WorldWideScience

Sample records for condensed phase reactions

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

    International Nuclear Information System (INIS)

    Coker, D.F.

    2003-01-01

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

  2. Investigation of Ultrafast Condensed Phase Reactions Between Nanopowders

    National Research Council Canada - National Science Library

    Puszynski, Jan

    2004-01-01

    .... These models predict qualitatively combustion from propagation in such reacting systems. It was also found that surface functionalization of aluminum nanopowders significantly slows down its reaction with moisture...

  3. Closure of the condensed-phase organic-nitrate reaction unreviewed safety question at Hanford site

    International Nuclear Information System (INIS)

    COWLEY, W.L.

    1999-01-01

    A discovery Unreviewed Safety Question (USQ) was declared on the underground waste storage tanks at the Hanford Site in May 1996. The USQ was for condensed-phase organic-nitrate reactions (sometimes called organic complexant reactions) in the tanks. This paper outlines the steps taken to close the USQ, and resolve the related safety issue. Several processes were used at the Hanford Site to extract and/or process plutonium. These processes resulted in organic complexants (for chelating multivalent cations) and organic extraction solvents being sent to the underground waste storage tanks. This paper addresses the organic complexant hazard. The organic complexants are in waste matrices that include inert material, diluents, and potential oxidizers. In the presence of oxidizing material, the complexant salts can be made to react exothermically by heating to high temperatures or by applying an external ignition source of sufficient energy. The first organic complexant hazard assessments focused on determining whether a hulk runaway reaction could occur, similar to the 1957 accident at Kyshtm (a reprocessing plant in the former U.S.S.R.). Early analyses (1977 through 1994) examined organic-nitrate reaction onset temperatures and concluded that a bulk runaway reaction could not occur at the Hanford Site because tank temperatures were well below that necessary for bulk runaway. Therefore, it was believed that organic-nitrate reactions were adequately described in the then current Authorization Basis (AB). Subsequent studies examined a different accident scenario, propagation resulting from an external ignition source (e.g., lightning or welding slag) that initiates a combustion front that propagates through the organic waste. A USQ evaluation determined that localized high energy ignition sources were credible, and that point source ignition of organic complexant waste was not adequately addressed i n the then existing AB. Consequently, the USQ was declared on the

  4. Some concepts in condensed phase chemical kinetics

    International Nuclear Information System (INIS)

    Adelman, S.A.

    1986-01-01

    Some concepts in condensed phase chemical kinetics which have emerged from a recent rigorous statistical mechanical treatment of condensed phase chemical reaction dynamics (S.A. Adelman, Adv. Chem. Phys.53:61 (1983)) are discussed in simple physical terms

  5. Modeling reaction histories to study chemical pathways in condensed phase detonation

    International Nuclear Information System (INIS)

    Scott Stewart, D.; Hernández, Alberto; Lee, Kibaek

    2016-01-01

    The estimation of pressure and temperature histories, which are required to understand chemical pathways in condensed phase explosives during detonation, is discussed. We argue that estimates made from continuum models, calibrated by macroscopic experiments, are essential to inform modern, atomistic-based reactive chemistry simulations at detonation pressures and temperatures. We present easy to implement methods for general equation of state and arbitrarily complex chemical reaction schemes that can be used to compute reactive flow histories for the constant volume, the energy process, and the expansion process on the Rayleigh line of a steady Chapman-Jouguet detonation. A brief review of state-of-the-art of two-component reactive flow models is given that highlights the Ignition and Growth model of Lee and Tarver [Phys. Fluids 23, 2362 (1980)] and the Wide-Ranging Equation of State model of Wescott, Stewart, and Davis [J. Appl. Phys. 98, 053514 (2005)]. We discuss evidence from experiments and reactive molecular dynamic simulations that motivate models that have several components, instead of the two that have traditionally been used to describe the results of macroscopic detonation experiments. We present simplified examples of a formulation for a hypothetical explosive that uses simple (ideal) equation of state forms and detailed comparisons. Then, we estimate pathways computed from two-component models of real explosive materials that have been calibrated with macroscopic experiments.

  6. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    Science.gov (United States)

    Basilevsky, M. V.; Odinokov, A. V.; Titov, S. V.; Mitina, E. A.

    2013-12-01

    present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.

  7. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    International Nuclear Information System (INIS)

    Basilevsky, M. V.; Mitina, E. A.; Odinokov, A. V.; Titov, S. V.

    2013-01-01

    existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems

  8. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    Energy Technology Data Exchange (ETDEWEB)

    Basilevsky, M. V.; Mitina, E. A. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); Odinokov, A. V. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow (Russian Federation); Titov, S. V. [Karpov Institute of Physical Chemistry, 3-1/12, Building 6, Obuha pereulok, Moscow (Russian Federation)

    2013-12-21

    kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.

  9. Golden rule kinetics of transfer reactions in condensed phase: the microscopic model of electron transfer reactions in disordered solid matrices.

    Science.gov (United States)

    Basilevsky, M V; Odinokov, A V; Titov, S V; Mitina, E A

    2013-12-21

    modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode∕medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target systems.

  10. Quantum and Statistical Mechanics Applied to Singlet Carbenes, Pericyclic Reactions, and Condensed Phase Phenomena

    Science.gov (United States)

    Evanseck, Jeffrey Donald

    The completed research covers a broad range of theoretical applications in organic chemistry. It is divided into three chapters which covers the chemistry of singlet carbenes (Chapter 1), substituent effects in pericyclic rearrangements (Chapter 2), and the effects of solvent on the reactivity of organic reactions (Chapter 3). The selectivity between 1,2- and 1,4-intramolecular additions to restricted diene systems has been investigated. A decrease in activation energy for the intramolecular cycloaddition is noted for systems which approach the idealized geometry found with intermolecular addition of carbenes to olefins. Direct substitution at the carbene site dramatically effects the predicted activation barriers for 1,2-hydrogen shifts. An excellent correlation between the activation energy and a substituents sigma_sp {rm R}{rm o} parameters has been demonstrated. The long standing problem of orbital alignment influences on the selectivity of 1,2-hydrogen arrangements shows significant geometric distortions, yet has little influence on the rates of singlet alkylcarbene rearrangements. The exo-selectivities observed for 1,2-shifts in rigid systems are explained by torsional and steric interactions which develop in the transition structures. Substituent effects on pericyclic reactions have been computed for several conrotatory and disrotatory electrocyclizations. The six-electron disrotatory electrocyclization of 1-substituted hexatrienes displays a strong electronic component in determining stereoselectivity, despite incredible steric interference. The eight-electron conrotatory electrocyclization transition structure of 1-substituted octatetraene has an unusual helical transition structure which does not differentiate between substituent position. The effects of solvents on the acidity differences between E and Z esters has supplemented earlier ab initio quantum mechanical results on the enhanced acidity of Meldrum's acid. Monte Carlo simulations predict a

  11. Interstellar silicate analogs for grain-surface reaction experiments: Gas-phase condensation and characterization of the silicate dust grains

    Energy Technology Data Exchange (ETDEWEB)

    Sabri, T.; Jäger, C. [Laboratory Astrophysics Group of the Max Planck Institute for Astronomy at the Friedrich Schiller University Jena Institute of Solid State Physics, Helmholtzweg 3, D-07743 Jena (Germany); Gavilan, L.; Lemaire, J. L.; Vidali, G. [Observatoire de Paris/Université de Cergy-Pontoise, 5 mail Gay Lussac, F-95000 Cergy-Pontoise (France); Mutschke, H. [Laboratory Astrophysics Group of the Astrophysical Institute and University Observatory, Friedrich Schiller University Jena Schillergässchen 3, D-07743 Jena (Germany); Henning, T., E-mail: tolou.sabri@uni-jena.de [Max Planck Institute for Astronomy Königstuhl 17, D-69117 Heidelberg (Germany)

    2014-01-10

    Amorphous, astrophysically relevant silicates were prepared by laser ablation of siliceous targets and subsequent quenching of the evaporated atoms and clusters in a helium/oxygen gas atmosphere. The described gas-phase condensation method can be used to synthesize homogeneous and astrophysically relevant silicates with different compositions ranging from nonstoichiometric magnesium iron silicates to pyroxene- and olivine-type stoichiometry. Analytical tools have been used to characterize the morphology, composition, and spectral properties of the condensates. The nanometer-sized silicate condensates represent a new family of cosmic dust analogs that can generally be used for laboratory studies of cosmic processes related to condensation, processing, and destruction of cosmic dust in different astrophysical environments. The well-characterized silicates comprising amorphous Mg{sub 2}SiO{sub 4} and Fe{sub 2}SiO{sub 4}, as well as the corresponding crystalline silicates forsterite and fayalite, produced by thermal annealing of the amorphous condensates, have been used as real grain surfaces for H{sub 2} formation experiments. A specifically developed ultra-high vacuum apparatus has been used for the investigation of molecule formation experiments. The results of these molecular formation experiments on differently structured Mg{sub 2}SiO{sub 4} and Fe{sub 2}SiO{sub 4} described in this paper will be the topic of the next paper of this series.

  12. Scrutinizing the pion condensed phase

    Energy Technology Data Exchange (ETDEWEB)

    Carignano, Stefano; Mammarella, Andrea; Mannarelli, Massimo [INFN, Laboratori Nazionali del Gran Sasso, Assergi (Italy); Lepori, Luca [Universita di Padova, Dipartimento di Fisica e Astronomia, Padova (Italy); Universita dell' Aquila, Dipartimento di Scienze Fisiche e Chimiche, Coppito-L' Aquila (Italy); Pagliaroli, Giulia [INFN, Laboratori Nazionali del Gran Sasso, Assergi (Italy); Gran Sasso Science Institute, L' Aquila (Italy)

    2017-02-15

    When the isospin chemical potential exceeds the pion mass, charged pions condense in the zero-momentum state forming a superfluid. Chiral perturbation theory provides a very powerful tool for studying this phase. However, the formalism that is usually employed in this context does not clarify various aspects of the condensation mechanism and makes the identification of the soft modes problematic. We re-examine the pion condensed phase using different approaches within the chiral perturbation theory framework. As a first step, we perform a low-density expansion of the chiral Lagrangian valid close to the onset of the Bose-Einstein condensation. We obtain an effective theory that can be mapped to a Gross-Pitaevskii Lagrangian in which, remarkably, all the coefficients depend on the isospin chemical potential. The low-density expansion becomes unreliable deep in the pion condensed phase. For this reason, we develop an alternative field expansion deriving a low-energy Lagrangian analog to that of quantum magnets. By integrating out the ''radial'' fluctuations we obtain a soft Lagrangian in terms of the Nambu-Goldstone bosons arising from the breaking of the pion number symmetry. Finally, we test the robustness of the second-order transition between the normal and the pion condensed phase when next-to-leading-order chiral corrections are included. We determine the range of parameters for turning the second-order phase transition into a first-order one, finding that the currently accepted values of these corrections are unlikely to change the order of the phase transition. (orig.)

  13. Heterogeneous catalysis in complex, condensed reaction media

    Energy Technology Data Exchange (ETDEWEB)

    Cantu, David C.; Wang, Yang-Gang; Yoon, Yeohoon; Glezakou, Vassiliki-Alexandra; Rousseau, Roger; Weber, Robert S.

    2017-07-01

    Many reactions required for the upgrading of biomass into fuels and chemicals—hydrogenation, hydrodeoxygenation, hydrocracking—are ostensibly similar to those practiced in the upgrading of petroleum into fuels. But, repurposing hydroprocessing catalysts from refinery operations to treat bio-oil has proved to be unsatisfactory. New catalysts are needed because the composition of the biogenic reactants differs from that of petroleum-derived feedstocks (e.g. the low concentration of sulfur in cellulose-derived biomass precludes use of metal sulfide catalysts unless sulfur is added to the reaction stream). New processes are needed because bio-oils oligomerize rapidly, forming intractable coke and “gunk”, at temperatures so low that the desired upgrading reactions are impractically slow, and so low that the bio-oil upgrading must be handled as a condensed fluid. Ideally, the new catalysts and processes would exploit the properties of the multiple phases present in condensed bio-oil, notably the polarizability and structure of the fluid near a catalyst’s surface in the cybotactic region. The results of preliminary modeling of the cybotactic region of different catalyst surfaces in the hydrogenation of phenol suggest that Pd catalysts supported on hydrophilic surfaces are more active than catalysts based on lipophilic supports because the former serve to enhance the concentration of the phenol in the vicinity of the Pd. The effect stems from thermodynamics, not the rate of mass transport. This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  14. Condensed phase preparation of 2,3-pentanedione

    Science.gov (United States)

    Miller, D.J.; Perry, S.M.; Fanson, P.T.; Jackson, J.E.

    1998-11-03

    A condensed phase process for the preparation of purified 2,3-pentanedione from lactic acid and an alkali metal lactate is described. The process uses elevated temperatures between about 200 to 360 C for heating a reaction mixture of lactic acid and an alkali metal lactate to produce the 2,3-pentanedione in a reaction vessel. The 2,3-pentanedione produced is vaporized from the reaction vessel and condensed with water. 5 figs.

  15. Deuterium isotope effects in condensed-phase thermochemical decomposition reactions of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

    International Nuclear Information System (INIS)

    Shackelford, S.A.; Coolidge, M.B.; Goshgarian, B.B.; Loving, B.A.; Rogers, R.N.; Janney, J.L.; Ebinger, M.H.

    1985-01-01

    The deuterium isotope effect was applied to condensed-phase thermochemical reactions of HMX and HMX-d 8 by using isothermal techniques. Dissimilar deuterium isotope effects revealed a mechanistic dependence of HMX upon different physical states which may singularly predominate in a specific type of thermal event. Solid-state HMX thermochemical decomposition produces a primary deuterium isotope effect (DIE), indicating that covalent C-H bond rupture is the rate-controlling step in this phase. An apparent inverse DIE is displayed by the mixed melt phase and can be attributed to C-H bond contraction during a weakening of molecular lattice forces as the solid HMX liquefies. The liquid-state decomposition rate appears to be controlled by ring C-N bond cleavage as evidenced by a secondary DIE and higher molecular weight products. These results reveal a dependence of the HMX decomposition process on physical state and lead to a broader mechanistic interpretation which explains the seemingly contradictory data found in current literature reviews. 33 references, 9 figures, 5 tables

  16. Nonperturbative quantum simulation of time-resolved nonlinear spectra: Methodology and application to electron transfer reactions in the condensed phase

    International Nuclear Information System (INIS)

    Wang Haobin; Thoss, Michael

    2008-01-01

    A quantum dynamical method is presented to accurately simulate time-resolved nonlinear spectra for complex molecular systems. The method combines the nonpertubative approach to describe nonlinear optical signals with the multilayer multiconfiguration time-dependent Hartree theory to calculate the laser-induced polarization for the overall field-matter system. A specific nonlinear optical signal is obtained by Fourier decomposition of the overall polarization. The performance of the method is demonstrated by applications to photoinduced ultrafast electron transfer reactions in mixed-valence compounds and at dye-semiconductor interfaces

  17. Characteristic aspects of pion-condensed phases

    International Nuclear Information System (INIS)

    Takatsuka, Tatsuyuki; Tamagaki, Ryozo; Tatsumi, Toshitaka.

    1993-01-01

    Characteristic aspects of pion-condensed phases are described in a simple model, for the system involving only nucleons and pions which interact through the π-N P-wave interaction. We consider one typical version in each of three kinds of pion condensation; the one of neutral pions (π 0 ), the one of charged pions (π C ) and the combined one in which both the π 0 and π C condensations are coexistent. Emphasis is put on the description to clarify the novel structures of the nucleon system which are realized in the pion-condensed phases. At first, it is shown that the π 0 condensation is equivalent to the particular nucleonic phase realized by a structure change of the nucleon system, where the attractive first-order effect of the one-pion-exchange (OPE) tensor force is brought about coherently. The aspects of this phase are characterized by the layered structure with a specific spin-isospin order with one-dimensional localization (named the ALS structure in short), which provides the source function for the condensed π 0 field. We utilize both descriptions with use of fields and potentials for the π 0 condensation. Next, the π C condensation realized in neutron-rich matter is described by adopting a version of the traveling condensed wave. In this phase, the nucleonic structure becomes the Fermi gas consisting of quasi-neutrons described by a superposition of neutron and proton. In this sense the structure change of the nucleon system for the π C condensation is moderate, and the field description is suitable. Finally, we describe a coexistent pion condensation, in which both the π 0 and π C condensations coexist without interference in such a manner that the π C condensation develops in the ALS structure. The model adopted here provides us with the characteristic aspects of the pion-condensed phases persisting in the realistic situation, where other ingredients affecting the pion condensation are taken into account. (author)

  18. Intermolecular interactions in the condensed phase

    DEFF Research Database (Denmark)

    Christensen, Anders S.; Kromann, Jimmy Charnley; Jensen, Jan Halborg

    2017-01-01

    To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy...... and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need...

  19. Condensation in a two-phase pool

    International Nuclear Information System (INIS)

    Duffey, R.B.; Hughes, E.D.

    1991-01-01

    We consider the case of vapor condensation in a liquid pool, when the heat transfer is controlled by heat losses through the walls. The analysis is based on drift flux theory for phase separation in the pool, and determines the two-phase mixture height for the pool. To our knowledge this is the first analytical treatment of this classic problem that gives an explicit result, previous work having established the result for the evaporative case. From conservation of mass and energy in a one-dimensional steady flow, together with a void relation between the liquid and vapor fluxes, we determine the increase in the mixture level from the base level of the pool. It can be seen that the thermal and hydrodynamic influences are separable. Thus, the thermal influence of the wall heat transfer appears through its effect on the condensing length L*, so that at high condensation rates the pool is all liquid, and at low rates overflows (the level swell or foaming effect). Similarly, the phase separation effect hydrodynamically determines the height via the relative velocity of the mixture to the entering flux. We examine some practical applications of this result to level swell in condensing flows, and also examine some limits in ideal cases

  20. Blockage-induced condensation controlled by a local reaction

    Science.gov (United States)

    Cirillo, Emilio N. M.; Colangeli, Matteo; Muntean, Adrian

    2016-10-01

    We consider the setup of stationary zero range models and discuss the onset of condensation induced by a local blockage on the lattice. We show that the introduction of a local feedback on the hopping rates allows us to control the particle fraction in the condensed phase. This phenomenon results in a current versus blockage parameter curve characterized by two nonanalyticity points.

  1. Hot atom chemistry of monovalent atoms in organic condensed phases

    International Nuclear Information System (INIS)

    Stoecklin, G.

