic study of ligand exchange reaction between 99m Tc- glucoheptonate( 99m Tc-GH) and EC was carried out. Materials and Methods: 99m Tc-EC is prepared as follows: 99m Tc-GH + EC → 99m Tc-EC + GH, labeling can be easily performed by adding 99m TcO 4 - (2∼6ml generator elute) to glucoheptonate solution containing SnCl 2 .2H 2 O solution to form 99m Tc-GH, then freshly prepared 99m Tc-GH is transferred to the aqueous solution of different concentrations of EC at different pH value, after being shaken, 99m Tc-EC was formed. Radiolabeling yield(RLY) and radiochemical purity(RCP) of 99m Tc-GH and 99m Tc-EC were measured by Xinhua No.1 paper with developing system of Me 2 CO/H 2 O/con.NH 3 .H 2 O=9/3/1(V/V). 99m Tc-GH(RCP must be over 98%, 80ul, 3.6∼7.4MBq) was added to 1ml of 0.5mol/L phosphate buffer(pH 12) containing different amount of EC(150, 75, 50 and 15ug), the sample was taken out at different time intervals and RCP was determined. The solution of EC(30ul, 5g/L) was added to 1ml of 0.5mol/L phosphate buffer at different pH value(pH11, 10, 9, 8, 7), after completely vortexed, 99m Tc-GH(RCP must be over 98%, 80ul, 3.6∼7.4MBq) was then added, the sample was taken out and RCP was determined as above. The rate constant(k) of ligand exchange reaction at different concentrations of EC and different reaction pH values were calculated out by integrating. Plot ln[1/(1-RLY)] vs t(time) showed a liner relationship, and the rate

The role of cell walls and pectins in cation exchange and surface area of plant roots.

Science.gov (United States)

Szatanik-Kloc, A; Szerement, J; Józefaciuk, G

2017-08-01

We aimed to assess role of cell walls in formation of cation exchange capacity, surface charge, surface acidity, specific surface, water adsorption energy and surface charge density of plant roots, and to find the input of the cell wall pectins to the above properties. Whole roots, isolated cell walls and the residue after the extraction of pectins from the cell walls of two Apiaceae L. species (celeriac and parsnip) were studied using potentiometric titration curves and water vapor adsorption - desorption isotherms. Total amount of surface charge, as well as the cation exchange capacity were markedly higher in roots than in their cell walls, suggesting large contribution of other cell organelles to the binding of cations by the whole root cells. Significantly lower charge of the residues after removal of pectins was noted indicating that pectins play the most important role in surface charge formation of cell walls. The specific surface was similar for all of the studied materials. For the separated cell walls it was around 10% smaller than of the whole roots, and it increased slightly after the removal of pectins. The surface charge density and water vapor adsorption energy were the highest for the whole roots and the lowest for the cell walls residues after removal of pectins. The results indicate that the cell walls and plasma membranes are jointly involved in root ion exchange and surface characteristics and their contribution depends upon the plant species. Copyright © 2017 Elsevier GmbH. All rights reserved.

Processes of Ammonia Air-Surface Exchange in a Fertilized Zea Mays Canopy

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Recent incorporation of coupled soil biogeochemical and bi-directional NH3 air-surface exchange algorithms into regional air quality models holds promise for further reducing uncertainty in estimates of NH3 emissions from fertilized soils. While this advancement represents a sig...

Sulfonation of cPTFE Film grafted Styrene for Proton Exchange Membrane Fuel Cell

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Yohan Yohan

2010-10-01

Full Text Available Sulfonation of γ-ray iradiated and styrene-grafted crosslinked polytetrafluoroethylene film (cPTFE-g-S film have been done. The aim of the research is to make hydropyl membrane as proton exchange membrane fuel cell. Sulfonation was prepared with chlorosulfonic acid in chloroethane under various conditions. The impact of the percent of grafting, the concentration of chlorosulfonic acid, the reaction time,and the reaction temperature on the properties of sulfonated film is examinated. The results show that sulfonation of surface-grafted films is incomplete at room  temperature. The increasing of concentration of chlorosulfonic acid and reaction temperature accelerates the reaction but they also add favor side reactions. These will lead to decreasing of the ion-exchange capacity, water uptake, and proton conductivity but increasing the resistance to oxidation in a perhidrol solution. The cPTFE-g-SS membrane which is resulted has stability in a H2O2 30% solution for 20 hours.

Bombarding energy dependence of nucleon exchange and energy dissipation in the strongly damped reaction 209Bi + 136Xe

International Nuclear Information System (INIS)

Wilcke, W.W.; Schroeder, W.U.; Huizenga, J.R.; Birkelund, J.R.; Randrup, J.

1980-01-01

Although considerable progress has been achieved in the understanding of strongly damped reactions at energies several MeV/u above the Coulomb barrier, some important experimental results are not yet clearly understood. Among these is the degree of correlation between the nucleon exchange and the large energy losses observed. Experimental evidence suggesting nucleon exchange as described by a one-body model to be the major component of the dissipation mechanism is discussed. It is concluded that the previously unexplained bombarding energy dependence between energy loss and fragment charge dispersion can be understood on the basis of a nucleon exchange model, provided the Pauli exclusion principle is taken into account. No necessity is seen to invoke further energy dissipation mechanisms. 7 figures

Effect of degree of polymerization and of temperature on the reactivity of poly(vinyl alcohol) by applying T-for-H exchange reaction

International Nuclear Information System (INIS)