    1975-01-01

    The advantages and disadvantages of hot atom studies in condensed organic phases are considered, and recent advances in condensed phase organic hot atom chemistry of recoil tritium and halogen atoms are discussed. Details are presented of the present status and understanding of liquid phase hot atom chemistry and also that of organic solids. The consequences of the Auger effect in condensed organic systems are also considered. (author)

  2. Heat transfer modelling of two-phase bubbles swarm condensing in three - phase direct - contact condenser

    Directory of Open Access Journals (Sweden)

    Mahood Hameed B.

    2016-01-01

    Full Text Available An analytical model for the convective heat transfer coefficient and the two-phase bubble size of a three-phase direct contact heat exchanger was developed. Until the present, there has only been a theoretical model available that deals with a single two-phase bubble and a bubble train condensation in an immiscible liquid. However, to understand the actual heat transfer process within the three-phase direct contact condenser, characteristic models are required. A quasi - steady energy equation in a spherical coordinate system with a potential flow assumption and a cell model configuration has been simplified and solved analytically. The convective heat transfer in terms of Nu number has been derived, and it was found to be a function to Pe number and a system void fraction. In addition, the two-phase bubble size relates to the system void fraction and has been developed by solving a simple energy balance equation and using the derived convective heat transfer coefficient expression. Furthermore, the model correlates well with previous experimental data and theoretical results.

  3. Modeling the Phase Composition of Gas Condensate in Pipelines

    Science.gov (United States)

    Dudin, S. M.; Zemenkov, Yu D.; Shabarov, A. B.

    2016-10-01

    Gas condensate fields demonstrate a number of thermodynamic characteristics to be considered when they are developed, as well as when gas condensate is transported and processed. A complicated phase behavior of the gas condensate system, as well as the dependence of the extracted raw materials on the phase state of the deposit other conditions being equal, is a key aspect. Therefore, when designing gas condensate lines the crucial task is to select the most appropriate methods of calculating thermophysical properties and phase equilibrium of the transported gas condensate. The paper describes a physical-mathematical model of a gas-liquid flow in the gas condensate line. It was developed based on balance equations of conservation of mass, impulse and energy of the transported medium within the framework of a quasi-1D approach. Constitutive relationships are given separately, and practical recommendations on how to apply the research results are provided as well.

  4. String-net condensation: A physical mechanism for topological phases

    International Nuclear Information System (INIS)

    Levin, Michael A.; Wen Xiaogang

    2005-01-01

    We show that quantum systems of extended objects naturally give rise to a large class of exotic phases--namely topological phases. These phases occur when extended objects, called ''string-nets,'' become highly fluctuating and condense. We construct a large class of exactly soluble 2D spin Hamiltonians whose ground states are string-net condensed. Each ground state corresponds to a different parity invariant topological phase. The models reveal the mathematical framework underlying topological phases: tensor category theory. One of the Hamiltonians--a spin-1/2 system on the honeycomb lattice--is a simple theoretical realization of a universal fault tolerant quantum computer. The higher dimensional case also yields an interesting result: we find that 3D string-net condensation naturally gives rise to both emergent gauge bosons and emergent fermions. Thus, string-net condensation provides a mechanism for unifying gauge bosons and fermions in 3 and higher dimensions

  5. Chemical reactions in organic monomolecular layers. Condensation of hydrazine on carbonyl functions

    International Nuclear Information System (INIS)

    Rosilio, Charles; Ruaudel-Teixier, Annie.

    1976-01-01

    Evidence is given for chemical reactions of hydrazine (NH 2 -NH 2 ) with different carbonyl functional groups of organic molecules in the solid state, in monomolecular layer structures. The condensation of hydrazine with these molecules leads to conjugated systems by bridging the N-N links, to cyclizations, and also to polycondensations. The reactions investigated were followed up by infrared spectrophotometry, by transmission and metallic reflection. These chemical reactions revealed in the solid phase constitute a polycondensation procedure which is valuable in obtaining organized polymers in monomolecular layers [fr

  6. Characterization of condensed phase nitric acid particles formed in the gas phase

    Institute of Scientific and Technical Information of China (English)

    Long Jia; Yongfu Xu

    2011-01-01

    The formation of nitric acid hydrates has been observed in a chamber during the dark reaction of NO2 with O3 in the presence of air.The size of condensed phase nitric acid was measured to be 40-100 nm and 20-65 nm at relative humidity (RH) ≤ 5% and RH = 67% under our experimental conditions, respectively.The nitric acid particles were collected on the glass fiber membrane and their chemical compositions were analyzed by infrared spectrum.The main components of nitric acid hydrates in particles are HNO3·3H2O and NO3-·xH2O (x≥ 4) at low RH, whereas at high RH HNO3·H2O, HNO3·2H2O, HNO3·3H2O and NO3-·xH2O (x≥ 4) all exist in the condensed phase.At high RH HNO3·xH2O (x ≤ 3) collected on the glass fiber membrane is greatly increased, while NO3-·xH2O (x ≥4) decreased, compared with low RH.To the best of our knowledge, this is the first time to report that condensed phase nitric acid can be generated in the gas phase at room temperature.

  7. The phase transition to an inhomogeneous condensate state

    International Nuclear Information System (INIS)

    Voskresensky, D.N.

    1984-01-01

    The Lagrangian (free energy) of the model with a complex scalar order parameter in which the phase transition to an inhomogeneous condensate state exists is constructed in the coordinate representation. In the case of condensation of charged particles (for example paired electrons) interaction with the electromagnetic field is included. The excitation spectrum in the presence of the condensate is found. The oscillations are strongly anisotropic. It is shown that superfluidity is absent for an uncharged system but that the charged one has the property of superconductivity. The important role of thermal fluctuations is demonstrated. They drastically change the behaviour of the condensate system. The condensation in a finite system is considered. A study is carried out for the behaviour of an inhomogeneous condensate in magnetic field. It is shown that the inhomogeneous condensate is a type II superconductor with Ginzburg-Landau parameter kappa >> 1, but that the structure of the mixed state of the system is unusual - consisting of plane layers of the normal phase, when Hsub(c1)< H< H'sub(c2). The distribution of condensate in the strong magnetic field H'sub(c2)< H< Hsub(c2) is also studied. (Auth.)

  8. Molybdenum(5) template action in acetone with ethylenediamine condensation reaction

    International Nuclear Information System (INIS)

    Ashurova, N.Kh.; Yakubov, K.G.; Tsivadze, A.Yu.; AN SSSR, Moscow

    1994-01-01

    Ability of molybdenum(5) oxopentahalides [MoOX 5 ] 2- (X = Cl - , Br - ) to show their template action in acetone with ethylenediamine condensation reaction is identified. Macrocyclic metallic complexes [MoO(Td)X]X 2 , where Td is 5,7,7,12,14,14 hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11 dien, are separated and identified. Perchlorate salt of Td·2HClO 4 macrocycle is obtained through action of concentrated perchloric acid on synthesized complexes. 13 refs.; 3 figs

  9. Fermion condensation quantum phase transition versus conventional quantum phase transitions

    International Nuclear Information System (INIS)

    Shaginyan, V.R.; Han, J.G.; Lee, J.

    2004-01-01

    The main features of fermion condensation quantum phase transition (FCQPT), which are distinctive in several aspects from that of conventional quantum phase transition (CQPT), are considered. We show that in contrast to CQPT, whose physics in quantum critical region is dominated by thermal and quantum fluctuations and characterized by the absence of quasiparticles, the physics of a Fermi system near FCQPT or undergone FCQPT is controlled by the system of quasiparticles resembling the Landau quasiparticles. Contrary to the Landau quasiparticles, the effective mass of these quasiparticles strongly depends on the temperature, magnetic fields, density, etc. This system of quasiparticles having general properties determines the universal behavior of the Fermi system in question. As a result, the universal behavior persists up to relatively high temperatures comparatively to the case when such a behavior is determined by CQPT. We analyze striking recent measurements of specific heat, charge and heat transport used to study the nature of magnetic field-induced QCP in heavy-fermion metal CeCoIn 5 and show that the observed facts are in good agreement with our scenario based on FCQPT and certainly seem to rule out the critical fluctuations related with CQPT. Our general consideration suggests that FCQPT and the emergence of novel quasiparticles near and behind FCQPT and resembling the Landau quasiparticles are distinctive features intrinsic to strongly correlated substances

  10. Condensation shocks in high momentum two-phase flows in condensing injectors

    International Nuclear Information System (INIS)

    Anand, G.; Christensen, R.N.

    1993-01-01

    This study presents a phenomenological and mathematical model of condensation shocks in high momentum two-phase flows in condensing injectors. The characteristics of the shock were related to the mode of vapor bubble collapse. Using cavitation terminology, the bubble collapse can be classified as inertially controlled or thermally controlled. Inertial bubble collapse occurs rapidly whereas, a thermally controlled collapse results in a significantly longer collapse time. The interdependence between the bubble collapse mode and the momentum and pressure of the flow, was analyzed in this study. For low-temperature-high-velocity flows a steep pressure rise with complete condensation was obtained. For a high-temperature-low velocity flow with noncondensables, low pressure recovery with incomplete condensation was observed. These trends are in agreement with previous experimental observations

  11. Evaporation and Condensation Flows of a Vapor-Gas Mixture from or onto the Condensed Phase with an Internal Structure

    National Research Council Canada - National Science Library

    Onishi, Yoshimoto; Yamada, Ken

    2005-01-01

    Transient motions of a vapor-gas mixture due to the evaporation and condensation processes from or onto the plane condensed phase, with a temperature field as its internal structure, have been studied...

  12. A Local Condensation Analysis Representing Two-phase Annular Flow in Condenser/radiator Capillary Tubes

    Science.gov (United States)

    Karimi, Amir

    1991-01-01

    NASA's effort for the thermal environmental control of the Space Station Freedom is directed towards the design, analysis, and development of an Active Thermal Control System (ATCS). A two phase, flow through condenser/radiator concept was baselined, as a part of the ATCS, for the radiation of space station thermal load into space. The proposed condenser rejects heat through direct condensation of ATCS working fluid (ammonia) in the small diameter radiator tubes. Analysis of the condensation process and design of condenser tubes are based on the available two phase flow models for the prediction of flow regimes, heat transfer, and pressure drops. The prediction formulas use the existing empirical relationships of friction factor at gas-liquid interface. An attempt is made to study the stability of interfacial waves in two phase annular flow. The formulation is presented of a stability problem in cylindrical coordinates. The contribution of fluid viscosity, surface tension, and transverse radius of curvature to the interfacial surface is included. A solution is obtained for Kelvin-Helmholtz instability problem which can be used to determine the critical and most dangerous wavelengths for interfacial waves.

  13. Solid‐Phase Synthesis of Structurally Diverse Heterocycles by an Amide–Ketone Condensation/N‐Acyliminium Pictet–Spengler Sequence

    DEFF Research Database (Denmark)

    Komnatnyy, Vitaly V.; Givskov, Michael Christian; Nielsen, Thomas Eiland

    2012-01-01

    An efficient approach for the solid‐phase synthesis of structurally diverse heterocyclic compounds is presented. Under acidic reaction conditions, peptidic levulinamides undergo intramolecular ketone–amide condensation reactions to form cyclic N‐acyliminium intermediates. In the presence...

  14. Condensers

    International Nuclear Information System (INIS)

    Andrieux, M.B.

    1984-01-01

    Characteristics of the condenser cooling waters of various French 900 MW nuclear power plants. Design and description of various types of condensers: condensers feeded directly with river water, condensers feeded by cooling towers, condensers feeded with sea water of brackish water. Presentation of the main problems encountered with the brass bundles (ammoniacal corrosion, erosion of the peripheral tubes, vibrations of the tubes), with the titanium bundles, with the tubular plates, the tubes-tubular plates assemblies, the coatings of the condenser water chamber (sea water), the vapor by-pass and with the air inlet. Analysis of the in service performances such as condensation pressure, oxygen content and availability [fr

  15. Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Barlow, Stephan E.

    2004-10-01

    Pacific Northwest National Laboratory (PNNL) hosted its first annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from May through September 2004. During this period, fourteen PNNL scientists hosted sixteen young scientists from eleven different universities. Of the sixteen participants, fourteen were graduate students; one was transitioning to graduate school; and one was a university faculty member.

  16. Assessment of tautomer distribution using the condensed reaction graph approach

    Science.gov (United States)

    Gimadiev, T. R.; Madzhidov, T. I.; Nugmanov, R. I.; Baskin, I. I.; Antipin, I. S.; Varnek, A.

    2018-03-01

    We report the first direct QSPR modeling of equilibrium constants of tautomeric transformations (logK T ) in different solvents and at different temperatures, which do not require intermediate assessment of acidity (basicity) constants for all tautomeric forms. The key step of the modeling consisted in the merging of two tautomers in one sole molecular graph ("condensed reaction graph") which enables to compute molecular descriptors characterizing entire equilibrium. The support vector regression method was used to build the models. The training set consisted of 785 transformations belonging to 11 types of tautomeric reactions with equilibrium constants measured in different solvents and at different temperatures. The models obtained perform well both in cross-validation (Q2 = 0.81 RMSE = 0.7 logK T units) and on two external test sets. Benchmarking studies demonstrate that our models outperform results obtained with DFT B3LYP/6-311 ++ G(d,p) and ChemAxon Tautomerizer applicable only in water at room temperature.

  17. Opportunities for sub-laser-cycle spectroscopy in condensed phase

    International Nuclear Information System (INIS)

    Ivanov, Misha; Smirnova, Olga

    2013-01-01

    Highlights: ► We discuss how sub-cycle attosecond spectroscopy can be extended from gas to condensed phase. ► We show that attosecond streaking measurements can be applied to bound electrons. ► We discuss time-resolving the formation of band structure in laser fields. - Abstract: To a large extent, progress of attosecond spectroscopy in the gas phase has been driven by designing approaches where time-resolution is not limited by the pulse duration. Instead, the time resolution comes from exploiting the sensitivity of electronic response to the oscillations of the electric field in the laser pulse and attosecond control over these oscillations. This paper discusses perspectives and opportunities for transporting the ideas of sub-cycle spectroscopy from gas to condensed phase

  18. A Facile, Choline Chloride/Urea Catalyzed Solid Phase Synthesis of Coumarins via Knoevenagel Condensation

    Directory of Open Access Journals (Sweden)

    Hosanagara N. Harishkumar

    2011-01-01

    Full Text Available The influence of choline chloride/urea ionic liquid in solid phase on the Knoevenagel condensation is demonstrated. The active methylene compounds such as meldrum’s acid, diethylmalonate, ethyl cyanoacetate, dimethylmalonate, were efficiently condensed with various salicylaldehydes in presence of choline chloride/urea ionic liquid without using any solvents or additional catalyst. The reaction is remarkably facile because of the air and water stability of the catalyst, and needs no special precautions. The reactions were completed within 1hr with excellent yields (95%. The products formed were sufficiently pure, and can be easily recovered. The use of ionic liquid choline chloride/urea in solid phase offered several significant advantages such as low cost, greater selectivity and easy isolation of products.

  19. Quantum mechanical force fields for condensed phase molecular simulations

    Science.gov (United States)

    Giese, Timothy J.; York, Darrin M.

    2017-09-01

    Molecular simulations are powerful tools for providing atomic-level details into complex chemical and physical processes that occur in the condensed phase. For strongly interacting systems where quantum many-body effects are known to play an important role, density-functional methods are often used to provide the model with the potential energy used to drive dynamics. These methods, however, suffer from two major drawbacks. First, they are often too computationally intensive to practically apply to large systems over long time scales, limiting their scope of application. Second, there remain challenges for these models to obtain the necessary level of accuracy for weak non-bonded interactions to obtain quantitative accuracy for a wide range of condensed phase properties. Quantum mechanical force fields (QMFFs) provide a potential solution to both of these limitations. In this review, we address recent advances in the development of QMFFs for condensed phase simulations. In particular, we examine the development of QMFF models using both approximate and ab initio density-functional models, the treatment of short-ranged non-bonded and long-ranged electrostatic interactions, and stability issues in molecular dynamics calculations. Example calculations are provided for crystalline systems, liquid water, and ionic liquids. We conclude with a perspective for emerging challenges and future research directions.

  20. Mining chemical reactions using neighborhood behavior and condensed graphs of reactions approaches.

    Science.gov (United States)

    de Luca, Aurélie; Horvath, Dragos; Marcou, Gilles; Solov'ev, Vitaly; Varnek, Alexandre

    2012-09-24

    This work addresses the problem of similarity search and classification of chemical reactions using Neighborhood Behavior (NB) and Condensed Graphs of Reaction (CGR) approaches. The CGR formalism represents chemical reactions as a classical molecular graph with dynamic bonds, enabling descriptor calculations on this graph. Different types of the ISIDA fragment descriptors generated for CGRs in combination with two metrics--Tanimoto and Euclidean--were considered as chemical spaces, to serve for reaction dissimilarity scoring. The NB method has been used to select an optimal combination of descriptors which distinguish different types of chemical reactions in a database containing 8544 reactions of 9 classes. Relevance of NB analysis has been validated in generic (multiclass) similarity search and in clustering with Self-Organizing Maps (SOM). NB-compliant sets of descriptors were shown to display enhanced mapping propensities, allowing the construction of better Self-Organizing Maps and similarity searches (NB and classical similarity search criteria--AUC ROC--correlate at a level of 0.7). The analysis of the SOM clusters proved chemically meaningful CGR substructures representing specific reaction signatures.

  1. Linking the gaseous and the condensed phases of matter: The slow electron and its interactions

    International Nuclear Information System (INIS)

    Christophorou, L.G.

    1993-01-01

    The interfacing of the gaseous and the condensed phases of matter as effected by interphase and cluster studies on the behavior of key reactions involving slow electrons either as reacting initial particles or as products of the reactions themselves is discussed. Emphasis is placed on the measurement of both the cross sections and the energetics involved, although most of the available information to date is on the latter. The discussion is selectively focussed on electron scattering (especially the role of negative ion states in gases, clusters, and dense matter), ionization, electron attachment and photodetachment. The dominant role of the electric polarization of the medium is emphasized

  2. Bose-Einstein condensation and chiral phase transition in linear sigma model

    International Nuclear Information System (INIS)

    Shu Song; Li Jiarong

    2005-01-01

    With the linear sigma model, we have studied Bose-Einstein condensation and the chiral phase transition in the chiral limit for an interacting pion system. A μ-T phase diagram including these two phenomena is presented. It is found that the phase plane has been divided into three areas: the Bose-Einstein condensation area, the chiral symmetry broken phase area and the chiral symmetry restored phase area. Bose-Einstein condensation can occur either from the chiral symmetry broken phase or from the restored phase. We show that the onset of the chiral phase transition is restricted in the area where there is no Bose-Einstein condensation

  3. Reactive simulation of the chemistry behind the condensed-phase ignition of RDX from hot spots.

    Science.gov (United States)

    Joshi, Kaushik L; Chaudhuri, Santanu

    2015-07-28

    Chemical events that lead to thermal initiation and spontaneous ignition of the high-pressure phase of RDX are presented using reactive molecular dynamics simulations. In order to initiate the chemistry behind thermal ignition, approximately 5% of RDX crystal is subjected to a constant temperature thermal pulse for various time durations to create a hot spot. After application of the thermal pulse, the ensuing chemical evolution of the system is monitored using reactive molecular dynamics under adiabatic conditions. Thermal pulses lasting longer than certain time durations lead to the spontaneous ignition of RDX after an incubation period. For cases where the ignition is observed, the incubation period is dominated by intermolecular and intramolecular hydrogen transfer reactions. Contrary to the widely accepted unimolecular models of initiation chemistry, N-N bond dissociations that produce NO2 species are suppressed in the condensed phase. The gradual temperature and pressure increase in the incubation period is accompanied by the accumulation of short-lived, heavier polyradicals. The polyradicals contain intact triazine rings from the RDX molecules. At certain temperatures and pressures, the polyradicals undergo ring-opening reactions, which fuel a series of rapid exothermic chemical reactions leading to a thermal runaway regime with stable gas-products such as N2, H2O and CO2. The evolution of the RDX crystal throughout the thermal initiation, incubation and thermal runaway phases observed in the reactive simulations contains a rich diversity of condensed-phase chemistry of nitramines under high-temperature/pressure conditions.

  4. Efficient, Long-Life Biocidal Condenser, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Environmental control systems for manned lunar and planetary bases will require condensing heat exchangers to control humidity. Condensing surfaces must be...

  5. The Condensation effect on the two-phase flow stability

    International Nuclear Information System (INIS)

    Abdou Mohamed, Hesham Nagah

    2005-01-01

    A one-dimensional analytical model has been developed to be used for the linear analysis of density-wave oscillations in a parallel heated channel and a natural circulation loop.The heater and the riser sections are divided into a single-phase and a two-phase region.The two-phase region is represented by the drift-flux model. The model accounts for aphasic slip and subcooled boiling.The localized friction at the heater and the riser exit is treated considering the two-phase mixture.Also the effects of the condensation in the riser and the change in the system pressure have been studied.The exact equation for the heated channel and the total loop pressure drop is perturbed around the steady state.he stability characteristics of the heated channel and the loop are investigated using the Root finding method criterion.The results are summarized on instability maps in the plane of subcooled boiling number vs. phase change number (i.e., inlet subcooling vs. heater heat flux).The predictions of the model are compared with experimental results published in open literature. The results show that, the treatment effect of localized friction in two-phase mixtures stabilizes the system and improves the agreement of the calculations with the experimental results.For a parallel heated channel, the results indicate a more stable system with high inlet restriction, low outlet restriction, and high inlet velocity. And for a natural circulation loop, an increase in the inlet restriction broadened the range of the continuous circulation mode and stabilized the system, a decrease in the exit restriction or the liquid charging level shifted to the right the range of the continuous circulation mode and stabilized the system and an increase in the riser condensation shifted to the right the range of the continuous circulation mode and stabilized the system.The results show that the model agrees well with the available experimental data. In particular, the results show the significance of

  6. Flows of a Vapor due to Phase Change Processes at the Condensed Phases with Temperature Fields as their Internal Structures

    National Research Council Canada - National Science Library

    Onishi, Yoshimoto; Ooshida, Takeshi

    2005-01-01

    Transient to steady motions of a vapor caused by the evaporation and condensation processes occurring at the condensed phases placed in parallel have been studied based on the Boltzmann equation of BGK type...

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

    Directory of Open Access Journals (Sweden)

    M. Lácova

    2005-08-01

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

  8. Reflection Patterns Generated by Condensed-Phase Oblique Detonation Interaction with a Rigid Wall

    Science.gov (United States)

    Short, Mark; Chiquete, Carlos; Bdzil, John; Meyer, Chad

    2017-11-01

    We examine numerically the wave reflection patterns generated by a detonation in a condensed phase explosive inclined obliquely but traveling parallel to a rigid wall as a function of incident angle. The problem is motivated by the characterization of detonation-material confiner interactions. We compare the reflection patterns for two detonation models, one where the reaction zone is spatially distributed, and the other where the reaction is instantaneous (a Chapman-Jouguet detonation). For the Chapman-Jouguet model, we compare the results of the computations with an asymptotic study recently conducted by Bdzil and Short for small detonation incident angles. We show that the ability of a spatially distributed reaction energy release to turn flow streamlines has a significant impact on the nature of the observed reflection patterns. The computational approach uses a shock-fit methodology.

  9. Angular distribution and atomic effects in condensed phase photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Davis, R.F.

    1981-11-01

    A general concept of condensed phase photoelectron spectroscopy is that angular distribution and atomic effects in the photoemission intensity are determined by different mechanisms, the former being determined largely by ordering phenomena such as crystal momentum conservation and photoelectron diffraction while the latter are manifested in the total (angle-integrated) cross section. In this work, the physics of the photoemission process is investigated in several very different experiments to elucidate the mechanisms of, and correlation between, atomic and angular distribution effects. Theoretical models are discussed and the connection betweeen the two effects is clearly established. The remainder of this thesis, which describes experiments utilizing both angle-resolved and angle-integrated photoemission in conjunction with synchrotron radiation in the energy range 6 eV less than or equal to h ν less than or equal to 360 eV and laboratory sources, is divided into three parts

  10. Study towards benzoin condensation and Baylis-Hillman reactions

    Indian Academy of Sciences (India)

    Abstract. New heterocyclic ring systems consisting of (±) methanodibenzodiazocine and imidazolium/ benzimidazolium salts were synthesized in very good yield. Subsequently, these halide salts were subjected to the anion exchange reaction with KPF6 to yield the corresponding azolium salts in excellent yield.

  11. Coherent Control of Multiphoton Transitions in the Gas and Condensed Phases with Shaped Ultrashort Pulses

    International Nuclear Information System (INIS)

    Dantus, Marcos

    2008-01-01

    Controlling laser-molecule interactions has become an integral part of developing devices and applications in spectroscopy, microscopy, optical switching, micromachining and photochemistry. Coherent control of multiphoton transitions could bring a significant improvement of these methods. In microscopy, multi-photon transitions are used to activate different contrast agents and suppress background fluorescence; coherent control could generate selective probe excitation. In photochemistry, different dissociative states are accessed through two, three, or more photon transitions; coherent control could be used to select the reaction pathway and therefore the yield-specific products. For micromachining and processing a wide variety of materials, femtosecond lasers are now used routinely. Understanding the interactions between the intense femtosecond pulse and the material could lead to technologically important advances. Pulse shaping could then be used to optimize the desired outcome. The scope of our research program is to develop robust and efficient strategies to control nonlinear laser-matter interactions using ultrashort shaped pulses in gas and condensed phases. Our systematic research has led to significant developments in a number of areas relevant to the AMO Physics group at DOE, among them: generation of ultrashort phase shaped pulses, coherent control and manipulation of quantum mechanical states in gas and condensed phases, behavior of isolated molecules under intense laser fields, behavior of condensed phase matter under intense laser field and implications on micromachining with ultrashort pulses, coherent control of nanoparticles their surface plasmon waves and their nonlinear optical behavior, and observation of coherent Coulomb explosion processes at 10 16 W/cm 2 . In all, the research has resulted in 36 publications (five journal covers) and nine invention disclosures, five of which have continued on to patenting

  12. Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

    Science.gov (United States)

    Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

    2018-06-01

    In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

  13. Probing the Rate-Determining Step of the Claisen-Schmidt Condensation by Competition Reactions

    Science.gov (United States)

    Mak, Kendrew K. W.; Chan, Wing-Fat; Lung, Ka-Ying; Lam, Wai-Yee; Ng, Weng-Cheong; Lee, Siu-Fung

    2007-01-01

    Competition experiments are a useful tool for preliminary study of the linear free energy relationship of organic reactions. This article describes a physical organic experiment for upper-level undergraduates to identify the rate-determining step of the Claisen-Schmidt condensation of benzaldehyde and acetophenone by studying the linear free…

  14. Phase transitions of W condensation for the universe with finite fermion density

    International Nuclear Information System (INIS)

    Kalashnikov, O.K.; Perez Rojas, H.; Institute of Cybernetics, Mathematics and Physics, Cuban Academy of Sciences, Havana, Cuba)

    1989-01-01

    The phase diagrams of W condensation are established in the electroweak theory with a finite fermion density under conditions of neutral and electric charge conservation. We found for the universe with a zero neutral charge density that the W condensate occurs at any small fermion density ρ. This appears at first near the point of symmetry restoration. This condensate exists only in the finite-temperature region and evaporates completely or partially, when the temperature goes to zero

  15. An atomic perspective of the photodissociation and geminate recombination of triiodide in condensed phases

    Energy Technology Data Exchange (ETDEWEB)

    Xian, Rui

    2016-11-15

    The thesis presents progress made towards a thorough understanding of the photodissociation and geminate recombination of triiodide anion (I{sub 3}{sup -}) in solution and solid state using novel time-resolved spectroscopic and structural methods that have matured in the past decade. An isolated I{sub 3}{sup -} has only three degrees of freedom, but in the condensed phase, the case of an open quantum system, its chemistry is transformed because other degrees of freedom from the surroundings (the bath) need to be fully taken into account. This system is a textbook example for understanding dissociation and recombination processes in condensed phases, but unresolved issues about the reaction pathways remain. To probe the issues, firstly, mid-UV pulse shaper-based closed-loop adaptive control as well as open-loop power and chirp control schemes were used in conjunction with single-color pump-probe detection of the yield of the photoproduct diiodide (I{sub 2}{sup -.}) to study the above reaction in ethanol solution. The experiments revealed a strong pump-chirp dependence of the I{sub 2}{sup -.}-yield (as much as 40% change). Subsequently, two possible mechanisms involving additional reaction channels were postulated in order to explain such effect. Secondly, pump-supercontinuum-probe spectroscopy and ultrafast electron diffraction were performed separately on solid state triiodide compound n-(C{sub 4}H{sub 9}){sub 4}NI{sub 3} (TBAT). This system was chosen to provide a well-defined lattice for the bath and to avail atomic resolution of the condensed phase reaction dynamics. In the optical experiment, coherent oscillations were observed within a probe delay of 1 ps that bear strong resemblance to the stretching modes of ground-state I{sub 3}{sup -} and I{sub 2}{sup -.} fragment, which makes it the first to reliably distinguish the two species in a single measurement. In addition, the spectroscopic signature of a novel intermediate, the tetraiodide anion (I{sub 4}{sup

  16. An atomic perspective of the photodissociation and geminate recombination of triiodide in condensed phases

    International Nuclear Information System (INIS)

    Xian, Rui

    2016-11-01

    The thesis presents progress made towards a thorough understanding of the photodissociation and geminate recombination of triiodide anion (I_3"-) in solution and solid state using novel time-resolved spectroscopic and structural methods that have matured in the past decade. An isolated I_3"- has only three degrees of freedom, but in the condensed phase, the case of an open quantum system, its chemistry is transformed because other degrees of freedom from the surroundings (the bath) need to be fully taken into account. This system is a textbook example for understanding dissociation and recombination processes in condensed phases, but unresolved issues about the reaction pathways remain. To probe the issues, firstly, mid-UV pulse shaper-based closed-loop adaptive control as well as open-loop power and chirp control schemes were used in conjunction with single-color pump-probe detection of the yield of the photoproduct diiodide (I_2"-".) to study the above reaction in ethanol solution. The experiments revealed a strong pump-chirp dependence of the I_2"-".-yield (as much as 40% change). Subsequently, two possible mechanisms involving additional reaction channels were postulated in order to explain such effect. Secondly, pump-supercontinuum-probe spectroscopy and ultrafast electron diffraction were performed separately on solid state triiodide compound n-(C_4H_9)_4NI_3 (TBAT). This system was chosen to provide a well-defined lattice for the bath and to avail atomic resolution of the condensed phase reaction dynamics. In the optical experiment, coherent oscillations were observed within a probe delay of 1 ps that bear strong resemblance to the stretching modes of ground-state I_3"- and I_2"-". fragment, which makes it the first to reliably distinguish the two species in a single measurement. In addition, the spectroscopic signature of a novel intermediate, the tetraiodide anion (I_4"-".), was identified and its origin is attributed to intermolecular interaction of the

  17. Mixtures of Charged Bosons Confined in Harmonic Traps and Bose-Einstein Condensation Mechanism for Low-Energy Nuclear Reactions and Transmutation Processes in Condensed Matters

    Science.gov (United States)

    Kim, Yeong E.; Zubarev, Alexander L.

    2006-02-01

    A mixture of two different species of positively charged bosons in harmonic traps is considered in the mean-field approximation. It is shown that depending on the ratio of parameters, the two components may coexist in same regions of space, in spite of the Coulomb repulsion between the two species. Application of this result is discussed for the generalization of the Bose-Einstein condensation mechanism for low-energy nuclear reaction (LENR) and transmutation processes in condensed matters. For the case of deutron-lithium (d + Li) LENR, the result indicates that (d + 6Li) reactions may dominate over (d + d) reactions in LENR experiments.

  18. Mixtures of charged bosons confined in harmonic traps and Bose-Einstein condensation mechanism for low-energy nuclear reactions and transmutation processes in condensed matters

    Energy Technology Data Exchange (ETDEWEB)

    Yeong, E. Kim; Zubarev, Alexander L. [Purdue Nuclear and Many-Body Theory Group (PNMBTG) Department of Physics, Purdue University, West Lafayette, IN 47907 (United States)

    2006-07-01

    A mixture of two different species of positively charged bosons in harmonic traps is considered in the mean-field approximation. It is shown that depending on the ratio of parameters, the two components may coexist in some regions of space, in spite of the Coulomb repulsion between the two species. Application of this result is discussed for the generalization of the Bose-Einstein condensation mechanism for low-energy nuclear reaction (LENR) and transmutation processes in condensed matters. For the case of deuteron-lithium (d + Li) LENR, the result indicates that (d + {sup 6}Li) reactions may dominate over (d + d) reactions in LENR experiments. (authors)

  19. Mixtures of charged bosons confined in harmonic traps and Bose-Einstein condensation mechanism for low-energy nuclear reactions and transmutation processes in condensed matters

    International Nuclear Information System (INIS)

    Yeong, E. Kim; Zubarev, Alexander L.

    2006-01-01

    A mixture of two different species of positively charged bosons in harmonic traps is considered in the mean-field approximation. It is shown that depending on the ratio of parameters, the two components may coexist in some regions of space, in spite of the Coulomb repulsion between the two species. Application of this result is discussed for the generalization of the Bose-Einstein condensation mechanism for low-energy nuclear reaction (LENR) and transmutation processes in condensed matters. For the case of deuteron-lithium (d + Li) LENR, the result indicates that (d + 6 Li) reactions may dominate over (d + d) reactions in LENR experiments. (authors)

  20. Condensation reactions of glucose and aromatic ring; Glucose to hokokan tono shukugo hanno

    Energy Technology Data Exchange (ETDEWEB)

    Komano, T.; Mashimo, K.; Wainai, T.; Tanaka, C.; Yoshioka, T. [Nihon University, Tokyo (Japan). College of Science and Technology; Sugimoto, Y.; Miki, Y. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

    1996-10-28

    For artificial coalification, condensation reactions of aromatic ring and activated compounds produced by dehydrating reaction of glucose were studied experimentally. In heat treatment experiment in water, three reaction specimens such as glucose, glucose and phenol, and glucose and benzaldehyde were fed into an autoclave together with distilled water, and subjected to reaction at 180{degree}C under spontaneous pressure for 50 hours. In hydrogenation experiment, the specimens were fed into an autoclave together with tetradecane and sulfurization catalyst, and subjected to reaction at 350{degree}C under initial pressure of 9.8MPa for 2 hours for gas chromatography (GC) analysis of products. As the experimental result, the reaction between glucose and aromatic ring in heat treatment in water occurred between aromatic ring and active fragment with a mean carbon number of 4-5 produced by decomposition of glucose. The reactivity was higher in benzaldehyde addition than phenol addition. 3 refs., 4 figs., 1 tab.

  1. Proton mixing in -condensed phase of neutron star matter

    Energy Technology Data Exchange (ETDEWEB)

    Takatsuka, Tatsuyuki

    1984-08-01

    The mixing of protons in neutron star matter under the occurrence of condensation is studied in the framework of the ALS (Alternating Layer Spin) model and with the effective interaction approach. It is found that protons are likely to mix under the situation and cause a remarkable energy gain from neutron matter as the density increases. The extent of proton mixing becomes larger by about a factor (1.5-2.5) according to the density rho asymptotically equals (2-5)rho0, rho0 being the nuclear density, as compared with that for the case without pion condensation. The reason can be attributed to the two-dimensional nature of the Fermi gas state characteristic of the nucleon system under condensation.

  2. Quark-antiquark condensates in the hadronic phase

    International Nuclear Information System (INIS)

    Tawfik, A.; Toublan, D.