Imaizumi, Hiroshi; Imai, Kazunari

1999-01-01

In order to reveal the effect of the degree of polymerization and of temperature on the reactivity of functional polymers, the hydrogen-isotope exchange reaction between poly(vinyl alcohol) (PVA) having each degree of polymerization and tritiated water vapor (HTO vapor) was dynamically observed at 35-80 deg C in a gas-solid system. The reason of the observation at 35 deg C is to clarify the possibility of the T-for-H exchange reaction at a temperature near the environment. The degree of polymerization of PVA used in this work was 500, 1000, 2000, 2800, or 3500. Applying the A''-McKay plot method to the data obtained in each observation, the rate constant (k) for each PVA in the reaction was calculated. Moreover, the Arrhenius plot for each PVA was made by using the k values. Comparing the k values and the results obtained previously, the following six matters have been clarified. In the temperature range of 35-80 deg C, the T-for-H exchange reaction between HTO vapor and each PVA occurred, and in this case, the atoms participating in the reaction are the H atoms in the OH groups in PVA and T atoms in HTO vapor. The reactivity of each PVA increases with rising temperature, and decreases with increasing the degree of polymerization. The rate of the decreasing of k with increasing the degree of polymerization changes at near the degree of polymerization of 1000, and the rate is fairly large under the degree of 1000. Under the degree of polymerization of 1000, the reactivity of PVA is more affected by the effect of the degree of polymerization than by the effect of temperature, and the reactivity is large when the degree of polymerization is small. Over the degree of polymerization of 1000, the reactivity of PVA is affected by both the degree of polymerization and temperature, and the reactivity is large when temperature is high. For the T-for-H exchange reaction in a gas-solid system, the reaction form is unchanged in the range of 35-80 deg C, and the reactivity at 35

Investigation of ammonia air-surface exchange processes in a ...

Science.gov (United States)

Recent assessments of atmospheric deposition in North America note the increasing importance of reduced (NHx = NH3 + NH4+) forms of nitrogen (N) relative to oxidized forms. This shift in in the composition of inorganic nitrogen deposition has both ecological and policy implications. Deposition budgets developed from inferential models applied at the landscape scale, as well as regional and global chemical transport models, indicate that NH3 dry deposition contributes a significant portion of inorganic N deposition in many areas. However, the bidirectional NH3 flux algorithms employed in these models have not been extensively evaluated for North American conditions (e.g, atmospheric chemistry, meteorology, biogeochemistry). Further understanding of the processes controlling NH3 air-surface exchange in natural systems is critically needed. Based on preliminary results from the Southern Appalachian Nitrogen Deposition Study (SANDS), this presentation examines processes of NH3 air-surface exchange in a deciduous montane forest at the Coweeta Hydrologic Laboratory in western North Carolina. A combination of measurements and modeling are used to investigate net fluxes of NH3 above the forest and sources and sinks of NH3 within the canopy and forest floor. Measurements of biogeochemical NH4+ pools are used to characterize emission potential and NH3 compensation points of canopy foliage (i.e., green vegetation), leaf litter, and soil and their relation to NH3 fluxes

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.

Metal-Exchanged β Zeolites as Catalysts for the Conversion of Acetone to Hydrocarbons

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Aurora J. Cruz-Cabeza

2012-01-01

Full Text Available Various metal-β zeolites have been synthesized under similar ion-exchange conditions. During the exchange process, the nature and acid strength of the used cations modified the composition and textural properties as well as the Brönsted and Lewis acidity of the final materials. Zeolites exchanged with divalent cations showed a clear decrease of their surface Brönsted acidity and an increase of their Lewis acidity. All materials were active as catalysts for the transformation of acetone into hydrocarbons. Although the protonic zeolite was the most active in the acetone conversion (96.8% conversion, the metal-exchanged zeolites showed varied selectivities towards different products of the reaction. In particular, we found the Cu-β to have a considerable selectivity towards the production of isobutene from acetone (over 31% yield compared to 7.5% of the protonic zeolite. We propose different reactions mechanisms in order to explain the final product distributions.

Beneficial Effect of Surface Decorations on the Surface Exchange of Lanthanum Strontium Ferrite and Dual Phase Composites

DEFF Research Database (Denmark)

Ovtar, Simona; Søgaard, Martin; Song, Jia

2016-01-01

. These perovskites possess a mixed ionic and electronic conductivity (MIEC), which can be highly beneficial for the processes on oxygen electrode surfaces. The oxygen transport through a MIEC is determined by the rate of the oxygen exchange over the gas-solid interface and the diffusivity of oxide ions and electrons...

Gas-phase ion/molecule isotope-exchange reactions: methodology for counting hydrogen atoms in specific organic structural environments by chemical ionization mass spectrometry

International Nuclear Information System (INIS)

Hunt, D.F.; Sethi, S.K.

1980-01-01

Ion/molecule reactions are described which facilitate exchange of hydrogens for deuteriums in a variety of different chemical environments. Aromatic hydrogens in alkylbenzenes, oxygenated benzenes, m-toluidine, m-phenylenediamine, thiophene, and several polycyclic aromatic hydrocarbons and metallocenes are exchanged under positive ion CI conditions by using either D 2 O, EtOD, or ND 3 as the reagent gas. Aromatic hydrogens, benzylic hydrogens, and hydrogens on carbon adjacent to carbonyl groups suffer exchange under negative ion CI conditions in ND 3 , D 2 O, and EtOD, respectively. A possible mechanism for the exchange process is discussed. 1 figure, 2 tables

Elastic scattering and charge exchange reaction studies with {sup 6}He, {sup 10,11}Be

Energy Technology Data Exchange (ETDEWEB)

Roussel-Chomaz, P; Cortina-Gil, M D; Mittig, W; Casandjian, J M; Chartier, M [Grand Accelerateur National d` Ions Lourds (GANIL), 14 - Caen (France); Alamanos, N; Auger, F; Fekou-Youmbi, V [CEA Centre d` Etudes de Saclay, 91 - Gif-sur-Yvette (France). Dept. d` Astrophysique, de la Physique des Particules, de la Physique Nucleaire et de l` Instrumentation Associee; Barrette, J [McGill Univ., Montreal, PQ (Canada); Blumenfeld, Y [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire; and others

1996-12-31

The elastic scattering and charge exchange reaction of {sup 6}He, {sup 10,11}Be secondary beams on proton and {sup 12}C targets have been measured. The combined use of SISSI and SPEG allowed to obtain very good quality data in terms of energy and angular resolution. Preliminary analyses of the angular distributions using global parameter set for the optical model potentials, as well as more microscopic approaches are presented. (author). 14 refs.