    2005-01-01

    We use a hadron resonance gas model to calculate the quark-antiquark condensates for light (up and down) and strange quark flavors at finite temperatures and chemical potentials. At zero chemical potentials, we find that at the temperature where the light quark-antiquark condensates entirely vanish the strange quark-antiquark condensate still keeps a relatively large fraction of its value in the vacuum. This is in agreement with results obtained in lattice simulations and in chiral perturbation theory at finite temperature and zero chemical potentials. Furthermore, we find that this effect slowly disappears at larger baryon chemical potential. These results might have significant consequences for our understanding of QCD at finite temperatures and chemical potentials. Concretely, our results imply that there might be a domain of temperatures where chiral symmetry is restored for light quarks, but still broken for strange quark that persists at small chemical potentials. This might have practical consequences for heavy ion collision experiments

  3. Disorder Induced Dynamic Equilibrium Localization and Random Phase Steps of Bose—Einstein Condensates

    International Nuclear Information System (INIS)

    Duan Ya-Fan; Xu Zhen; Qian Jun; Sun Jian-Fang; Jiang Bo-Nan; Hong Tao

    2011-01-01

    We numerically analyze the dynamic behavior of Bose—Einstein condensate (BEC) in a one-dimensional disordered potential before it completely loses spatial quantum coherence. We find that both the disorder statistics and the atom interactions produce remarkable effects on localization. We also find that the single phase of the initial condensate is broken into many small pieces while the system approaches localization, showing a counter-intuitive step-wise phase but not a thoroughly randomized phase. Although the condensates as a whole show less flow and expansion, the currents between adjacent phase steps retain strong time dependence. Thus we show explicitly that the localization of a finite size Bose—Einstein condensate is a dynamic equilibrium state. (general)

  4. Microwave Assisted Condensation Reactions of 2-Aryl Hydrazonopropanals with Nucleophilic Reagents and Dimethyl Acetylenedicarboxylate

    Directory of Open Access Journals (Sweden)

    Rita M. Borik

    2007-08-01

    Full Text Available The reaction of methyl ketones 1a-g with dimethylformamide dimethylacetal (DMFDMA afforded the enaminones 2a-g, which were coupled with diazotized aromatic amines 3a,b to give the corresponding aryl hydrazones 6a-h. Condensation of compounds 6a-h with some aromatic heterocyclic amines afforded iminoarylhydrazones 9a-m. Enaminoazo compounds 12a,b could be obtained from condensation of 6c with secondary amines. The reaction of 6e,h with benzotriazolylacetone yielded 14a,b. Also, the reaction of 6a,b,d-f,h with glycine and hippuric acid in acetic anhydride afforded pyridazinone derivatives 17a-f. Synthesis of pyridazine carboxylic acid derivatives 22a,b from the reaction of 6b,e with dimethyl acetylenedicarboxylate (DMAD in the presence of triphenylphosphine at room temperature is also reported. Most of these reactions were conducted under irradiation in a microwave oven in the absence of solvent in an attempt to improve the product yields and to reduce the reaction times.

  5. Catalytic performance of Metal-Organic-Frameworks vs.extra-large porezeolite UTL in condensation reactions

    Czech Academy of Sciences Publication Activity Database

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, O. V.; Čejka, Jiří

    2013-01-01

    Roč. 1, AUG 2013 (2013), s. 1-11 ISSN 2296-2646 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : condensation reactions * MOFs * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry http://www.frontiersin.org/Journal/10.3389/fchem.2013.00011/abstract

  6. Metal Organic Frameworks as Solid Catalysts in Condensation Reactions of Carbonyl Groups

    Czech Academy of Sciences Publication Activity Database

    Dhakshinamoorthy, A.; Opanasenko, Maksym; Čejka, Jiří; Garcia, H.

    2013-01-01

    Roč. 355, 2-3 (2013), s. 247-268 ISSN 1615-4150 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : alcohol condensation * green chemistry * Henry reaction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.542, year: 2013

  7. Recommendations for the presentation of infrared absorption spectra in data collections condensed phases

    CERN Document Server

    Becker, E D

    2013-01-01

    Recommendations for the Presentation of Infrared Absorption Spectra in Data Collections-A. Condensed Phases presents the recommendations related to the infrared spectra of condensed phase materials that are proposed for permanent retention in data collections. These recommendations are based on two reports published by the Coblentz Society. This book emphasizes the three levels of quality evaluation for infrared spectra as designated by the Coblentz Society, including critically defined physical data, research quality analytical spectra, and approved analytical spectra. This text discusses the

  8. Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

    Science.gov (United States)

    Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

    2018-04-01

    In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard-sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-molecular dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients. We use this approach to examine atomic condensation onto 6-56-atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity (v) between atom and cluster and the initial impact parameter (b). In all cases, there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard-sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms and for 14- and 28-atom Mg clusters, as cluster equilibration temperature increases, the condensation rate coefficient drops to values below the hard-sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (>1000 m s-1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). The presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.

  9. Gas phase reactions of nitrogen oxides with olefins

    Energy Technology Data Exchange (ETDEWEB)

    Altshuller, A P; Cohen, I

    1961-01-01

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

  10. Numerical simulation of condensation phase change flow in an inclined tube with bend

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Jong Chull; Shin, Byung Soo; Do, Kyu Sik [Korea Institute of Nuclear Safety, Daejeon (Korea, Republic of); Lee, Yong Kap [Anflux Co., Seoul (Korea, Republic of)

    2012-10-15

    The new PWR design named APR+ incorporates a passive auxiliary feedwater system (PAFS) as shown in Fig.1. The PAFS consists of two separate divisions. Each division is equipped with one passive condensation heat exchanger (PCHX), isolation or drain or vent valves, check valves, instrumentation and control, and pipes. It is aligned to feed condensed water to its corresponding steam generator (SG). During the PAFS normal operation, steam being produced in the SG secondary side by the residual heat moves up due to buoyancy force and then flows into the PCHX where steam is condensed on the inner surface of the tubes of which the outer surfaces are cooled by the water stored in the passive condensation cooling tank (PCCT). The condensate is passively fed into the SG economizer by gravity. Because the thermal hydraulic characteristics in the PCHT determine the condensation mass rate and the possibility of system instability and water hammer, it is important to understand the condensation phase change flow in the PCHT. This paper presents a numerical simulation of the condensation phase change flow in the PCHX adopted for the APR+ PAFS.

  11. Phase Diagram for Magnon Condensate in Yttrium Iron Garnet Film

    Science.gov (United States)

    Li, Fuxiang; Saslow, Wayne M.; Pokrovsky, Valery L.

    2013-01-01

    Recently, magnons, which are quasiparticles describing the collective motion of spins, were found to undergo Bose-Einstein condensation (BEC) at room temperature in films of Yttrium Iron Garnet (YIG). Unlike other quasiparticle BEC systems, this system has a spectrum with two degenerate minima, which makes it possible for the system to have two condensates in momentum space. Recent Brillouin Light Scattering studies for a microwave-pumped YIG film of thickness d = 5 μm and field H = 1 kOe find a low-contrast interference pattern at the characteristic wavevector Q of the magnon energy minimum. In this report, we show that this modulation pattern can be quantitatively explained as due to unequal but coherent Bose-Einstein condensation of magnons into the two energy minima. Our theory predicts a transition from a high-contrast symmetric state to a low-contrast non-symmetric state on varying the d and H, and a new type of collective oscillation. PMID:23455849

  12. Studies of cluster-assembled materials: From gas phase to condensed phase

    Science.gov (United States)

    Gao, Lin

    . After being mass gated in a reflectron equipped time-of-flight mass spectrometer (TOF-MS) and deposited onto TEM grids, the resultant specimens can be loaded onto high-resolution TEM investigation via electron diffraction. In conclusion, soft-landing of mass selected clusters has been shown to be a successful approach to obtain structural information on Zr-Met-Car cluster-assembled materials collected from the gas phase. TEM images indicate the richness of the morphologies associated with these cluster crystals. However, passivation methods are expected to be examined further to overcome the limited stabilities of these novel clusters. From this initial study, it's shown the promising opportunity to study other Met-Cars species and more cluster-based materials. Experimental results of reactions run with a solvothermal synthesis method obtained while searching for new Zr-C cluster assembled materials, are reported. One unexpected product in single crystal form was isolated and tentatively identified by X-ray diffraction to be [Zr6i O(OH)O12·2(Bu)4], with space group P2 1/n and lattice parameters of a = 12.44 A, b = 22.06 A, c = 18.40 A, alpha = 90°, beta = 105°, gamma = 90°, V = 4875 A3 and R 1 = 3.15% for the total observed data (I ≥ 2 sigma I) and oR2 = 2.82%. This novel hexanuclear Zr(IV)-oxo-hydroxide cluster anion may be the first member in polyoxometalates class with metal atoms from the IVB group and having Oh symmetry. Alternatively, it may be the first member in {[(Zr6Z)X 12]X6}m- class with halides replaced by oxo- and hydroxyl groups and with an increased oxidation state of Zr. It is predicted to bear application potentials directed by both families. This work could suggest a direction in which the preparation of Zr-C cluster-assembled materials in a liquid environment may be eventually fulfilled. 1,3-Bis(diethylphosphino)propane (depp) protected small gold clusters are studied via multiple techniques, including Electrospray Ionization Mass Spectrometry

  13. SOLGASMIX-PV, Chemical System Equilibrium of Gaseous and Condensed Phase Mixtures

    International Nuclear Information System (INIS)

    Besmann, T.M.

    1986-01-01

    1 - Description of program or function: SOLGASMIX-PV, which is based on the earlier SOLGAS and SOLGASMIX codes, calculates equilibrium relationships in complex chemical systems. Chemical equilibrium calculations involve finding the system composition, within certain constraints, which contains the minimum free energy. The constraints are the preservation of the masses of each element present and either constant pressure or volume. SOLGASMIX-PV can calculate equilibria in systems containing a gaseous phase, condensed phase solutions, and condensed phases of invariant and variable stoichiometry. Either a constant total gas volume or a constant total pressure can be assumed. Unit activities for condensed phases and ideality for solutions are assumed, although nonideal systems can be handled provided activity coefficient relationships are available. 2 - Restrictions on the complexity of the problem: The program is designed to handle a maximum of 20 elements, 99 substances, and 10 mixtures, where the gas phase is considered a mixture. Each substance is either a gas or condensed phase species, or a member of a condensed phase mixture

  14. Phase transition in dense nuclear matter with quark and gluon condensates

    International Nuclear Information System (INIS)

    Ellis, J.; Kapusta, J.I.; Olive, K.A.

    1991-01-01

    Nuclear matter is expected to modify the expectation values of the quark and gluon condensates. We utilize the chiral and scale symmetries of QCD to describe the interaction between these condensates and hadrons. We solve the resulting equations self-consistently in the relativistic mean field approximation. In order that these QCD condensates be driven towards zero at high density their coupling to sigma and vector mesons must be such that the masses of these mesons do not decrease with density. In this case a physically sensible phase transition to quark matter ensures. (orig.)

  15. Wetting phase transition of two segregated Bose–Einstein condensates restricted by a hard wall

    Energy Technology Data Exchange (ETDEWEB)

    Thu, Nguyen Van [Department of Physics, Hanoi Pedagogical University No. 2, Hanoi (Viet Nam); Phat, Tran Huu [Vietnam Atomic Energy Commission, 59 Ly Thuong Kiet, Hanoi (Viet Nam); Song, Pham The, E-mail: thesong80@icloud.com [Tay Bac University, Son La (Viet Nam)

    2016-04-01

    Highlights: • System of two segregated Bose–Einstein condensates limited by a wall is studied. • Double-parabola approximation is applied to Gross–Pitaevskii theory. • Interface tension and wetting phase diagram are established. - Abstract: The wetting phase transition in the system of two segregated Bose–Einstein condensates (BECs) restricted by a hard wall is studied by means of the double-parabola approximation (DPA) applied to the Gross–Pitaevskii (GP) theory. We found the interfacial tension and the wetting phase diagram which depend weakly on the spatial restriction.

  16. A hybrid formulation for the numerical simulation of condensed phase explosives

    Science.gov (United States)

    Michael, L.; Nikiforakis, N.

    2016-07-01

    In this article we present a new formulation and an associated numerical algorithm, for the simulation of combustion and transition to detonation of condensed-phase commercial- and military-grade explosives, which are confined by (or in general interacting with one or more) compliant inert materials. Examples include confined rate-stick problems and interaction of shock waves with gas cavities or solid particles in explosives. This formulation is based on an augmented Euler approach to account for the mixture of the explosive and its products, and a multi-phase diffuse interface approach to solve for the immiscible interaction between the mixture and the inert materials, so it is in essence a hybrid (augmented Euler and multi-phase) model. As such, it has many of the desirable features of the two approaches and, critically for our applications of interest, it provides the accurate recovery of temperature fields across all components. Moreover, it conveys a lot more physical information than augmented Euler, without the complexity of full multi-phase Baer-Nunziato-type models or the lack of robustness of augmented Euler models in the presence of more than two components. The model can sustain large density differences across material interfaces without the presence of spurious oscillations in velocity and pressure, and it can accommodate realistic equations of state and arbitrary (pressure- or temperature-based) reaction-rate laws. Under certain conditions, we show that the formulation reduces to well-known augmented Euler or multi-phase models, which have been extensively validated and used in practice. The full hybrid model and its reduced forms are validated against problems with exact (or independently-verified numerical) solutions and evaluated for robustness for rate-stick and shock-induced cavity collapse case-studies.

  17. Interfacial Charge Transfer States in Condensed Phase Systems

    Science.gov (United States)

    Vandewal, Koen

    2016-05-01

    Intermolecular charge transfer (CT) states at the interface between electron-donating (D) and electron-accepting (A) materials in organic thin films are characterized by absorption and emission bands within the optical gap of the interfacing materials. CT states efficiently generate charge carriers for some D-A combinations, and others show high fluorescence quantum efficiencies. These properties are exploited in organic solar cells, photodetectors, and light-emitting diodes. This review summarizes experimental and theoretical work on the electronic structure and interfacial energy landscape at condensed matter D-A interfaces. Recent findings on photogeneration and recombination of free charge carriers via CT states are discussed, and relations between CT state properties and optoelectronic device parameters are clarified.

  18. Local-order metric for condensed-phase environments

    Science.gov (United States)

    Martelli, Fausto; Ko, Hsin-Yu; Oǧuz, Erdal C.; Car, Roberto

    2018-02-01

    We introduce a local order metric (LOM) that measures the degree of order in the neighborhood of an atomic or molecular site in a condensed medium. The LOM maximizes the overlap between the spatial distribution of sites belonging to that neighborhood and the corresponding distribution in a suitable reference system. The LOM takes a value tending to zero for completely disordered environments and tending to one for environments that perfectly match the reference. The site-averaged LOM and its standard deviation define two scalar order parameters, S and δ S , that characterize with excellent resolution crystals, liquids, and amorphous materials. We show with molecular dynamics simulations that S , δ S , and the LOM provide very insightful information in the study of structural transformations, such as those occurring when ice spontaneously nucleates from supercooled water or when a supercooled water sample becomes amorphous upon progressive cooling.

  19. Carbon in condensed hydrocarbon phases, steels and cast irons

    Directory of Open Access Journals (Sweden)

    GAFAROVA Victoria Alexandrovna

    2017-11-01

    Full Text Available The article presents a review of studies carried out mainly by the researchers of the Ufa State Petroleum Technological University, which are aimed at detection of new properties of carbon in such condensed media as petroleum and coal pitches, steels and cast irons. Carbon plays an important role in the industry of construction materials being a component of road and roof bitumen and setting the main mechanical properties of steels. It was determined that crystal-like structures appear in classical glass-like substances – pitches which contain several thousands of individual hydrocarbons of various compositions. That significantly extends the concept of crystallinity. In structures of pitches, the control parameter of the staged structuring process is paramagnetism of condensed aromatic hydrocarbons. Fullerenes were detected in steels and cast irons and identified by various methods of spectrometry and microscopy. Fullerene С60, which contains 60 carbon atoms, has diameter of 0,7 nm and is referred to the nanoscale objects, which have a significant influence on the formation of steel and cast iron properties. It was shown that fullerenes appear at all stages of manufacture of cast irons; they are formed during introduction of carbon from the outside, during crystallization of metal in welded joints. Creation of modified fullerene layers in steels makes it possible to improve anticorrosion and tribological properties of structural materials. At the same time, outside diffusion of carbon from the carbon deposits on the metal surface also leads to formation of additional amount of fullerenes. This creates conditions for occurrence of local microdistortions of the structure, which lead to occurrence of cracks. Distribution of fullerenes in iron matrix is difficult to study as the method is labor-intensive, it requires dissolution of the matrix in the hydrofluoric acid and stage fullerene separation with further identification by spectral methods.

  20. Anomalous interfacial tension temperature dependence of condensed phase drops in magnetic fluids

    Science.gov (United States)

    Ivanov, Aleksey S.

    2018-05-01

    Interfacial tension temperature dependence σ(T) of the condensed phase (drop-like aggregates) in magnetic fluids undergoing field induced phase transition of the "gas-liquid" type was studied experimentally. Numerical analysis of the experimental data has revealed the anomalous (if compared to ordinary one-component fluids) behavior of the σ(T) function for all tested magnetic colloid samples: the condensed phase drops at high T ≈ 75 C exhibit higher σ(T) than the drops condensed at low T ≈ 20 C. The σ(T) behavior is explained by the polydispersity of magnetic colloids: at high T, only the largest colloidal particles are able to take part in the field induced condensation; thus, the increase of T causes the growth of the average particle diameters inside the drop-like aggregates, what in its turn results in the growth of σ(T). The result is confirmed by qualitative theoretical estimations and qualitative experimental observation of the condensed phase "evaporation" process after the applied magnetic field is removed: the drops that are formed due to capillary instability of the drop-like aggregates retract by one order of magnitude faster at high T, and the evaporation of the drops slows down at high T.

  1. Phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles: Specific characteristics of the condensed phases.

    Science.gov (United States)

    Vollhardt, D

    2015-08-01

    For understanding the role of amide containing amphiphiles in inherently complex biological processes, monolayers at the air-water interface are used as simple biomimetic model systems. The specific characteristics of the condensed phases and phase transition in insoluble and adsorbed monolayers of amide amphiphiles are surveyed to highlight the effect of the chemical structure of the amide amphiphiles on the interfacial interactions in model monolayers. The mesoscopic topography and/or two-dimensional lattice structures of selected amino acid amphiphiles, amphiphilic N-alkylaldonamide, amide amphiphiles with specific tailored headgroups, such as amide amphiphiles based on derivatized ethanolamine, e.g. acylethanolamines (NAEs) and N-,O-diacylethanolamines (DAEs) are presented. Special attention is devoted the dominance of N,O-diacylated ethanolamine in mixed amphiphilic acid amide monolayers. The evidence that a first order phase transition can occur in adsorption layers and that condensed phase domains of mesoscopic scale can be formed in adsorption layers was first obtained on the basis of the experimental characteristics of a tailored amide amphiphile. New thermodynamic and kinetic concepts for the theoretical description of the characteristics of amide amphiphile's monolayers were developed. In particular, the equation of state for Langmuir monolayers generalized for the case that one, two or more phase transitions occur, and the new theory for phase transition in adsorbed monolayers are experimentally confirmed at first by amide amphiphile monolayers. Despite the significant progress made towards the understanding the model systems, these model studies are still limited to transfer the gained knowledge to biological systems where the fundamental physical principles are operative in the same way. The study of biomimetic systems, as described in this review, is only a first step in this direction. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Generalized modeling of multi-component vaporization/condensation phenomena for multi-phase-flow analysis

    International Nuclear Information System (INIS)

    Morita, K.; Fukuda, K.; Tobita, Y.; Kondo, Sa.; Suzuki, T.; Maschek, W.