Chemical uranium enrichment with ion exchanger

International Nuclear Information System (INIS)

Takeda, Kunihiko; Onitsuka, Hatsuki; Obanawa, Heiichiro

1991-01-01

The uranium enrichment by using ion-exchange has been studied and developed since 1972. The ion-exchange rate has been improved approx. 3000 times and the electron exchange reaction, which occurs with ion-exchange reaction, was also accelerated with catalyst. Flow disturbance in a ion-exchange column has been fully studied and the value of turbulence has been reduced to 150μm. These results allowed us to design a very fine separation column, in which about 10000 stages can be obtained even when the column is more than 1 m in diameter. In the course of the development, a self-regenerating reaction between the redox agents was discovered and incorporated into the process, and has resulted in a reduction of 70 % in the separation energy requirement. (author)

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.

Fe atom exchange between aqueous Fe2+ and magnetite.

Science.gov (United States)

Gorski, Christopher A; Handler, Robert M; Beard, Brian L; Pasakarnis, Timothy; Johnson, Clark M; Scherer, Michelle M

2012-11-20

The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.

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.

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

Science.gov (United States)

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Potential for Small Unmanned Aircraft Systems Applications for Identifying Groundwater-Surface Water Exchange in a Meandering River Reach

Science.gov (United States)

Pai, H.; Malenda, H. F.; Briggs, M. A.; Singha, K.; González-Pinzón, R.; Gooseff, M. N.; Tyler, S. W.

2017-12-01

The exchange of groundwater and surface water (GW-SW), including dissolved constituents and energy, represents a critical yet challenging characterization problem for hydrogeologists and stream ecologists. Here we describe the use of a suite of high spatial resolution remote sensing techniques, collected using a small unmanned aircraft system (sUAS), to provide novel and complementary data to analyze GW-SW exchange. sUAS provided centimeter-scale resolution topography and water surface elevations, which are often drivers of exchange along the river corridor. Additionally, sUAS-based vegetation imagery, vegetation-top elevation, and normalized difference vegetation index mapping indicated GW-SW exchange patterns that are difficult to characterize from the land surface and may not be resolved from coarser satellite-based imagery. We combined these data with estimates of sediment hydraulic conductivity to provide a direct estimate of GW "shortcutting" through meander necks, which was corroborated by temperature data at the riverbed interface.

Two approaches to the clinical dilemma of treating TTP with therapeutic plasma exchange in patients with a history of anaphylactic reactions to plasma.

Science.gov (United States)

Sidhu, Davinder; Snyder, Edward L; Tormey, Christopher A

2017-06-01

Thrombotic thrombocytopenic purpura (TTP) is a rare but serious disease caused by autoantibody-mediated deficiency in von Willebrand factor (VWF) cleaving protease, ADAMTS-13. The primary acute treatment is therapeutic plasma exchange (TPE). However, some patients can develop allergic/anaphylactic reactions to the replacement (i.e., donor) plasma over time. Two potential treatment strategies for patients with TTP who demonstrate severe allergic reactions to plasma used for exchange were examined. Two patients with TTP exacerbations who developed severe allergic reactions to donor plasma were identified. One patient's TPE was re-initiated with Octaplas, a lot-batched solvent and detergent treated, type-specific, pooled donor plasma product. The other patient was exchanged with primarily albumin, followed by slow incremental exposures to donor plasma to mitigate exposures and allergic risks. Both patients were assessed for anaphylaxis. Both treatment strategies were successful in preventing any further clinically significant allergic/anaphylactic reactions and facilitated both patients' TTP remissions. Based on our experience with two similar patients with TTP exacerbations and history of anaphylactic reactions to plasma during TPE, we have identified two possible treatment protocols to achieve remission in this clinical dilemma. Substituting Octaplas for standard plasma or, alternatively, using albumin with slowly increasing amounts of standard plasma may help to mitigate the risk of further anaphylactic adverse events. J. Clin. Apheresis 32:158-162, 2017. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Quasi-elastic transfer and charge-exchange reactions in collisions of 48Ti on 42Ca and 26Mg

International Nuclear Information System (INIS)

Brendel, C.

1985-01-01

At the GSI magnetic spectrometer quasi-elastic transfer and charge-exchange reactions of the system 48 Ti + 42 Ca at incident energies E lab = 240, 300, and 385 MeV and additionally at the higher projectile energy the system 48 Ti + 26 Mg were studied each in the excitation energy range up to E x ≅ 80 MeV. The transition strength was for each particle-hole configuration of the final system calculated by means of the DWBA and subsequently folded with a Breit-Wigner distribution. The localization of the strength of the cross section and the specific structure of the energy spectra were at incident energies between 6 and 8 MeV/amu for all angles well reproduced. By an extension of the core-excitation model to many-stage reactions the charge-exchange reaction 48 Ti + 42 Ca → 48 Sc + 42 Sc could be described as sequential two-stage process. In the two-neutron stripping reaction 48 Ti + 42 Ca → 46 Ti + 44 Ca a surprisingly narrow line with a width of the experimental resolution and an excitation energy of E x = 17.8 MeV was measured at angles smaller than the grazing angle. In the 48 Ti + 26 Mg system the corresponding 46 Ti spectra show also under forward angles structures at excitation energies between 8 and 16 MeV. These lines can be explained as two-neutron states with high spin. (orig./HSI) [de

Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

Science.gov (United States)

Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

2017-08-01

Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

Ratiometric analysis in hyperpolarized NMR (I): test of the two-site exchange model and the quantification of reaction rate constants.

Science.gov (United States)

Li, Lin Z; Kadlececk, Stephen; Xu, He N; Daye, Dania; Pullinger, Benjamin; Profka, Harrilla; Chodosh, Lewis; Rizi, Rahim

2013-10-01

Conventional methods for the analysis of in vivo hyperpolarized (13) C NMR data from the lactate dehydrogenase (LDH) reaction usually make assumptions on the stability of rate constants and/or the validity of the two-site exchange model. In this study, we developed a framework to test the validity of the assumption of stable reaction rate constants and the two-site exchange model in vivo via ratiometric fitting of the time courses of the signal ratio L(t)/P(t). Our analysis provided evidence that the LDH enzymatic kinetics observed by hyperpolarized NMR are in near-equilibrium and satisfy the two-site exchange model for only a specific time window. In addition, we quantified both the forward and reverse exchange rate constants of the LDH reaction for the transgenic and mouse xenograft models of breast cancer using the ratio fitting method developed, which includes only two modeling parameters and is less sensitive to the influence of instrument settings/protocols, such as flip angles, degree of polarization and tracer dosage. We further compared the ratio fitting method with a conventional two-site exchange modeling method, i.e. the differential equation fitting method, using both the experimental and simulated hyperpolarized NMR data. The ratio fitting method appeared to fit better than the differential equation fitting method for the reverse rate constant on the mouse tumor data, with less relative errors on average, whereas the differential equation fitting method also resulted in a negative reverse rate constant for one tumor. The simulation results indicated that the accuracy of both methods depends on the width of the transport function, noise level and rate constant ratio; one method may be more accurate than the other based on the experimental/biological conditions aforementioned. We were able to categorize our tumor models into specific conditions of the computer simulation and to estimate the errors of rate quantification. We also discussed possible

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

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

Air-side performance of a micro-channel heat exchanger in wet surface conditions

Directory of Open Access Journals (Sweden)

Srisomba Raviwat

2017-01-01

Full Text Available The effects of operating conditions on the air-side heat transfer, and pressure drop of a micro-channel heat exchanger under wet surface conditions were studied experimentally. The test section was an aluminum micro-channel heat exchanger, consisting of a multi-louvered fin and multi-port mini-channels. Experiments were conducted to study the effects of inlet relative humidity, air frontal velocity, air inlet temperature, and refrigerant temperature on air-side performance. The experimental data were analyzed using the mean enthalpy difference method. The test run was performed at relative air humidities ranging between 45% and 80%; air inlet temperature ranges of 27, 30, and 33°C; refrigerant-saturated temperatures ranging from 18 to 22°C; and Reynolds numbers between 128 and 166. The results show that the inlet relative humidity, air inlet temperature, and the refrigerant temperature had significant effects on heat transfer performance and air-side pressure drop. The heat transfer coefficient and pressure drop for the micro-channel heat exchanger under wet surface conditions are proposed in terms of the Colburn j factor and Fanning f factor.

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

International Nuclear Information System (INIS)

Osborn, David L.

2017-01-01

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

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

Science.gov (United States)

Osborn, David L.

2017-05-01

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

Reaction of water vapor with a clean liquid uranium surface

International Nuclear Information System (INIS)

Siekhaus, W.

1985-01-01

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

Contribution to the study of isotopic exchange of oxygen between nickel oxide and the gases arising from the oxidation reaction of carbon monoxide; Contribution a l'etude de l'echange isotopique de l'oxygene entre l'oxyde de nickel et les gaz de la reaction d'oxydation de l'oxyde de carbone

Energy Technology Data Exchange (ETDEWEB)

Bailly, J C [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1967-12-01

The 3 isotopic reactions of oxygen: C{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O + Ni{sup 18}O, {sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} {sup 16}O{sub 2} + Ni{sup 18}O, and C{sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O{sub 2} + Ni{sup 18}O between CO, CO{sub 2}, O{sub 2} and NiO are studied using a mass spectrometer. The isotopic gaseous mixtures are prepared from oxygen-18 enriched water. A first order kinetic law has been found for these reactions in the gaseous phase, and the activation energies have been determined. Only CO and CO{sub 2} exchange oxygen, at room temperature, but only with part of the oxide surface. Gaseous O{sub 2} reacts with the whole surface at 250 C, the slow step of the exchange process, in the gaseous phase, being certainly the mobility of oxygen ions on the surface of NiO. (author) [French] Les 3 reactions d'echange isotopique de l'oxygene: C{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O + Ni{sup 18}O, {sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} {sup 16}O{sub 2} + Ni{sup 18}O, et C{sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O{sub 2} + Ni{sup 18}O entre l'oxyde de carbone, l'oxygene gazeux, le gaz carbonique et l'oxyde de nickel sont etudiees par spectrometrie de masse. Les melanges isotopiques gazeux sont prepares a partir d'une eau enrichie en isotope 18 de l'oxygene. Une loi cinetique du premier ordre a ete trouvee pour les trois reactions d'echange en phase gazeuse, et des energies d'activation de ces reactions ont ete determinees. Seuls CO et CO{sub 2} echangent l'oxygene, des la temperature ambiante, mais avec une fraction seulement de la surface de l'oxyde. O{sub 2} gazeux reagit avec toute la surface du solide a 250 C, l'etape lente du processus d'echange en phase gazeuse etant vraisemblablement liee a la mobilite des ions oxygene superficiels de NiO. (auteur)

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.