    2003-01-01

    A new multi-component vaporization/condensation (V/C) model was developed to provide a generalized model for safety analysis codes of liquid metal cooled reactors (LMRs). These codes simulate thermal-hydraulic phenomena of multi-phase, multi-component flows, which is essential to investigate core disruptive accidents of LMRs such as fast breeder reactors and accelerator driven systems. The developed model characterizes the V/C processes associated with phase transition by employing heat transfer and mass-diffusion limited models for analyses of relatively short-time-scale multi-phase, multi-component hydraulic problems, among which vaporization and condensation, or simultaneous heat and mass transfer, play an important role. The heat transfer limited model describes the non-equilibrium phase transition processes occurring at interfaces, while the mass-diffusion limited model is employed to represent effects of non-condensable gases and multi-component mixture on V/C processes. Verification of the model and method employed in the multi-component V/C model of a multi-phase flow code was performed successfully by analyzing a series of multi-bubble condensation experiments. The applicability of the model to the accident analysis of LMRs is also discussed by comparison between steam and metallic vapor systems. (orig.)

  3. Phase Transitions of the Polariton Condensate in 2D Dirac Materials.

    Science.gov (United States)

    Lee, Ki Hoon; Lee, Changhee; Min, Hongki; Chung, Suk Bum

    2018-04-13

    For the quantum well in an optical microcavity, the interplay of the Coulomb interaction and the electron-photon (e-ph) coupling can lead to the hybridizations of the exciton and the cavity photon known as polaritons, which can form the Bose-Einstein condensate above a threshold density. Additional physics due to the nontrivial Berry phase comes into play when the quantum well consists of the gapped two-dimensional Dirac material such as the transition metal dichalcogenide MoS_{2} or WSe_{2}. Specifically, in forming the polariton, the e-ph coupling from the optical selection rule due to the Berry phase can compete against the Coulomb electron-electron (e-e) interaction. We find that this competition gives rise to a rich phase diagram for the polariton condensate involving both topological and symmetry breaking phase transitions, with the former giving rise to the quantum anomalous Hall and the quantum spin Hall phases.

  4. Phase Transitions of the Polariton Condensate in 2D Dirac Materials

    Science.gov (United States)

    Lee, Ki Hoon; Lee, Changhee; Min, Hongki; Chung, Suk Bum

    2018-04-01

    For the quantum well in an optical microcavity, the interplay of the Coulomb interaction and the electron-photon (e -ph) coupling can lead to the hybridizations of the exciton and the cavity photon known as polaritons, which can form the Bose-Einstein condensate above a threshold density. Additional physics due to the nontrivial Berry phase comes into play when the quantum well consists of the gapped two-dimensional Dirac material such as the transition metal dichalcogenide MoS2 or WSe2 . Specifically, in forming the polariton, the e -ph coupling from the optical selection rule due to the Berry phase can compete against the Coulomb electron-electron (e -e ) interaction. We find that this competition gives rise to a rich phase diagram for the polariton condensate involving both topological and symmetry breaking phase transitions, with the former giving rise to the quantum anomalous Hall and the quantum spin Hall phases.

  5. Application of microwave irradiation to organic liquid phase reactions

    International Nuclear Information System (INIS)

    Huang Kun; Liu Hua; Ji Xuelin

    1994-01-01

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

  6. Structures of the particles of the condensed dispersed phase in solid fuel combustion products plasma

    International Nuclear Information System (INIS)

    Samaryan, A.A.; Chernyshev, A.V.; Nefedov, A.P.; Petrov, O.F.; Fortov, V.E.; Mikhailov, Yu.M.; Mintsev, V.B.

    2000-01-01

    The results of experimental investigations of a type of dusty plasma which has been least studied--the plasma of solid fuel combustion products--were presented. Experiments to determine the parameters of the plasma of the combustion products of synthetic solid fuels with various compositions together with simultaneous diagnostics of the degree of ordering of the structures of the particles of the dispersed condensed phase were performed. The measurements showed that the charge composition of the plasma of the solid fuels combustion products depends strongly on the easily ionized alkali-metal impurities which are always present in synthetic fuel in one or another amount. An ordered arrangement of the particles of a condensed dispersed phase in structures that form in a boundary region between the high-temperature and condensation zones was observed for samples of aluminum-coated solid fuels with a low content of alkali-metal impurities

  7. Alternative interpretation of low-energy nuclear reaction processes with deuterated metals based on the Bose-Einstein condensation mechanism

    International Nuclear Information System (INIS)

    Yeong, E. Kim; Passell, Thomas O.

    2006-01-01

    Recently, a generalization of the Bose-Einstein condensation (BEC) mechanism has been made to a ground-state mixture of two different species of positively charged bosons in harmonic traps. The theory has been used to describe (D + Li) reactions in the low energy nuclear reaction (LENR) processes in condensed matter and predicts that the (D + Li) reaction rates can be larger than (D + D) reaction rates by as much as a factor of ∼ 50, implying that (D + Li) reactions may be occurring in addition to the (D + D) reactions. A survey of the existing data from LENR experiments is carried out to check the validity of the theoretical prediction. We conclude that there is compelling experimental evidence which support the theoretical prediction. New experimental tests of the theoretical prediction are suggested. (authors)

  8. Alternative Interpretation of Low-Energy Nuclear Reaction Processes with Deuterated Metals Based on the Bose-Einstein Condensation Mechanism

    Science.gov (United States)

    Kim, Yeong E.; Passell, Thomas O.

    2006-02-01

    Recently, a generalization of the Bose-Einstein condensation (BEC) mechanism has been made to a ground-state mixture of two different species of positively charged bosons in harmonic traps. The theory has been used to describe (D + Li) reactions in the low energy nuclear reaction (LENR) processes in condensed matter and predicts that the (D + Li) reaction rates can be larger than (D + D) reaction rates by as much as a factor of ~50, implying that (D + Li) reactions may be occuring in addition to the (D + D) reactions. A survey of the existing data from LENR experiments is carried out to check the validity of the theoretical prediction. We conclude that there is compelling experimental evidence which support the theoretical prediction. New experimental tests of the theoretical prediction are suggested.

  9. Alternative interpretation of low-energy nuclear reaction processes with deuterated metals based on the Bose-Einstein condensation mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Yeong, E. Kim [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States); Passell, Thomas O. [TOP Consulting, PO Box 336, Palo Alto, CA 94302-0336 (United States)

    2006-07-01

    Recently, a generalization of the Bose-Einstein condensation (BEC) mechanism has been made to a ground-state mixture of two different species of positively charged bosons in harmonic traps. The theory has been used to describe (D + Li) reactions in the low energy nuclear reaction (LENR) processes in condensed matter and predicts that the (D + Li) reaction rates can be larger than (D + D) reaction rates by as much as a factor of {approx} 50, implying that (D + Li) reactions may be occurring in addition to the (D + D) reactions. A survey of the existing data from LENR experiments is carried out to check the validity of the theoretical prediction. We conclude that there is compelling experimental evidence which support the theoretical prediction. New experimental tests of the theoretical prediction are suggested. (authors)

  10. Large scale electronic structure calculations in the study of the condensed phase

    NARCIS (Netherlands)

    van Dam, H.J.J.; Guest, M.F.; Sherwood, P.; Thomas, J.M.H.; van Lenthe, J.H.; van Lingen, J.N.J.; Bailey, C.L.; Bush, I.J.

    2006-01-01

    We consider the role that large-scale electronic structure computations can now play in the modelling of the condensed phase. To structure our analysis, we consider four distict ways in which today's scientific targets can be re-scoped to take advantage of advances in computing resources: 1. time to

  11. Constructing a unique two-phase compressibility factor model for lean gas condensates

    Energy Technology Data Exchange (ETDEWEB)

    Moayyedi, Mahmood; Gharesheikhlou, Aliashghar [Research Institute of Petroleum Industry (RIPI), Tehran (Iran, Islamic Republic of); Azamifard, Arash; Mosaferi, Emadoddin [Amirkabir University of Technology (AUT), Tehran (Iran, Islamic Republic of)

    2015-02-15

    Generating a reliable experimental model for two-phase compressibility factor in lean gas condensate reservoirs has always been demanding, but it was neglected due to lack of required experimental data. This study presents the main results of constructing the first two-phase compressibility factor model that is completely valid for Iranian lean gas condensate reservoirs. Based on a wide range of experimental data bank for Iranian lean gas condensate reservoirs, a unique two-phase compressibility factor model was generated using design of experiments (DOE) method and neural network technique (ANN). Using DOE, a swift cubic response surface model was generated for two-phase compressibility factor as a function of some selected fluid parameters for lean gas condensate fluids. The proposed DOE and ANN models were finally validated using four new independent data series. The results showed that there is a good agreement between experimental data and the proposed models. In the end, a detailed comparison was made between the results of proposed models.

  12. Operando Spectroscopy of the Gas-Phase Aldol Condensation of Propanal over Solid Base Catalysts

    NARCIS (Netherlands)

    Hernández-giménez, Ana M.; Ruiz-martínez, Javier; Puértolas, Begoña; Pérez-ramírez, Javier; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

    2017-01-01

    The gas-phase aldol condensation of propanal, taken as model for the aldehyde components in bio-oils, has been studied with a combined operando set-up allowing to perform FT-IR & UV–Vis diffuse reflectance spectroscopy (DRS) with on-line mass spectrometry (MS). The selected solid base catalysts, a

  13. Out of equilibrium phase transitions and a toy model for disoriented chiral condensates

    International Nuclear Information System (INIS)

    Bedaque, P.F.; Das, A.

    1993-07-01

    We study the dynamics of a second order phase transition in a situation that mimics a sudden quench to a temperature below the critical temperature in a model with dynamical symmetry breaking. In particular we show that the domains of correlated values of the condensate grow as √t and that this result seems to be largely model independent. (author). 9 refs

  14. Nonlinear optical response in condensed phases : A microscopic theory using the multipolar Hamiltonian

    NARCIS (Netherlands)

    Knoester, Jasper; Mukamel, Shaul

    1990-01-01

    A general scheme is presented for calculating the nonlinear optical response in condensed phases that provides a unified picture of excitons, polaritons, retardation, and local-field effects in crystals and in disordered systems. A fully microscopic starting point is taken by considering the

  15. Constructing a unique two-phase compressibility factor model for lean gas condensates

    International Nuclear Information System (INIS)

    Moayyedi, Mahmood; Gharesheikhlou, Aliashghar; Azamifard, Arash; Mosaferi, Emadoddin

    2015-01-01

    Generating a reliable experimental model for two-phase compressibility factor in lean gas condensate reservoirs has always been demanding, but it was neglected due to lack of required experimental data. This study presents the main results of constructing the first two-phase compressibility factor model that is completely valid for Iranian lean gas condensate reservoirs. Based on a wide range of experimental data bank for Iranian lean gas condensate reservoirs, a unique two-phase compressibility factor model was generated using design of experiments (DOE) method and neural network technique (ANN). Using DOE, a swift cubic response surface model was generated for two-phase compressibility factor as a function of some selected fluid parameters for lean gas condensate fluids. The proposed DOE and ANN models were finally validated using four new independent data series. The results showed that there is a good agreement between experimental data and the proposed models. In the end, a detailed comparison was made between the results of proposed models

  16. 2005 Annual Report Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Barlow, Stephan E.

    2005-11-15

    The Pacific Northwest National Laboratory (PNNL) hosted its second annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from May through September 2005. During this period, sixteen PNNL scientists hosted fourteen young scientists from eleven different universities. Of the fourteen participants, twelve were graduate students; one was a postdoctoral fellow; and one was a university faculty member.

  17. Sub-shot-noise phase sensitivity with a Bose-Einstein condensate Mach-Zehnder interferometer

    International Nuclear Information System (INIS)

    Pezze, L.; Smerzi, A.; Collins, L.A.; Berman, G.P.; Bishop, A.R.

    2005-01-01

    Bose-Einstein condensates (BEC), with their coherence properties, have attracted wide interest for their possible application to ultraprecise interferometry and ultraweak force sensors. Since condensates, unlike photons, are interacting, they may permit the realization of specific quantum states needed as input of an interferometer to approach the Heisenberg limit, the supposed lower bound to precision phase measurements. To this end, we study the sensitivity to external weak perturbations of a representative matter-wave Mach-Zehnder interferometer whose input are two Bose-Einstein condensates created by splitting a single condensate in two parts. The interferometric phase sensitivity depends on the specific quantum state created with the two condensates, and, therefore, on the time scale of the splitting process. We identify three different regimes, characterized by a phase sensitivity Δθ scaling with the total number of condensate particles N as (i) the standard quantum limit Δθ∼1/N 1/2 (ii) the sub shot-noise Δθ∼1/N 3/4 , and the (iii) the Heisenberg limit Δθ∼1/N. However, in a realistic dynamical BEC splitting, the 1/N limit requires a long adiabaticity time scale, which is hardly reachable experimentally. On the other hand, the sub-shot-noise sensitivity Δθ∼1/N 3/4 can be reached in a realistic experimental setting. We also show that the 1/N 3/4 scaling is a rigorous upper bound in the limit N→∞, while keeping constant all different parameters of the bosonic Mach-Zehnder interferometer

  18. Anisotropic properties of phase separation in two-component dipolar Bose-Einstein condensates

    Science.gov (United States)

    Wang, Wei; Li, Jinbin

    2018-03-01

    Using Crank-Nicolson method, we calculate ground state wave functions of two-component dipolar Bose-Einstein condensates (BECs) and show that, due to dipole-dipole interaction (DDI), the condensate mixture displays anisotropic phase separation. The effects of DDI, inter-component s-wave scattering, strength of trap potential and particle numbers on the density profiles are investigated. Three types of two-component profiles are present, first cigar, along z-axis and concentric torus, second pancake (or blood cell), in xy-plane, and two non-uniform ellipsoid, separated by the pancake and third two dumbbell shapes.

  19. Oscillatory solitons and time-resolved phase locking of two polariton condensates

    International Nuclear Information System (INIS)

    Christmann, Gabriel; Tosi, Guilherme; Baumberg, Jeremy J; Berloff, Natalia G; Tsotsis, Panagiotis; Eldridge, Peter S; Hatzopoulos, Zacharias; Savvidis, Pavlos G

    2014-01-01

    When pumped nonresonantly, semiconductor microcavity polaritons form Bose–Einstein condensates that can be manipulated optically. Using tightly-focused excitation spots, radially expanding condensates can be formed in close proximity. Using high time resolution streak camera measurements we study the time dependent properties of these macroscopic coherent states. By coupling this method with interferometry we observe directly the phase locking of two independent condensates in time, showing the effect of polariton–polariton interactions. We also directly observe fast spontaneous soliton-like oscillations of the polariton cloud trapped between the pump spots, which can be either dark or bright solitons. This transition from dark to bright is a consequence of the change of sign of the nonlinearity which we propose is due to the shape of the polariton dispersion leading to either positive or negative polariton effective mass. (paper)

  20. Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces.

    Science.gov (United States)

    Spezia, Riccardo; Martínez-Nuñez, Emilio; Vazquez, Saulo; Hase, William L

    2017-04-28

    In this Introduction, we show the basic problems of non-statistical and non-equilibrium phenomena related to the papers collected in this themed issue. Over the past few years, significant advances in both computing power and development of theories have allowed the study of larger systems, increasing the time length of simulations and improving the quality of potential energy surfaces. In particular, the possibility of using quantum chemistry to calculate energies and forces 'on the fly' has paved the way to directly study chemical reactions. This has provided a valuable tool to explore molecular mechanisms at given temperatures and energies and to see whether these reactive trajectories follow statistical laws and/or minimum energy pathways. This themed issue collects different aspects of the problem and gives an overview of recent works and developments in different contexts, from the gas phase to the condensed phase to excited states.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).

  1. Phase-driven collapse of the Cooper condensate in a nanosized superconductor

    Science.gov (United States)

    Ronzani, Alberto; D'Ambrosio, Sophie; Virtanen, Pauli; Giazotto, Francesco; Altimiras, Carles

    2017-12-01

    Superconductivity can be understood in terms of a phase transition from an uncorrelated electron gas to a condensate of Cooper pairs in which the relative phases of the constituent electrons are coherent over macroscopic length scales. The degree of correlation is quantified by a complex-valued order parameter, whose amplitude is proportional to the strength of the pairing potential in the condensate. Supercurrent-carrying states are associated with nonzero values of the spatial gradient of the phase. The pairing potential and several physical observables of the Cooper condensate can be manipulated by means of temperature, current bias, dishomogeneities in the chemical composition, or application of a magnetic field. Here we show evidence of complete suppression of the energy gap in the local density of quasiparticle states (DOS) of a superconducting nanowire upon establishing a phase difference equal to π over a length scale comparable to the superconducting coherence length. These observations are consistent with a complete collapse of the pairing potential in the center of the wire, in accordance with theoretical modeling based on the quasiclassical theory of superconductivity in diffusive systems. Our spectroscopic data, fully exploring the phase-biased states of the condensate, highlight the profound effect that extreme phase gradients exert on the amplitude of the pairing potential. Moreover, the sharp magnetic response (up to 27 mV/Φ0) observed near the onset of the superconducting gap collapse regime is exploited to realize magnetic flux detectors with noise-equivalent resolution as low as 260 n Φ0/√{Hz} .

  2. Spectrophotometric Determination of Reboxetine through Condensation and Diazo-Coupling Reactions

    Directory of Open Access Journals (Sweden)

    K. Srikanth

    2011-01-01

    Full Text Available In the present study, two simple, sensitive and reproducible visible spectrophotometric methods were developed for the determination of reboxetine in pure form and in pharmaceutical formulations. The methods involve acid hydrolysis of reboxetine methane sulphonate (Reboxetine as methane sulphonate and the product obtained was used for the estimation. Out of the two methods developed in the laboratory, the first method involves the condensation reaction of hydrolysed reboxetine methane sulphonate with ethyl acetoacetate in sulphuric acid medium and the second method involves the diazocoupling reaction of hydrolysed reboxetine methane sulphonate with diazotized p-sulphanilic acid in alkaline medium. They have absorption maxima at 400 nm and 430 nm respectively and obey Beer’s law in the concentration ranges of 0.5 - 0.3 μgmL-1 and 1.0 - 7.5 μgmL-1 respectively. Results of analysis were validated statistically and by recovery studies. The apparent molar absorptivity values (∈max obtained are 7.549 x 104 L mol-1 cm-11 and 2.656x104 Lmol-1cm-1 respectively. Both these have correlation coefficient value of 0.9999. The proposed methods have good precision and accuracy.

  3. Aromaticity of benzene in condensed phases. A case of a benzene-water system

    Science.gov (United States)

    Zborowski, Krzysztof K.

    2014-05-01

    A theoretical Density Functional Theory study was performed for a benzene molecule in water cages. Two DFT functionals (B3LYP and BLYP) were employed. The optimized geometries of the studied clusters were used to calculate the aromaticity of benzene in a condensed phase using the aromaticity indices: HOMA, NICS, PDI, and H. The results were compared with aromaticity of a single benzene molecule in the gas phase and in the solvent environment provided by the PCM continuum model. It is argued that high aromaticity of benzene in the gas phase is retained in the water environment.

  4. Cross-Aldol condensation of isobutyraldehyde and formaldehyde using phase transfer catalyst

    Directory of Open Access Journals (Sweden)

    Azhar Hashmi

    2016-09-01

    Full Text Available The hydroxypivaldehyde (HPA precursor intermediate for the synthesis of neopentyl glycol (NPG is prepared by novel cross Aldol condensation of isobutyraldehyde and formaldehyde at 20 °C using benzyltrimethylammonium hydroxide, a basic phase transfer catalyst. A feed mole ratio of 1.1:1.0:0.04 (isobutyraldehyde:formaldehyde:benzyltrimethylammonium hydroxide afforded hydroxypivaldehyde as white solid in almost quantitative yield with ∼100% selectivity.

  5. Cross-Aldol condensation of isobutyraldehyde and formaldehyde using phase transfer catalyst

    OpenAIRE

    Azhar Hashmi

    2016-01-01

    The hydroxypivaldehyde (HPA) precursor intermediate for the synthesis of neopentyl glycol (NPG) is prepared by novel cross Aldol condensation of isobutyraldehyde and formaldehyde at 20 °C using benzyltrimethylammonium hydroxide, a basic phase transfer catalyst. A feed mole ratio of 1.1:1.0:0.04 (isobutyraldehyde:formaldehyde:benzyltrimethylammonium hydroxide) afforded hydroxypivaldehyde as white solid in almost quantitative yield with ∼100% selectivity.

  6. 2006 Annual Report Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Avery, Nikki B.; Barlow, Stephan E.

    2006-11-10

    The Pacific Northwest National Laboratory (PNNL) hosted its third annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from May through September 2006. During this period, twenty PNNL scientists hosted twenty-seven scientists from twenty-five different universities. Of the twenty-seven participants, one was a graduating senior; twenty-one were graduate students; one was a postdoctoral fellow; and four were university faculty members.

  7. Phase-locking in quantum and classical oscillators: polariton condensates, lasers, and arrays of Josephson junctions

    OpenAIRE

    EASTHAM, PAUL

    2003-01-01

    PUBLISHED We connect three phenomena in which a coherent electromagnetic field could be generated: polariton condensation, phase-locking in arrays of underdamped Josephson junctions, and lasing. All these phenomena have been described using Dicke-type models of spins coupled to a single photon mode. These descriptions may be distinguished by whether the spins are quantum or classical, and whether they are strongly or weakly damped.

  8. Method of measuring interface area of activated carbons in condensed phase

    Science.gov (United States)

    Dmitriyev, D. S.; Agafonov, D. V.; Kiseleva, E. A.; Mikryukova, M. A.

    2018-01-01

    In this work, we investigated the correlation between the heat of wetting of super-capacitor electrode material (activated carbon) with condensed phases (electrolytes based on homologous series of phosphoric acid esters) and the capacity of the supercapacitor. The surface area of the electrode-electrolyte interface was calculated according to the obtained correlations using the conventional formula for calculating the capacitance of a capacitor.

  9. 2007 Annual Report Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Kenneth M.

    2007-10-31

    The Pacific Northwest National Laboratory (PNNL) hosted its fourth annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from April through September 2007. During this time, 21 PNNL scientists hosted 23 participants from 20 different universities. Of the 23 participants, 20 were graduate students, 1 was a postdoctoral fellow, and 2 were university faculty members. This report covers the essense of the program and the research the participants performed.

  10. Photothermal experiments on condensed phase samples of agricultural interest : optical and thermal characterization

    OpenAIRE

    Favier, J.P.

    1997-01-01


    A rapidly increasing number of photothermal (PT) techniques has had a considerable impact on agriculture and environmental sciences in the last decade. It was the purpose of the work described here to develop and apply new PT techniques in this specific field of research.

    Chapter I is a general introduction with an overview of PT techniques used in this research. Two different photoacoustic (PA) techniques used for optical characterization of a variety of condensed phase sa...

  11. Simulating the control of molecular reactions via modulated light fields: from gas phase to solution

    Science.gov (United States)

    Thallmair, Sebastian; Keefer, Daniel; Rott, Florian; de Vivie-Riedle, Regina

    2017-04-01

    Over the past few years quantum control has proven to be very successful in steering molecular processes. By combining theory with experiment, even highly complex control aims were realized in the gas phase. In this topical review, we illustrate the past achievements on several examples in the molecular context. The next step for the quantum control of chemical processes is to translate the fruitful interplay between theory and experiment to the condensed phase and thus to the regime where chemical synthesis can be supported. On the theory side, increased efforts to include solvent effects in quantum control simulations were made recently. We discuss two major concepts, namely an implicit description of the environment via the density matrix algorithm and an explicit inclusion of solvent molecules. By application to chemical reactions, both concepts conclude that despite environmental perturbations leading to more complex control tasks, efficient quantum control in the condensed phase is still feasible.

  12. Examination of transient characteristics of two-phase natural circulation within a Freon-113 boiling/condensation loop

    International Nuclear Information System (INIS)

    Tanimoto, K.; Ishii, M.

    1998-01-01

    Transient characteristics of two-phase natural circulation within a Freon-113 loop with a large condenser have been examined mainly focused on the flashing phenomenon. General behavior was described and parametric studies were performed. The items observed were the period and duration of flashing, peak flow rate, amount of flow carryover per flashing, lowest-peak liquid level within the condenser, and the peak void distribution in the riser section. The parameters considered were the heater power input, valve friction at the heater inlet (simulating the loopwise friction), condenser cooling, degree of subcooling at the heater inlet, and the heat loss to the surroundings. As a whole, the heater power input, valve friction, and the rate of condenser cooling played important roles in flashing while the other effects being marginal. In general, the flow appeared to be more unstable with the larger condensing surface which causes the condensation-induced flashing. (orig.)

  13. Phase zone plates as condensers for the Gottingen scanning x-ray microscope

    International Nuclear Information System (INIS)

    Hilkenbach, R.; Thieme

    1987-01-01

    With the Gottingen scanning x-ray microscope the synchrotron source is image by x-ray optics into a monochromatic small scan spot, through which a specimen can be moved. Hereby one part of the optics, the condenser zone plate and a pinhole, works as a linear monochromator in the wavelength region of λ = 2.36 nm to λ = 4.5 nm. The efficiency of such a condenser should be as high as possible to minimize the loss of radiation. Phase zone plates have a four times higher efficiency in the first order of diffraction than amplitude zone plates. Two condenser zone plates, KZP4 and KZP5, have been constructed so that they are well suited for the use in the scanning microscope. These zone plates have been made holographically by superposing two wavefronts of laser light in an specific designed optical arrangement and exposing the zone plate structure into a photoresist. Using reactive ion etching (RIE) the structure has been transformed into Germanium. The thickness of the zone plate has been chosen to show at λ = 2.36 nm a phase effect. The efficiency has been measured at the Berliner Elektronenspeircherring Gesellschaft fur Synchrotronstrahlung m.b.H., Berlin

  14. Condensation in gas transmission pipelines. Phase behavior of mixtures of hydrogen with natural gas

    Energy Technology Data Exchange (ETDEWEB)

    Schouten, J.A.; Michels, J.P.J. [Amsterdam Univ. (Netherlands). Van der Waals-Zeeman Inst.; Rosmalen, R.J. van [Energy, Roden (Netherlands)

    2005-05-01

    Several pressure and temperature reductions occur along gas transmission lines. Since the pressure and temperature conditions of the natural gas in the pipeline are often close to the dew point curve, liquid dropout can occur. Injection of hydrogen into the natural gas will change the phase envelope and thus the liquid dropout. This condensation of the heavy hydrocarbons requires continuous operational attention and a positive effect of hydrogen may affect the decision to introduce hydrogen. In this paper we report on calculations of the amount of condensate in a natural gas and in this natural gas mixed with 16.7% hydrogen. These calculations have been performed at conditions prevailing in gas transport lines. The results will be used to discuss the difference in liquid dropout in a natural gas and in a mixture with hydrogen at pressure reduction stations, at crossings under waterways, at side-branching, and at separators in the pipelines. (author)

  15. Switching moving boundary models for two-phase flow evaporators and condensers

    Science.gov (United States)

    Bonilla, Javier; Dormido, Sebastián; Cellier, François E.

    2015-03-01

    The moving boundary method is an appealing approach for the design, testing and validation of advanced control schemes for evaporators and condensers. When it comes to advanced control strategies, not only accurate but fast dynamic models are required. Moving boundary models are fast low-order dynamic models, and they can describe the dynamic behavior with high accuracy. This paper presents a mathematical formulation based on physical principles for two-phase flow moving boundary evaporator and condenser models which support dynamic switching between all possible flow configurations. The models were implemented in a library using the equation-based object-oriented Modelica language. Several integrity tests in steady-state and transient predictions together with stability tests verified the models. Experimental data from a direct steam generation parabolic-trough solar thermal power plant is used to validate and compare the developed moving boundary models against finite volume models.

  16. Theoretical insights into the sites and mechanisms for base catalyzed esterification and aldol condensation reactions over Cu.

    Science.gov (United States)

    Neurock, Matthew; Tao, Zhiyuan; Chemburkar, Ashwin; Hibbitts, David D; Iglesia, Enrique

    2017-04-28

    Condensation and esterification are important catalytic routes in the conversion of polyols and oxygenates derived from biomass to fuels and chemical intermediates. Previous experimental studies show that alkanal, alkanol and hydrogen mixtures equilibrate over Cu/SiO 2 and form surface alkoxides and alkanals that subsequently promote condensation and esterification reactions. First-principle density functional theory (DFT) calculations were carried out herein to elucidate the elementary paths and the corresponding energetics for the interconversion of propanal + H 2 to propanol and the subsequent C-C and C-O bond formation paths involved in aldol condensation and esterification of these mixtures over model Cu surfaces. Propanal and hydrogen readily equilibrate with propanol via C-H and O-H addition steps to form surface propoxide intermediates and equilibrated propanal/propanol mixtures. Surface propoxides readily form via low energy paths involving a hydrogen addition to the electrophilic carbon center of the carbonyl of propanal or via a proton transfer from an adsorbed propanol to a vicinal propanal. The resulting propoxide withdraws electron density from the surface and behaves as a base catalyzing the activation of propanal and subsequent esterification and condensation reactions. These basic propoxides can readily abstract the acidic C α -H of propanal to produce the CH 3 CH (-) CH 2 O* enolate, thus initiating aldol condensation. The enolate can subsequently react with a second adsorbed propanal to form a C-C bond and a β-alkoxide alkanal intermediate. The β-alkoxide alkanal can subsequently undergo facile hydride transfer to form the 2-formyl-3-pentanone intermediate that decarbonylates to give the 3-pentanone product. Cu is unique in that it rapidly catalyzes the decarbonylation of the C 2n intermediates to form C 2n-1 3-pentanone as the major product with very small yields of C 2n products. This is likely due to the absence of Brønsted acid sites

  17. Intermolecular interactions in the condensed phase: Evaluation of semi-empirical quantum mechanical methods.

    Science.gov (United States)

    Christensen, Anders S; Kromann, Jimmy C; Jensen, Jan H; Cui, Qiang

    2017-10-28

    To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy in solution is computed via a thermodynamic cycle that integrates dimer binding energy in the gas phase at the coupled cluster level and solute-solvent interaction with density functional theory; the estimated uncertainty of such calculated interaction energy is ±1.5 kcal/mol. The dataset is used to benchmark the performance of a set of semi-empirical quantum mechanical (SQM) methods that include DFTB3-D3, DFTB3/CPE-D3, OM2-D3, PM6-D3, PM6-D3H+, and PM7 as well as the HF-3c method. We find that while all tested SQM methods tend to underestimate binding energies in the gas phase with a root-mean-squared error (RMSE) of 2-5 kcal/mol, they overestimate binding energies in the solution phase with an RMSE of 3-4 kcal/mol, with the exception of DFTB3/CPE-D3 and OM2-D3, for which the systematic deviation is less pronounced. In addition, we find that HF-3c systematically overestimates binding energies in both gas and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need to be treated in a balanced fashion.

  18. Intermolecular interactions in the condensed phase: Evaluation of semi-empirical quantum mechanical methods

    Science.gov (United States)

    Christensen, Anders S.; Kromann, Jimmy C.; Jensen, Jan H.; Cui, Qiang

    2017-10-01

    To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy in solution is computed via a thermodynamic cycle that integrates dimer binding energy in the gas phase at the coupled cluster level and solute-solvent interaction with density functional theory; the estimated uncertainty of such calculated interaction energy is ±1.5 kcal/mol. The dataset is used to benchmark the performance of a set of semi-empirical quantum mechanical (SQM) methods that include DFTB3-D3, DFTB3/CPE-D3, OM2-D3, PM6-D3, PM6-D3H+, and PM7 as well as the HF-3c method. We find that while all tested SQM methods tend to underestimate binding energies in the gas phase with a root-mean-squared error (RMSE) of 2-5 kcal/mol, they overestimate binding energies in the solution phase with an RMSE of 3-4 kcal/mol, with the exception of DFTB3/CPE-D3 and OM2-D3, for which the systematic deviation is less pronounced. In addition, we find that HF-3c systematically overestimates binding energies in both gas and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need to be treated in a balanced fashion.

  19. Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization.

    Science.gov (United States)

    Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C

    2015-03-01

    We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Microwave-assisted solid-phase Ugi four-component condensations

    DEFF Research Database (Denmark)

    Nielsen, John

    1999-01-01

    An 18-member library was constructed from 2 isocyanides, 3 aldehydes and 3 carboxylic acids via microwave-assisted solid-phase Ugi reactions on TentaGel S RAM. Products of high purity were obtained in moderate to excellent yields after reaction times of 5 minutes or less (irradiation at 60W). (C...

  1. Cold storage condensation heat recovery system with a novel composite phase change material

    International Nuclear Information System (INIS)

    Xia, Mingzhu; Yuan, Yanping; Zhao, Xudong; Cao, Xiaoling; Tang, Zhonghua

    2016-01-01

    Highlights: • Cold storage condensation heat recovery system using PCM was proposed. • CW with a phase change temperature of nearly 80 °C was selected as the potential PCM. • The optimal mass ratio between the CW and EG was 10:1. • The thermal and physical performances of the CW/EG were investigated. • The thermal reliability was demonstrated by 1000 cycles. - Abstract: Using condensation heat from cold storage refrigeration systems to provide heat for domestic hot water preparation and industrial hot water supply promotes energy conservation. However, few studies have investigated cold storage condensation heat recovery using phase change materials (PCMs). In this study, a cold storage condensation heat recovery system that uses PCMs has been designed and analysed. According to the principle of energy cascade recycling, different operation modes could be effectively switched to recycle condensation heat. Furthermore, a novel and suitable phase change composite material is developed for cold storage condensation heat recovery, which has a relatively large latent heat, high thermal conductivity, and an appropriate phase change temperature (i.e. 80 °C). With carnauba wax (CW) as the PCM and expanded graphite (EG) as the additive, a composite was developed with an optimal mass ratio of CW:EG = 10:1. The thermal and physical properties and the interior structure of the composite were then investigated using a scanning electron microscope (SEM), thermal constants analyser (Hot Disk), differential scanning calorimeter (DSC), and Fourier transform infrared spectrometer (FT-IR). Furthermore, experiments on the melting and solidification processes and accelerated thermal cycling were also conducted. It was found that at the optimal mass ratio of 10:1, the temperatures of the CW/EG composite in the melting and solidification processes were 81.98 °C and 80.43 °C, respectively, while the corresponding latent heats were 150.9 J/g and 142.6 J/g, respectively

  2. Quantum phase transition of Bose-Einstein condensates on a nonlinear ring lattice

    International Nuclear Information System (INIS)

    Zhou Zhengwei; Zhang Shaoliang; Zhou Xiangfa; Guo Guangcan; Zhou Xingxiang; Pu Han

    2011-01-01

    We study the phase transitions in a one-dimensional Bose-Einstein condensate on a ring whose atomic scattering length is modulated periodically along the ring. By using a modified Bogoliubov method to treat such a nonlinear lattice in the mean-field approximation, we find that the phase transitions are of different orders when the modulation period is 2 and greater than 2. We further perform a full quantum mechanical treatment based on the time-evolving block decimation algorithm which confirms the mean-field results and reveals interesting quantum behavior of the system. Our studies yield important knowledge of competing mechanisms behind the phase transitions and the quantum nature of this system.

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

    Data.gov (United States)

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

  4. The Impact of Condensed-Phase Viscosity on Multiphase Oxidation Kinetics Involving O3, NO3, and OH

    Science.gov (United States)

    Li, J.; Forrester, S. M.; Knopf, D. A.

    2017-12-01

    Organic aerosol (OA) particles are ubiquitous in the atmosphere and have a significant influence on air quality, human health, cloud formation processes and global climate. By now it is well-recognized that organic particulate species can be amorphous in nature, existing in liquid, semi-solid and solid (glassy) phase states. The phase state is modulated by particle composition and environmental conditions such as relative humidity and temperature. These modifications can influence particle viscosity and molecular diffusion and, therefore, impact the reactive uptake of gas-phase oxidants and radicals by the organic substrate. In this study, we determined the reactive uptake coefficients (γ) of O3 by canola oil, NO3 by levoglucosan (LEV) and a LEV/xylitol mixture, and OH by glucose/sulfuric acid mixtures and glucose/1,2,6-hexanetriol mixtures under dry conditions and for temperatures ranging from 293 K to 213 K. Uptake coefficients have been measured employing a chemical ionization mass spectrometer coupled to a temperature-controlled rotating-wall flow reactor. Glass transition temperatures (Tg) of applied substrates were estimated by the Gordon-Taylor equation. Phase states were qualitatively probed via poking experiment using a temperature-controlled cooling stage. Shattering of the substrates indicated the formation of a glassy state. Results show a significant impact of condensed phase state on reactive uptake kinetics whereby γ changed most profoundly around estimated Tg. For example, γ decreases from 6.5×10-4 to 1.9 ×10-5 for O3 uptake by canola oil and from 8.3×10-4 to 3.1×10-4 for NO3 uptake by the LEV/xylitol mixture, respectively. The decrease in γ will be discussed with regard to phase state, desorption lifetime, and Arrhenius temperature dependence of reaction rates. First results of OH uptakes at low temperatures are presented, together with a discussion of the relevant atmospheric implications.