Hydrothermal reaction of albite and a sodium aluminosilicate glass: A solid-state NMR study

Science.gov (United States)

Yang, Wang-hong Alex; Kirkpatrick, R. James

1989-04-01

We present here a solid-state NMR study of the structure and chemical composition of the products and mechanisms of the reaction of crystalline low albite and a glass of nearly albite composition with aqueous solutions of pH from 1 to 11 at 250°C. For the crystalline albite, there are no detectable bulk or surface structural changes due to aqueous attack, consistent with the idea that both cation exchange and disruption of the aluminosilicate framework occur only near the mineral/solution interface and that the hydrated surface layer, if it exists, is not more than about 30 Å thick. This reaction occurs by solution/reprecipitation, and its rate decreases with increasing solution pH, supporting the idea that the dissolution of feldspar is initiated by cation-exchange. For the glass, the reaction proceeds by cation exchange of protons for Na +, incorporation of molecular water into the bulk glass, and a small amount of depolymerization of the aluminosilicate framework in the interior of the glass. Cation exchange becomes less important with increasing solution pH. The incorporation of molecular water and cation-exchange cause structural changes in the glass via solidstate adjustment without dissolution/reprecipitation. The large cations in the hydrated glass (Na and K) probably have a shell of water molecules around them, with a maximum average coordination number of six. The secondary phases formed from both albite and the glass are often amorphous and can be well characterized by NMR. The compositional and structural variations of the amorphous phases are important factors in these reactions and cannot be ignored in theoretical models of aluminosilicate dissolution. As expected, the aluminum coordination in the secondary phases changes from six-fold to four-fold as the solution pH increases.

Uncertainty quantification of surface-water/groundwater exchange estimates in large wetland systems using Python

Science.gov (United States)

Hughes, J. D.; Metz, P. A.

2014-12-01

Most watershed studies include observation-based water budget analyses to develop first-order estimates of significant flow terms. Surface-water/groundwater (SWGW) exchange is typically assumed to be equal to the residual of the sum of inflows and outflows in a watershed. These estimates of SWGW exchange, however, are highly uncertain as a result of the propagation of uncertainty inherent in the calculation or processing of the other terms of the water budget, such as stage-area-volume relations, and uncertainties associated with land-cover based evapotranspiration (ET) rate estimates. Furthermore, the uncertainty of estimated SWGW exchanges can be magnified in large wetland systems that transition from dry to wet during wet periods. Although it is well understood that observation-based estimates of SWGW exchange are uncertain it is uncommon for the uncertainty of these estimates to be directly quantified. High-level programming languages like Python can greatly reduce the effort required to (1) quantify the uncertainty of estimated SWGW exchange in large wetland systems and (2) evaluate how different approaches for partitioning land-cover data in a watershed may affect the water-budget uncertainty. We have used Python with the Numpy, Scipy.stats, and pyDOE packages to implement an unconstrained Monte Carlo approach with Latin Hypercube sampling to quantify the uncertainty of monthly estimates of SWGW exchange in the Floral City watershed of the Tsala Apopka wetland system in west-central Florida, USA. Possible sources of uncertainty in the water budget analysis include rainfall, ET, canal discharge, and land/bathymetric surface elevations. Each of these input variables was assigned a probability distribution based on observation error or spanning the range of probable values. The Monte Carlo integration process exposes the uncertainties in land-cover based ET rate estimates as the dominant contributor to the uncertainty in SWGW exchange estimates. We will discuss

Optimization of acidified oil esterification catalyzed by sulfonated cation exchange resin using response surface methodology

International Nuclear Information System (INIS)

Ma, Lingling; Han, Ying; Sun, Kaian; Lu, Jie; Ding, Jincheng

2015-01-01

Highlights: • As lipid source, acidified oil are from industrial wastes for renewable energy. • The predicted conversion rate of FFAs was 75.24% under the RSM optimized conditions. • The adsorption system was employed to remove the water produced to shift the equilibrium toward ethyl ester production. • Maximum conversion rate of 98.32% was obtained using adsorption system at optimum process parameters. • Compared with tradition methods, molecular sieve dehydration method improved the conversion rate by 23.08%. - Abstract: The esterification of acidified oil with ethanol catalyzed by sulfonated cation exchange resins (SCER) was optimized using the response surface methodology (RSM). The effects of the molar ratio of ethanol to acidified oil, reaction time and catalyst loading on the conversion rate of free fatty acids (FFAs) were investigated at the temperature of the boiling point of ethanol. Results showed that the highest conversion rate of 75.24% was obtained at the molar ratio of ethanol to acidified oil of 23.2, reaction time of 8.0 h and catalyst loading of 35.0 wt.%. Moreover, the conversion rate of FFAs was increased to 98.32% by using a water adsorption apparatus under the RSM optimized conditions. Scanning electronic microscopic–energy dispersive spectrometric (SEM–EDS), X-ray diffractometric (XRD) and thermogravimetric–derivative thermogravimetric (TG–DTG) analyses confirmed that the morphology of catalysts did not change much and the mechanical and thermal stabilities were still good after the reaction. Furthermore, SCER exhibited a high catalytic activity and stability after being reused for five successive times. The fuel properties of the biodiesel were comparable to that of ASTM, EN and GB biodiesel standard

Research on Land Surface Thermal-Hydrologic Exchange in Southern China under Future Climate and Land Cover Scenarios

Directory of Open Access Journals (Sweden)

Jianwu Yan

2013-01-01

Full Text Available Climate change inevitably leads to changes in hydrothermal circulation. However, thermal-hydrologic exchanging caused by land cover change has also undergone ineligible changes. Therefore, studying the comprehensive effects of climate and land cover changes on land surface water and heat exchanges enables us to well understand the formation mechanism of regional climate and predict climate change with fewer uncertainties. This study investigated the land surface thermal-hydrologic exchange across southern China for the next 40 years using a land surface model (ecosystem-atmosphere simulation scheme (EASS. Our findings are summarized as follows. (i Spatiotemporal variation patterns of sensible heat flux (H and evapotranspiration (ET under the land cover scenarios (A2a or B2a and climate change scenario (A1B are unanimous. (ii Both H and ET take on a single peak pattern, and the peak occurs in June or July. (iii Based on the regional interannual variability analysis, H displays a downward trend (10% and ET presents an increasing trend (15%. (iv The annual average H and ET would, respectively, increase and decrease by about 10% when woodland converts to the cultivated land. Through this study, we recognize that land surface water and heat exchanges are affected greatly by the future climate change as well as land cover change.

Non-coherent contributions in charge-exchange reactions and η-η{sup '} mixing

Energy Technology Data Exchange (ETDEWEB)

Nekrasov, M.L. [NRC ' ' Kurchatov Institute' ' , Institute for High Energy Physics, Protvino (Russian Federation)

2017-05-15

We analyse K{sup -}p → (η,η{sup '},π{sup 0})Λ on the basis of the fit of data in a wide region of energies, and π{sup -}p → (η,η{sup '})n at the energies of GAMS-4π. We show that disagreements between the data and the predictions of Regge theory may be explained by the mode change of summation of intermediate contributions at increasing energy, from coherent to non-coherent. A method of experimental measurement of the non-coherent contributions is proposed. On the basis of available data on the charge-exchange reactions the η-η{sup '} mixing is estimated. (orig.)

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.

Quantifying Hyporheic Exchanges in a Large Scale River Reach Using Coupled 3-D Surface and Subsurface Computational Fluid Dynamics Simulations.

Energy Technology Data Exchange (ETDEWEB)

Hammond, Glenn Edward; Bao, J; Huang, M; Hou, Z; Perkins, W; Harding, S; Titzler, S; Ren, H; Thorne, P; Suffield, S; Murray, C; Zachara, J

2017-03-01

Hyporheic exchange is a critical mechanism shaping hydrological and biogeochemical processes along a river corridor. Recent studies on quantifying the hyporheic exchange were mostly limited to local scales due to field inaccessibility, computational demand, and complexity of geomorphology and subsurface geology. Surface flow conditions and subsurface physical properties are well known factors on modulating the hyporheic exchange, but quantitative understanding of their impacts on the strength and direction of hyporheic exchanges at reach scales is absent. In this study, a high resolution computational fluid dynamics (CFD) model that couples surface and subsurface flow and transport is employed to simulate hyporheic exchanges in a 7-km long reach along the main-stem of the Columbia River. Assuming that the hyporheic exchange does not affect surface water flow conditions due to its negligible magnitude compared to the volume and velocity of river water, we developed a one-way coupled surface and subsurface water flow model using the commercial CFD software STAR-CCM+. The model integrates the Reynolds-averaged Navier-Stokes (RANS) equation solver with a realizable κ-ε two-layer turbulence model, a two-layer all y⁺ wall treatment, and the volume of fluid (VOF) method, and is used to simulate hyporheic exchanges by tracking the free water-air interface as well as flow in the river and the subsurface porous media. The model is validated against measurements from acoustic Doppler current profiler (ADCP) in the stream water and hyporheic fluxes derived from a set of temperature profilers installed across the riverbed. The validated model is then employed to systematically investigate how hyporheic exchanges are influenced by surface water fluid dynamics strongly regulated by upstream dam operations, as well as subsurface structures (e.g. thickness of riverbed and subsurface formation layers) and hydrogeological properties (e.g. permeability). The results

MAX phase – Alumina composites via elemental and exchange reactions in the Ti{sub n+1}AC{sub n} systems (A=Al, Si, Ga, Ge, In and Sn)

Energy Technology Data Exchange (ETDEWEB)

Cuskelly, Dylan, E-mail: dylan.cuskelly@uon.edu.au; Richards, Erin; Kisi, Erich, E-mail: Erich.Kisi@newcastle.edu.au

2016-05-15

Extension of the aluminothermal exchange reaction synthesis of M{sub n+1}AX{sub n} phases to systems where the element ‘A’ is not the reducing agent was investigated in systems TiO{sub 2}–A–Al–C for A=Al, Si, Ga, Ge, In and Sn as well as Cr{sub 2}O{sub 3}–Ga–Al–C. MAX phase-Al{sub 2}O{sub 3} composites were made in all systems except those with A=Ga or In. The effectiveness of conversion to MAX phases was generally in the range 63–96% without optimisation of starting ratios. Optimisation in the Ti–Si–C system gave a MAX phase component with >98% Ti{sub 3}SiC{sub 2}. - Graphical abstract: A range of Ti{sub n+1}AX{sub n} phases with different A elements were synthesised directly from the M oxide via exchange reactions. The process has now been shown to be general in all the systems marked in green in the table. - Highlights: • Ti{sub n+1}AC{sub n} phases were produced via a single step exchange reaction. • 3 MAX phase systems were successful via this method for the first time. • Cr{sub 2}GeC was also able to be produced via an exchange reaction. • The interconversion reaction in MAX phases is more general than previously thought.

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

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

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.

Variation in surface water-groundwater exchange with land use in an urban stream

Science.gov (United States)

Ryan, Robert J.; Welty, Claire; Larson, Philip C.

2010-10-01

SummaryA suite of methods is being utilized in the Baltimore metropolitan area to develop an understanding of the interaction between groundwater and surface water at multiple space and time scales. As part of this effort, bromide tracer experiments were conducted over two 10-day periods in August 2007 and May 2008 along two sections (each approximately 900 m long) of Dead Run, a small urban stream located in Baltimore County, Maryland, to investigate the influence of distinct zones of riparian land cover on surface-subsurface exchange and transient storage under low and high baseflow conditions. Riparian land cover varied by reach along a gradient of land use spanning parkland, suburban/residential, commercial, institutional, and transportation, and included wooded, meadow, turf grass, and impervious cover. Under summer low baseflow conditions, surface water-groundwater exchange, defined by gross inflow and gross outflow, was larger and net inflow (gross inflow minus gross outflow) had greater spatial variability, than was observed under spring high baseflow conditions. In addition, the fraction of nominal travel time attributable to transient storage ( Fmed) was lower and was more spatially variable under high baseflow conditions than under low baseflow conditions. The influence of baseflow condition on surface water-ground water exchange and transient storage was most evident in the subreaches with the least riparian forest cover and these effects are attributed to a lack of shading in reaches with little riparian forest cover. We suggest that under summer low baseflow conditions, the lack of shading allowed excess in-channel vegetation growth which acted as a transient storage zone and a conduit for outflow (i.e. uptake and evapotranspiration). Under spring high baseflow conditions the transient storage capacity of the channel was reduced because there was little in-channel vegetation.