  5. Current-phase relation of a Bose-Einstein condensate flowing through a weak link

    International Nuclear Information System (INIS)

    Piazza, F.; Smerzi, A.; Collins, L. A.

    2010-01-01

    We study the current-phase relation of a Bose-Einstein condensate flowing through a repulsive square barrier by solving analytically the one-dimensional Gross-Pitaevskii equation. The barrier height and width fix the current-phase relation j(δφ), which tends to j∼cos(δφ/2) for weak barriers and to the Josephson sinusoidal relation j∼sin(δφ) for strong barriers. Between these two limits, the current-phase relation depends on the barrier width. In particular, for wide-enough barriers, we observe two families of multivalued current-phase relations. Diagrams belonging to the first family, already known in the literature, can have two different positive values of the current at the same phase difference. The second family, new to our knowledge, can instead allow for three different positive currents still corresponding to the same phase difference. Finally, we show that the multivalued behavior arises from the competition between hydrodynamic and nonlinear-dispersive components of the flow, the latter due to the presence of a soliton inside the barrier region.

  6. 2008 Summer Research Institute Interfacial and Condensed Phase Chemical Physics Annual Report

    Energy Technology Data Exchange (ETDEWEB)

    Garrett, Bruce C.; Tonkyn, Russell G.; Avery, Nachael B.

    2008-11-01

    For the fifth year, the Pacific Northwest National Laboratory in Richland, Washington, invited graduate students, postdoctoral fellows, university faculty, and students entering graduate students from around the world to participate in the Summer Research Institute in Interfacial and Condensed Phase Chemical Physics. The institute offers participants the opportunity to gain hands-on experience in top-notch research laboratories while working along internationally respected mentors. Of the 38 applicants, 20 were accepted for the 8- to 10-week program. The participants came from universities as close as Seattle and Portland and as far away as Germany and Singapore. At Pacific Northwest National Laboratory, the 20 participants were mentored by 13 scientists. These mentors help tailor the participant’s experience to the needs of that person. Further, the mentors provide guidance on experimental and theoretical techniques, research design and completion, and other aspects of scientific careers in interfacial and condensed phase chemical physics. The research conducted at the institute can result in tangible benefits for the participants. For example, many have co-authored papers that have been published in peer-reviewed journals, including top-rated journals such as Science. Also, they have presented their research at conferences, such as the Gordon Research Conference on Dynamics at Surfaces and the AVS national meeting. Beyond that, many of the participants have started building professional connections with researchers at Pacific Northwest National Laboratory, connections that will serve them well during their careers.

  7. A green route to methyl acrylate and acrylic acid by an aldol condensation reaction over H-ZSM-35 zeolite catalysts.

    Science.gov (United States)

    Ma, Zhanling; Ma, Xiangang; Liu, Hongchao; He, Yanli; Zhu, Wenliang; Guo, Xinwen; Liu, Zhongmin

    2017-08-10

    A one-step aldol condensation reaction to produce MA and AA is a green and promising strategy. Here, the aldol condensation reaction was first conducted with DMM and MAc over different types of zeolite catalysts. The H-ZSM-35 zeolite demonstrates excellent catalytic performance with a DMM conversion of 100% and a MA + AA selectivity of up to 86.2% and superior regeneration ability, with great potential for industrial operation.

  8. Spatial energy distribution around energetic ions in condensed phases. Study by thermoluminescence

    International Nuclear Information System (INIS)

    Montret-Brugerolle, M.

    1980-01-01

    One describes a model that allows the calculation of the spatial energy distribution around a heavy ion trajectory within the physical step of the phenomena involved (10 -13 s). Experimental data are collected in order to chek the model in the condensed phase. The experimental procedure is thermoluminescence (TL). LiF : Mg, Ti, CaF 2 : Dy and CaF 2 : Mn crystals are irradiated with 60 Co-γ rays and with heavy ions: He, Ne, Cu, Kr of various incident energies. An extensive study of the TL light induced by heavy ions bombardment is carried out as a function of the energy and density of the impinging ions. It is shown that the different response observed with respect to γ-irradiation is due neither to TL traps destruction nor to the recombination of a larger amount of charge-carriers. Experimental data and those obtained from the distribution of energy density are compared, and the agreement is satisfactory. Hence, it is thought that the model may be extended to condensed media [fr

  9. Numerical simulation of gas-liquid two-phase flow behavior with condensation heat transfer

    International Nuclear Information System (INIS)

    Takamori, Kazuhide; Murase, Michio; Baba, Yoshikazu; Aihara, Tsuyoshi.

    1995-01-01

    In this study, condensation heat transfer experiments were performed in order to verify a condensation heat transfer model coupled with a three-dimensional two-phase flow analysis. In the heat transfer model, the liquid film flow rate on the heat transfer tubes was calculated by a mass balance equation and the liquid film thickness was calculated from the liquid film flow rate using Nusselt's laminar flow model and Fujii's equation for steam velocity effect. In the experiments, 112 horizontal staggered tubes with an outer diameter of 16 mm and length of 0.55 m were used. Steam and spray water were supplied to the test section, and inlet quality was controlled by the spray water flow rate. The temperature was 100degC and the pressure was 0.1 MPa. The overall heat transfer coefficients were measured for inlet quality of 13-100%. From parameter calculations for the falling liquid film ratio from the upper tubes to the lower tubes, the calculated overall heat transfer coefficients agreed with the data to within ±5% at the falling liquid film ratio of 0.7. (author)

  10. Ultrastructural organization of premature condensed chromosomes at S-phase as observed by atomic force microscopy

    International Nuclear Information System (INIS)

    Fan Yihui; Zhang Xiaohong; Bai Jing; Mao Renfang; Zhang Chunyu; Lei Qingquan; Fu Songbin

    2007-01-01

    In this study, we used calyculin A to induce premature condensed chromosomes (PCC). S-phase PCC is as 'pulverized' appearance when viewed by light microscopy. Then, we applied atomic force microscopy (AFM) to investigate the ultrastructual organization of S-phase PCC. S-phase PCC shows ridges and grooves as observed by AFM. After trypsin treatment, chromosome surface roughness is increased and chromosome thickness is decreased. At high magnification, the ridges are composed of densely packed 30 nm chromatin fibers which form chromosome axis. Around the ridges, many 30 nm chromatin fibers radiate from center. Some of the 30 nm chromatin fibers are free ends. The grooves are not real 'gap', but several 30 nm chromatin fibers which connect two ridges and form 'grid' structure. There are four chromatin fibers detached from chromosome: two free straight 30 nm chromatin fibers, one loop chromatin fiber and one straight combining with loop chromatin fiber. These results suggested that the S-phase PCC was high-order organization of 30 nm chromatin fibers and the 30 nm chromatin fibers could exist as loops and free ends

  11. Heat-transfer enhancement of two-phase closed thermosyphon using a novel cross-flow condenser

    Science.gov (United States)

    Aghel, Babak; Rahimi, Masoud; Almasi, Saeed

    2017-03-01

    The present study reports the heat-transfer performance of a two-phase closed thermosyphon (TPCT) equipped with a novel condenser. Distillated water was used as working fluid, with a volumetric liquid filling ratio of 75 %. An increase in heat flux was used to measure the response of the TPCT, including variations in temperature distribution, thermal resistance, average temperature of each section of TPCT and overall thermal difference. Results show that for various power inputs from 71 to 960 W, the TPCT with the novel condenser had a lower wall-temperature difference between the evaporator and condenser sections than did the unmodified TPCT. Given the experimental data for heat-transfer performance, it was found that the thermal resistance in the TPCT equipped with the proposed condenser was between 10 and 17 % lower than in the one without.

  12. Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics

    International Nuclear Information System (INIS)

    Huo, Pengfei; Miller, Thomas F. III; Coker, David F.

    2013-01-01

    A partial linearized path integral approach is used to calculate the condensed phase electron transfer (ET) rate by directly evaluating the flux-flux/flux-side quantum time correlation functions. We demonstrate for a simple ET model that this approach can reliably capture the transition between non-adiabatic and adiabatic regimes as the electronic coupling is varied, while other commonly used semi-classical methods are less accurate over the broad range of electronic couplings considered. Further, we show that the approach reliably recovers the Marcus turnover as a function of thermodynamic driving force, giving highly accurate rates over four orders of magnitude from the normal to the inverted regimes. We also demonstrate that the approach yields accurate rate estimates over five orders of magnitude of inverse temperature. Finally, the approach outlined here accurately captures the electronic coherence in the flux-flux correlation function that is responsible for the decreased rate in the inverted regime

  13. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    Energy Technology Data Exchange (ETDEWEB)

    Annapureddy, HVR; Motkuri, RK; Nguyen, PTM; Truong, TB; Thallapally, PK; McGrail, BP; Dang, LX

    2014-02-05

    In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni-2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol.

  14. Field induced magnetic phase transition as a magnon Bose Einstein condensation

    Directory of Open Access Journals (Sweden)

    Teodora Radu et al

    2007-01-01

    Full Text Available We report specific heat, magnetocaloric effect and magnetization measurements on single crystals of the frustrated quasi-2D spin -½ antiferromagnet Cs2CuCl4 in the external magnetic field 0≤B≤12 T along a-axis and in the temperature range 0.03 K≤T≤6 K. Decreasing the applied magnetic field B from high fields leads to the closure of the field induced gap in the magnon spectrum at a critical field Bcsimeq8.44 T and a long-range incommensurate state below Bc. In the vicinity of Bc, the phase transition boundary is well described by the power law TN~(Bc-B1/phi with the measured critical exponent phisimeq1.5. These findings provide experimental evidence that the scaling law of the transition temperature TN can be described by the universality class of 3D Bose–Einstein condensation (BEC of magnons.

  15. Recondensation phenomena of a hot two-phase fluid in the presence of non condensable gases

    International Nuclear Information System (INIS)

    Berthoud, G.

    1983-09-01

    The condensation rates obtained during the expansion of a large hot bubble containing non condensable gases in its cold liquid is studied. The failure of theories derived from the Nusselt model for liquid metals led to use the kinetic theory of condensation. The additionnal resistance due to the presence of non condensable gases is expressed by the vapor diffusion through the layer of gases which accumulates at the interface. This model is then used to interprete experiments [fr

  16. Mars Ascent Vehicle Reaction Control System, Phase I

    Data.gov (United States)

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

  17. Experimental and phenomenological comparison between Piezonuclear reactions and Condensed Matter Nuclear Science phenomenology

    OpenAIRE

    Cardone, F.; Mignani, R.; Petrucci, A.

    2011-01-01

    The purpose of this paper is to place side by side the experimental results of Piezonu- clear reactions, which have been recently unveiled, and those collected during the last twenty years of experiments on low energy nuclear reactions (LENR). We will briefy re- port the results of our campaign of piezonuclear reactions experiments where ultrasounds and cavitation were applied to solutions of stable elements. These outcomes will be shown to be compatible with the results and evidences obtaine...

  18. One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

    KAUST Repository

    Wang, Xinbo; Pan, Yupeng; Huang, Kuo-Wei; Lai, Zhiping

    2015-01-01

    A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction

  19. Bifunctional nanocrystalline MgO for chiral epoxy ketones via Claisen-Schmidt condensation-asymmetric epoxidation reactions.

    Science.gov (United States)

    Choudary, Boyapati M; Kantam, Mannepalli L; Ranganath, Kalluri V S; Mahendar, Koosam; Sreedhar, Bojja

    2004-03-24

    Design and development of a truly nanobifunctional heterogeneous catalyst for the Claisen-Schmidt condensation (CSC) of benzaldehydes with acetophenones to yield chalcones quantitatively followed by asymmetric epoxidation (AE) to afford chiral epoxy ketones with moderate to good yields and impressive ee's is described. The nanomagnesium oxide (aerogel prepared) NAP-MgO was found to be superior over the NA-MgO and CM-MgO in terms of activity and enantioselectivity as applicable in these reactions. An elegant strategy for heterogenization of homogeneous catalysts is presented here to evolve single-site chiral catalysts for AE by a successful transfer of molecular chemistry to surface metal-organic chemistry with the retention of activity, selectivity/enantioselectivity. Brønsted hydroxyls are established as sole contributors for the epoxidation reaction, while they add on to the CSC, which is largely driven by Lewis basic O2-sites. Strong hydrogen-bond interactions between the surface -OH on MgO and -OH groups of diethyl tartrate are found inducing enantioselectivity in the AE reaction. Thus, the nanocrystalline NAP-MgO with its defined shape, size, and accessible OH groups allows the chemisorption of TBHP, DET, and olefin on its surface to accomplish single-site chiral catalysts to provide optimum ee's in AE reactions.

  20. GASCON and MHDGAS: FORTRAN IV computer codes for calculating gas and condensed-phase compositions in the coal-fired open-cycle MHD system

    Energy Technology Data Exchange (ETDEWEB)

    Blackburn, P E

    1977-12-01

    Fortran IV computer codes have been written to calculate the equilibrium partial pressures of the gaseous phase and the quantity and composition of the condensed phases in the open-cycle MHD system. The codes are based on temperature-dependent equilibrium constants, mass conservation, the mass action law, and assumed ideal solution of compounds in each of two condensed phases. It is assumed that the phases are an oxide-silicate phase and a sulfate-carbonate-hydroxide phase. Calculations are iterated for gas and condensate concentrations while increasing or decreasing the total moles of elements, but keeping mole ratios constant, to achieve the desired total pressure. During iteration the oxygen partial pressure is incrementally changed. The decision to increase or decrease the oxygen pressure in this process depends on comparison of the oxygen content calculated in the gas and condensate phases with the initial amount of oxygen in the ash, coal, seed, and air. This process, together with a normalization step, allows the elements to converge to their initial quantities. Two versions of the computer code have been written. GASCON calculates the equilibrium gas partial pressures and the quantity and composition of the condensed phases in steps of thirteen temperature and pressure combinations in which the condensate is removed after each step, simulating continuous slag removal from the MHD system. MHDGAS retains the condensate for each step, simulating flow of condensate (and gas) through the MHD system.

  1. Temperature-Dependent Change of Packing Structure of Condensed-Phase in a Micro-Phase Separated Langmuir Monolayer Studied by Grazing-Incidence X-ray Diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Iimura, Ken-ichi [Department of Applied Chemisty, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Utsunomiya (Japan); Kato, Teiji [Department of Applied Chemisty, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Utsunomiya (Japan); Brezesinski, Gerald [Max-Planck Instutite of Colloids and Interfaces, Research Campus Golm, D-14476 Potsdam (Germany)

    2007-10-15

    Packing structure of condensed-phase in a binary mixed Langmuir monolayer of behenic acid (C22) and perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoic acid (PFPE) on a cadmium acetate aqueous solution was studied by grazing incidence X-ray diffraction (GIXD) as a function of the subphase temperature. The measurements were made during temperature scan at a fixed molecular area to explain the morphological change of the condensed-phase domains due to a thermal treatment reported previously. Analysis of GIXD data implies that the condensed-phase domains are composed of only the C22 molecules perpendicularly oriented and very closely packed in a centered rectangular unit cell with orthorhombic distortion at low temperatures. As the temperature increases the area occupied by molecule increases, and above 25 deg. C the lattice becomes disordered, which would allow morphological transformation of the condensed-phase domains. The process of packing structure change is almost reversible except for non-equilibrium phases observed for the monolayer spread at a low temperature, 5.5 deg. C.

  2. Temperature-Dependent Change of Packing Structure of Condensed-Phase in a Micro-Phase Separated Langmuir Monolayer Studied by Grazing-Incidence X-ray Diffraction

    International Nuclear Information System (INIS)

    Iimura, Ken-ichi; Kato, Teiji; Brezesinski, Gerald

    2007-01-01

    Packing structure of condensed-phase in a binary mixed Langmuir monolayer of behenic acid (C22) and perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoic acid (PFPE) on a cadmium acetate aqueous solution was studied by grazing incidence X-ray diffraction (GIXD) as a function of the subphase temperature. The measurements were made during temperature scan at a fixed molecular area to explain the morphological change of the condensed-phase domains due to a thermal treatment reported previously. Analysis of GIXD data implies that the condensed-phase domains are composed of only the C22 molecules perpendicularly oriented and very closely packed in a centered rectangular unit cell with orthorhombic distortion at low temperatures. As the temperature increases the area occupied by molecule increases, and above 25 deg. C the lattice becomes disordered, which would allow morphological transformation of the condensed-phase domains. The process of packing structure change is almost reversible except for non-equilibrium phases observed for the monolayer spread at a low temperature, 5.5 deg. C

  3. Triplet--Triplet Absorption Spectra of Organic Molecules in Condensed Phases

    International Nuclear Information System (INIS)

    Carmichael, I.; Hug, G.L.

    1986-01-01

    We present a compilation of spectral parameters associated with triplet--triplet absorption of organic molecules in condensed media. The wavelengths of maximum absorbance and the corresponding extinction coefficients, where known, have been critically evaluated. Other data, for example, lifetimes, energies and energy transfer rates, relevant to the triplet states of these molecules are included by way of comments but have not been subjected to a similar scrutiny. Work in the gas phase has been omitted, as have theoretical studies. We provide an introduction to triplet state processes in solution and solids, developing the conceptual background and offering an historical perspective on the detection and measurement of triplet state absorption. Techniques employed to populate the triplet state are reviewed and the various approaches to the estimation of the extinction coefficient of triplet--triplet absorption are critically discussed. A statistical analysis of the available data is presented and recommendations for a hierarchical choice of extinction coefficients are made. Data collection is expected to be complete through the end of 1984. Compound name, molecular formula and author indexes are appended

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

    Science.gov (United States)

    Black, Ariel

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

  5. Condensed tannins. Base-catalysed reactions of polymeric procyanidins with phloroglucinol: Intramolecular rearrangements

    Science.gov (United States)

    Peter E. Laks; Richard W. Hemingway; Anthony H. Conner

    1987-01-01

    Reactions of polymeric procyanidins with phloroglucinol at pH 12.0 and temperatures of 23 or 50°C gave epicatechin-(4β)-phloroglucinol (7), by cleavage of the interflavanoid bond between procyanidin units with subsequent addition of phloroglucinol, and (+)-catechin from the terminal unit. The phloroglucinol adduct (7) rearranged to an enolic form of 8-(3,4-...