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation

DEFF Research Database (Denmark)

Wellendorff, Jess; Lundgård, Keld Troen; Møgelhøj, Andreas

2012-01-01

A methodology for semiempirical density functional optimization, using regularization and cross-validation methods from machine learning, is developed. We demonstrate that such methods enable well-behaved exchange-correlation approximations in very flexible model spaces, thus avoiding the overfit......A methodology for semiempirical density functional optimization, using regularization and cross-validation methods from machine learning, is developed. We demonstrate that such methods enable well-behaved exchange-correlation approximations in very flexible model spaces, thus avoiding...... the energetics of intramolecular and intermolecular, bulk solid, and surface chemical bonding, and the developed optimization method explicitly handles making the compromise based on the directions in model space favored by different materials properties. The approach is applied to designing the Bayesian error...... sets validates the applicability of BEEF-vdW to studies in chemistry and condensed matter physics. Applications of the approximation and its Bayesian ensemble error estimate to two intricate surface science problems support this....

Retardation of heat exchanger surfaces mineral fouling by water-based diethylenetriamine pentaacetate-treated CNT nanofluids

International Nuclear Information System (INIS)

Teng, K.H.; Amiri, Ahmad; Kazi, S.N.; Bakar, M.A.; Chew, B.T.; Al-Shamma’a, A.; Shaw, A.

2017-01-01

Highlights: • Decoration EDTA on MWCNT surface to retard the rate of fouling. • Preparation of DTPA-treated MWCNT/water nanofluid. • Evaluating the mitigation of DTPA-treated MWCNT-based water nanofluids. • Retarding of calcium carbonate crystals by MWCNT-DTPA additives. • The effect of additive on the rate of fouling. - Abstract: Mineral scale deposition on heat exchanging surfaces increases the thermal resistance and reduces the operating service life. The effect is usually intensified at higher temperatures due to the inverse temperature solubility characteristics of some minerals in the cooling water. Scale formation build up when dissolved salt crystallize from solution onto the heated surface, forming an adherent deposit. It is very important for heat transfer applications to cope with the fouling problems in industry. In this present study, a set of fouling experiments was conducted to evaluate the mitigation of calcium carbonate scaling by applying DTPA-treated MWCNT-based water nanofluids on heat exchanger surfaces. Investigation of additive DTPA-treated MWCNT-based water nanofluids (benign to the environment) on fouling rate of deposition was performed. 300 mg L −1 of artificially-hardened calcium carbonate solution was prepared as a fouling solution for deposit analysis. Assessment of the deposition of calcium carbonate on the heat exchanger surface with respect to the inhibition of crystal growth was conducted by Scanning Electron Microscope (SEM). The results showed that the formation of calcium carbonate crystals can be retarded significantly by adding MWCNT-DTPA additives as inhibition in the solution.

Synthesis and characterization of an octaimidazolium-based polyhedral oligomeric silsesquioxanes ionic liquid by an ion-exchange reaction.

Science.gov (United States)

Tan, Jinglin; Ma, Depeng; Sun, Xingrong; Feng, Shengyu; Zhang, Changqiao

2013-04-07

Preparation of POSS-min-DS, an octaimidazolium-based polyhedral oligomeric silsesquioxanes (POSS) room temperature ionic liquid, by an ion-exchange reaction between POSS and sodium dodecyl sulfate was reported. Octaimidazolium-based POSS was synthesized with more than 98% yield within 3 h. POSS-min-DS and octaimidazolium-based POSS were confirmed by (1)H, (13)C, and (29)Si NMR, FT-IR and elemental analysis.

Chemical reactions in the presence of surface modulation and stirring

OpenAIRE

Kamhawi, Khalid; Náraigh, Lennon Ó

2009-01-01

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

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

Science.gov (United States)

Dulnee, Siriwan; Scheinost, Andreas C

2014-08-19

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

Bifluoride-catalysed sulfur(VI) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates

Science.gov (United States)

Gao, Bing; Zhang, Linda; Zheng, Qinheng; Zhou, Feng; Klivansky, Liana M.; Lu, Jianmei; Liu, Yi; Dong, Jiajia; Wu, Peng; Sharpless, K. Barry

2017-11-01

Polysulfates and polysulfonates possess exceptional mechanical properties making them potentially valuable engineering polymers. However, they have been little explored due to a lack of reliable synthetic access. Here we report bifluoride salts (Q+[FHF]-, where Q+ represents a wide range of cations) as powerful catalysts for the sulfur(VI) fluoride exchange (SuFEx) reaction between aryl silyl ethers and aryl fluorosulfates (or alkyl sulfonyl fluorides). The bifluoride salts are significantly more active in catalysing the SuFEx reaction compared to organosuperbases, therefore enabling much lower catalyst-loading (down to 0.05 mol%). Using this chemistry, we are able to prepare polysulfates and polysulfonates with high molecular weight, narrow polydispersity and excellent functional group tolerance. The process is practical with regard to the reduced cost of catalyst, polymer purification and by-product recycling. We have also observed that the process is not sensitive to scale-up, which is essential for its future translation from laboratory research to industrial applications.

Simultaneous heat and mass transfer to air from a compact heat exchanger with water spray precooling and surface deluge cooling

International Nuclear Information System (INIS)

Zhang, Feini; Bock, Jessica; Jacobi, Anthony M.; Wu, Hailing

2014-01-01

Various methods are available to enhance heat exchanger performance with evaporative cooling. In this study, evaporative mist precooling, deluge cooling, and combined cooling schemes are examined experimentally and compared to model predictions. A flexible model of a compact, finned-tube heat exchanger with a wetted surface is developed by applying the governing conservation and rate equations and invoking the heat and mass transfer analogy. The model is applicable for dry, partially wet, or fully wet surface conditions and capable of predicting local heat/mass transfer, wetness condition, and pressure drop of the heat exchanger. Experimental data are obtained from wind tunnel experiments using a louver-fin flat-tube heat exchanger with single-phase tube-side flow. Total capacity, pressure drop, and water drainage behavior under various water usage rates and air face velocities are analyzed and compared to data for dry-surface conditions. A heat exchanger partitioning method for evaporative cooling is introduced to study partially wet surface conditions, as part of a consistent and general method for interpreting wet-surface performance data. The heat exchanger is partitioned into dry and wet portions by introducing a wet surface factor. For the wet part, the enthalpy potential method is used to determine the air-side sensible heat transfer coefficient. Thermal and hydraulic performance is compared to empirical correlations. Total capacity predictions from the model agree with the experimental results with an average deviation of 12.6%. The model is also exercised for four water augmentation schemes; results support operating under a combined mist precooling and deluge cooling scheme. -- Highlights: • A new spray-cooled heat exchanger model is presented and is validated with data. • Heat duty is shown to be asymptotic with spray flow rate. • Meaningful heat transfer coefficients for partially wet conditions are obtained. • Colburn j wet is lower than j dry

Oxygen exchange and transport in dual phase ceramic composite electrodes.

Science.gov (United States)

Druce, John; Téllez, Helena; Ishihara, Tatsumi; Kilner, John A

2015-01-01

Composites consisting of a perovskite-based electronic or mixed conductor with a fluorite-structured ionic conductor are often used as electrodes in solid oxide electrochemical energy conversion devices. After sintering the materials, there is often evidence for inter-reaction between the two phases, or inter-diffusion of cations or impurities between the two phases. We studied the (18)O exchange properties of a composite consisting of CGO and LSCF in a 50 : 50 ratio. High resolution ToF-SIMS mapping reveals that the (18)O fraction at the very outer surface of grains of the CGO phase is much higher than expected from D* and k* values for the single-phase parent material. Surface compositional analysis by ToF-SIMS and low energy ion scattering (LEIS) spectroscopy suggests that the surfaces of the CGO grains in the composite do not show the impurities which typically segregate to the surface in single-phase CGO. Thus, the "cleaning" of impurities from the CGO surface by dissolution into the perovskite phase may be one explanation for the apparent enhanced surface exchange for CGO in these composites.

Experimental study of the role of nanoparticles in sodium–water reaction

International Nuclear Information System (INIS)

Park, Gunyeop; Kim, Soo Jae; Kim, Moo Hwan; Park, Hyun Sun

2014-01-01

Highlights: • We experimentally research the effect of nanoparticles in sodium–water reaction. • We present sodium–water reaction experiments and observed the mitigated reaction rate of sodium nanofluid. • We indicate nanoparticles settled on the surface of liquid sodium affect to mitigate chemical reactivity of sodium during sodium–water reaction. - Abstract: This paper presents an experimental study of the effect of Titanium (Ti) nanoparticles (NPs) on the mechanism of Sodium–Water chemical Reaction (SWR). Sodium–Titanium Nano Fluid (NaTiNF), i.e., liquid sodium that includes dispersed Ti NPs (≤100 nm) at 0.214 vol.% was produced. To simulate an accident in a sodium–water heat exchanger in a Sodium-cooled Fast Reactor, SWR was conducted by injecting liquid water directly onto the surface of liquid sodium. The reaction behavior of NaTiNF was quantitatively compared with that of bare sodium. Experiment results present that NaTiNF shows mitigated reactivity with water and lower reaction rate than bare sodium. These results imply that NPs dispersed in liquid sodium affect the mechanism of SWR

Heterogeneously catalyzed deuterium separation processes: Hydrogen-water exchange studies at elevated temperatures and pressures

International Nuclear Information System (INIS)

Halliday, J.D.; Rolston, J.H.; Au, J.C.; Den Hartog, J.; Tremblay, R.R.

1985-01-01

New processes for the separation of hydrogen isotopes are required to produce heavy water for CANDU nuclear reactors and to extract tritium formed in the moderator during reactor operation. Wetproofed platinum catalysts capable of promoting rapid exchange of isotopes between countercurrent flows of hydrogen and liquid water in packed columns have been developed at CRNL over the past 15 years. These catalysts provide a catalystic surface for the gas phase exchange reaction H/sub 2/O/sub (v)/ + HD/sub (g)/ ↔ HDO/sub (v)/ + H/sub 2(g)/ as well as a large liquid surface for the liquid phase isotope transfer reaction HDO/sub (v)/ + H/sub 2/O/sub (iota)/↔HDO/sub (iota)/+H/sub 2/O/sub (v)/. Any economic stand-alone heavy water separation process, based on bithermal hydrogen-water exchange over wetproofed platinum catalysts, requires rapid overall exchange of isotopes between two phases at two temperatures. Catalysts developed for cold tower operation at 25-60 0 C are now being tested in a laboratory scale stainless steel trickle bed reactor for performance and stability at simulated hot tower conditions, 150 0 C and 2.0 MPa pressure. Catalytically active layers containing platinum supported on carbon or crystalline silica and wetproofed with Teflon have been prepared on ceramic spheres and stainless steel screening and tested in both random and ordered bed columns