  6. Quantum control of the photoinduced Wolff rearrangement of diazonaphthoquinone in the condensed phase

    Energy Technology Data Exchange (ETDEWEB)

    Wolpert, Daniel; Gerber, Gustav; Brixner, Tobias [Physikalisches Institut, Universitaet Wuerzburg, Am Hubland, 97074 Wuerzburg (Germany); Schade, Marco; Langhojer, Florian [Institut fuer Physikalische Chemie, Universitaet Wuerzburg, Am Hubland, 97074 Wuerzburg (Germany)], E-mail: brixner@phys-chemie.uni-wuerzburg.de

    2008-04-14

    A shaped UV pump-MIR probe setup is employed for quantum control of the photoinduced Wolff rearrangement reaction of diazonaphthoquinone (DNQ) dissolved in methanol, yielding a ketene photoproduct. Time-resolved vibrational spectroscopy is a well-suited tool to monitor a photoreaction in the liquid phase as the narrow vibrational lines allow the observation of structural changes. Especially in the mid-infrared region, marker modes originating from different photoproducts can be identified unambiguously providing suitable feedback signals for open-loop or closed-loop control schemes. We report an experiment where the initiation of a complicated structural change of a molecule, involving bond cleavage and rearrangement, in the liquid phase can be controlled and mechanistic insight is obtained. Single-parameter scans show that the molecule is sensitive to intrapulse dumping during the excitation. Adaptive optimizations lead to pulse structures which can be understood consistently with this dumping mechanism.

  7. An order-by-disorder process in the cyclic phase of spin-2 condensate with a weak magnetic field

    International Nuclear Information System (INIS)

    Zheng, Gong-Ping; Xu, Lei-Kuan; Qin, Shuai-Feng; Jian, Wen-Tian; Liang, J.-Q.

    2013-01-01

    We present in this paper a model study on the “order-by-disorder” process in the cyclic phase of spin-2 condensate, which forms a family of incommensurable, spiral degenerate ground states. On the basis of the ordering mechanism of entropic splitting, it is demonstrated that the energy corrections resulting from quantum fluctuations of disorder lift the accidental degeneracy of the cyclic configurations and thus lead to an eventual spiral order called the cyclic order. The order-by-disorder phenomenon is then realized even if the magnetic field exists. Finally, we show that our theoretic observations can be verified experimentally by direct detection of the cyclic order in the 87 Rb condensate of a spin-2 manifold with a weak magnetic field. -- Highlights: •A model for the order-by-disorder process in the cyclic phase of spin-2 condensate is presented. •The second-order quantum fluctuations of the mean-field states are studied. •The energy corrections lift the accidental degeneracy of the cyclic configurations. •The order-by-disorder phenomenon is realized even if a magnetic field exists. •The theoretic observations can be verified experimentally for 87 Rb condensate

  8. Electronically excited and ionized states in condensed phase: Theory and applications

    Science.gov (United States)

    Sadybekov, Arman

    Predictive modeling of chemical processes in silico is a goal of XXI century. While robust and accurate methods exist for ground-state properties, reliable methods for excited states are still lacking and require further development. Electronically exited states are formed by interactions of matter with light and are responsible for key processes in solar energy harvesting, vision, artificial sensors, and photovoltaic applications. The greatest challenge to overcome on our way to a quantitative description of light-induced processes is accurate inclusion of the effect of the environment on excited states. All above mentioned processes occur in solution or solid state. Yet, there are few methodologies to study excited states in condensed phase. Application of highly accurate and robust methods, such as equation-of-motion coupled-cluster theory EOM-CC, is limited by a high computational cost and scaling precluding full quantum mechanical treatment of the entire system. In this thesis we present successful application of the EOM-CC family of methods to studies of excited states in liquid phase and build hierarchy of models for inclusion of the solvent effects. In the first part of the thesis we show that a simple gasphase model is sufficient to quantitatively analyze excited states in liquid benzene, while the latter part emphasizes the importance of explicit treatment of the solvent molecules in the case of glycine in water solution. In chapter 2, we use a simple dimer model to describe exciton formation in liquid and solid benzene. We show that sampling of dimer structures extracted from the liquid benzene is sufficient to correctly predict exited-state properties of the liquid. Our calculations explain experimentally observed features, which helped to understand the mechanism of the excimer formation in liquid benzene. Furthermore, we shed light on the difference between dimer configurations in the first solvation shell of liquid benzene and in unit cell of solid

  9. Extending atomistic scale chemistry to mesoscale model of condensed-phase deflagration

    Science.gov (United States)

    Joshi, Kaushik; Chaudhuri, Santanu

    2017-01-01

    Predictive simulations connecting chemistry that follow the shock or thermal initiation of energetic materials to subsequent deflagration or detonation events is currently outside the realm of possibilities. Molecular dynamics and first-principles based dynamics have made progress in understanding reactions in picosecond to nanosecond time scale. Results from thermal ignition of different phases of RDX show a complex reaction network and emergence of a deterministic behavior for critical temperature before ignition and hot spot growth rates. The kinetics observed is dependent on the hot spot temperature, system size and thermal conductivity. For cases where ignition is observed, the incubation period is dominated by intermolecular and intramolecular hydrogen transfer reactions. The gradual temperature and pressure increase in the incubation period is accompanied by accumulation of heavier polyradicals. The challenge of connecting such chemistry in mesoscale simulations remain in reducing the complexity of chemistry. The hot spot growth kinetics in RDX grains and interfaces is an important challenge for reactive simulations aiming to fill in the gaps in our knowledge in the nanoseconds to microseconds time scale. The results discussed indicate that the mesoscale chemistry may include large polyradical molecules in dense reactive mix reaching an instability point at certain temperatures and pressures.

  10. Sensitive inexpensive spectrophotometric and spectrofluorimetric analysis of ezogabine, levetiracetam and topiramate in tablet formulations using Hantzsch condensation reaction

    Science.gov (United States)

    Ibrahim, F. A.; El-Yazbi, A. F.; Wagih, M. M.; Barary, M. A.

    2017-09-01

    Two highly sensitive, simple and selective spectrophotometric and spectrofluorimetric assays have been investigated for the analysis of ezogabine, levetiracetam and topiramate in their pure and in pharmaceutical dosage forms. The suggested methods depend on the condensation of the primary amino-groups in the three drugs with acetylacetone and formaldehyde according to Hantzsch reaction yielding highly fluorescent yellow colored dihydropyridine derivatives. The reaction products of ezogabine, levetiracetam and topiramate were measured spectrophotometrically at 418, 390 and 380 nm or spectrofluorimetrically at λem/ex of 495/425 nm, 490/415 nm and 488/410 nm, respectively. Various experimental conditions have been carefully studied to maximize the reaction yield. At the optimum reaction conditions, the calibration curves were rectilinear over the concentration ranges of 8-25, 60-180 and 80-200 μg/mL spectrophotometrically and 0.02-0.2, 0.2-1.2 and 0.2-1.5 μg/mL spectrofluorimetrically for ezogabine, levetiracetam and topiramate, respectively with good correlation coefficients. The suggested methods were applied successfully for the analysis of ezogabine, levetiracetam and topiramate in their commercial tablets with high percentage recoveries and negligible interference from various excipients in pharmaceutical dosage forms. The results were statistically analyzed and showed the absence of any significant difference between both developed and published methods. The procedures were validated and evaluated by the ICH guidelines revealing good reproducibility and accuracy. Therefore, the two proposed methods may be considered of high interest for practical and reliable analysis of ezogabine, levetiracetam and topiramate in pharmaceutical dosage forms.

  11. Long-Life, Hydrophilic, Antimicrobial Coating for Condensing Heat Exchangers, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Environmental control systems for manned exploration spacecraft and lunar/planetary bases will need a condensing heat exchanger (CHX) to control humidity in crew...

  12. Crystal phase evolution of TiO2 nanoparticles with reaction time in acidic solutions studied via freeze-drying method

    International Nuclear Information System (INIS)

    Shin, Hyunho; Jung, Hyun Suk; Hong, Kug Sun; Lee, Jung-Kun

    2005-01-01

    The crystal phase evolution of TiO 2 nanoparticles, during hydrolysis and condensation of titanium tetraisopropoxide, was quenched at various reaction times by a freeze-drying method, followed by various characterizations. Three types of solutions with different acid input times were studied: (1) addition in infinite time (no addition) (2) addition at 24h after the hydrolysis/condensation reaction started, and (3) addition from the beginning of the reaction. The acid-free solution yielded amorphous TiO 2 , which transformed to anatase very slowly. The acid input in 24h resulted in a fast transformation of amorphous to a metastable anatase having a highly distorted atomic arrangement: thereby its transformation to a more stable phase, rutile, was suitable. The acid addition from the beginning of the reaction yielded the formation of a relatively stable anatase from the hydrolysis seed, thereby the subsequent transformation to rutile was sluggish

  13. The effect of the number of condensed phases modeled on aerosol behavior during an induced steam generator tube rupture sequence

    International Nuclear Information System (INIS)

    Bixler, N.E.; Schaperow, J.H.

    1998-06-01

    VICTORIA is a mechanistic computer code designed to analyze fission product behavior within a nuclear reactor coolant system (RCS) during a severe accident. It provides detailed predictions of the release of radioactive and nonradioactive materials from the reactor core and transport and deposition of these materials within the RCS. A recently completed independent peer review of VICTORIA, while confirming the overall adequacy of the code, recommended a number of modeling improvements. One of these recommendations, to model three rather than a single condensed phase, is the focus of the work reported here. The recommendation has been implemented as an option so that either a single or three condensed phases can be treated. Both options have been employed in the study of fission product behavior during an induced steam generator tube rupture sequence. Differences in deposition patterns and mechanisms predicted using these two options are discussed

  14. Atomic-phase interference devices based on ring-shaped Bose-Einstein condensates: Two-ring case

    International Nuclear Information System (INIS)

    Anderson, B.P.; Dholakia, K.; Wright, E.M.

    2003-01-01

    We theoretically investigate the ground-state properties and quantum dynamics of a pair of adjacent ring-shaped Bose-Einstein condensates that are coupled via tunneling. This device, which is the analog of a symmetric superconducting quantum interference device, is the simplest version of what we term an atomic-phase interference device (APHID). The two-ring APHID is shown to be sensitive to rotation

  15. Non-Markovian response of ultrafast coherent electronic ring currents in chiral aromatic molecules in a condensed phase

    International Nuclear Information System (INIS)

    Mineo, H.; Lin, S. H.; Fujimura, Y.; Xu, J.; Xu, R. X.; Yan, Y. J.

    2013-01-01

    Results of a theoretical study on non-Markov response for femtosecond laser-driven coherent ring currents in chiral aromatic molecules embedded in a condensed phase are presented. Coherent ring currents are generated by coherent excitation of a pair of quasi-degenerated π-electronic excited states. The coherent electronic dynamical behaviors are strongly influenced by interactions between the electronic system and phonon bath in a condensed phase. Here, the bath correlation time is not instantaneous but should be taken to be a finite time in ultrashort time-resolved experiments. In such a case, Markov approximation breaks down. A hierarchical master equation approach for an improved semiclassical Drude dissipation model was adopted to examine the non-Markov effects on ultrafast coherent electronic ring currents of (P)-2,2 ′ -biphenol in a condensed phase. Time evolution of the coherent ring current derived in the hierarchical master equation approach was calculated and compared with those in the Drude model in the Markov approximation and in the static limit. The results show how non-Markovian behaviors in quantum beat signals of ring currents depend on the Drude bath damping constant. Effects of temperatures on ultrafast coherent electronic ring currents are also clarified

  16. Rotational symmetry breaking and topological phase transition in the exciton-polariton condensate of gapped 2D Dirac material

    Science.gov (United States)

    Lee, Ki Hoon; Lee, Changhee; Jeong, Jae-Seung; Min, Hongki; Chung, Suk Bum

    For the quantum well in an optical microcavity, the interplay of the Coulomb interaction and the electron-photon coupling can lead to the emergence of bosonic quasiparticles consisting of the exciton and the cavity photon known as polariton, which can form the Bose-Einstein condensate above a threshold density. Additional physics due to the nontrivial Berry phase comes into play when the quantum well consists of the gapped Dirac material such as the transition metal dichalcogenide (TMD) MoS2 or WTe2. Specifically, in forming excitons, the electron-photon coupling from the optical selection rule due to the Berry phase competes against, rather than cooperates with, the Coulomb interaction. We find that this competition gives rise to the spontaneous breaking of the rotational symmetry in the polariton condensate and also drives topological phase transition, both novel features in polariton condensation. We also investigate the possible detection of this competition through photoluminescence. This work was supported in part by the Institute for Basic Science of Korea (IBS) under Grant IBS-R009-Y1 and by the National Research Foundation of Korea (NRF) under the Basic Science Research Program Grant No. 2015R1D1A1A01058071.

  17. Plant polyketide synthases: a chalcone synthase-type enzyme which performs a condensation reaction with methylmalonyl-CoA in the biosynthesis of C-methylated chalcones.

    Science.gov (United States)

    Schröder, J; Raiber, S; Berger, T; Schmidt, A; Schmidt, J; Soares-Sello, A M; Bardshiri, E; Strack, D; Simpson, T J; Veit, M; Schröder, G

    1998-06-09

    Heterologous screening of a cDNA library from Pinusstrobus seedlings identified clones for two chalcone synthase (CHS) related proteins (PStrCHS1 and PStrCHS2, 87.6% identity). Heterologous expression in Escherichia coli showed that PStrCHS1 performed the typical CHS reaction, that it used starter CoA-esters from the phenylpropanoid pathway, and that it performed three condensation reactions with malonyl-CoA, followed by the ring closure to the chalcone. PstrCHS2 was completely inactive with these starters and also with linear CoA-esters. Activity was detected only with a diketide derivative (N-acetylcysteamine thioester of 3-oxo-5-phenylpent-4-enoic acid) that corresponded to the CHS reaction intermediate postulated after the first condensation reaction. PstrCHS2 performed only one condensation, with 6-styryl-4-hydroxy-2-pyrone derivatives as release products. The enzyme preferred methylmalonyl-CoA against malonyl-CoA, if only methylmalonyl-CoA was available. These properties and a comparison with the CHS from Pinus sylvestris suggested for PstrCHS2 a special function in the biosynthesis of secondary products. In contrast to P. sylvestris, P. strobus contains C-methylated chalcone derivatives, and the methyl group is at the position predicted from a chain extension with methylmalonyl-CoA in the second condensation of the biosynthetic reaction sequence. We propose that PstrCHS2 specifically contributes the condensing reaction with methylmalonyl-CoA to yield a methylated triketide intermediate. We discuss a model that the biosynthesis of C-methylated chalcones represents the simplest example of a modular polyketide synthase.

  18. Possible mechanism of structural incorporation of Al into diatomite during the deposition process I. Via a condensation reaction of hydroxyl groups.

    Science.gov (United States)

    Liu, Dong; Yu, Wenbin; Deng, Liangliang; Yuan, Weiwei; Ma, Lingya; Yuan, Peng; Du, Peixin; He, Hongping

    2016-01-01

    The structural incorporation of aluminium (Al) into diatomite is investigated by preparing several Al-diatomite composites by loading an Al precursor, hydroxyl aluminum polymer (Al13), onto the surface of diatomite and heating at various temperatures. The results indicate that Al was incorporated and implanted into the structure of diatomite by the condensation reaction of the hydroxyl groups of Al13 and diatomite, and the Si-O-Al(OH) groups were formed during the condensation reaction. Al incorporation by the condensation reaction of hydroxyl groups of Al13 with single silanols of diatomite occurred more readily than that with geminal silanols. The Al incorporation increased solid acidity of diatomite after Al incorporation. The acidity improvement was various for different types of acid sites, depending on the preparation temperature of the Al-incorporated diatomite. Both Brønsted and Lewis acid sites increased greatly after heating at 250 and 350 °C, but only L acid sites significantly improved after heating at 500 °C. These results demonstrate that the structural incorporation of Al(3+) ions into diatomite can occur by the condensation reaction of the hydroxyl groups of the Al precursors and diatomite. Moreover, the rich solid acid sites of Al-incorporated diatomite show its promising application as a solid acid catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Condensed tannins: Base-catalysed reactions of polymeric procyanidins with toluene-α-thiol, liability of the interflavanoid bond and pyran ring

    Science.gov (United States)

    Peter E. Laks; Richard W. Hemingway

    1987-01-01

    Reaction of polymeric procyanidins (condensed tannins) with toluene-α-thiol at pH 12.0 and 23°C gave predominantly one stereoisomer of 1.3-bisbenzylthio-1-(3,4-dihydroxyphenyl)-3-(2,4,6-trihydroxyphenyl) propan-2-ol (10) by stereoselective reaction at C-4 and C-2 of the Quinone methide derived from the upper 2,3-cis procyanidin units....

  20. Performance of a passive emergency heat removal system of advanced reactors in two-phase flow and with high concentration of non-condensable

    International Nuclear Information System (INIS)

    Macedo, Luiz Alberto

    2008-01-01

    The research and the development of passive emergency cooling systems are necessary for the new generation of thermo-nuclear systems. Some basic information on the operation of these systems require the research of some relative processes to the natural circulation, mainly in conditions of two-phase flow involving processes of condensation in the presence of non-condensable gases, because many found situations are new. The experimental facility called Bancada de Circulacao Natural (BCN) was used for the realization of tests with diverse concentrations of non-condensable and power levels. The non-condensable gas present in the circuit decreases the rate of heat transfer for the secondary of the heat exchanger, determining low efficiency of the heat exchanger. High concentration of non-condensable in the vapor condensation, determines negative pressure, and cause the inversion of the flow in the circuit. The initial concentration of non-condensable and the geometry of the circuit, in the inlet of the heat exchanger, determines the establishment of transitory with two-phase flow. The BCN was performed with the computational code of Analysis of Accidents and Thermal-Hydraulics RELAP5/MOD 3.3 and, the calculated values had been compared with the experimental data, presenting good agreement for small non-condensable concentrations. The values calculated for high concentrations of non-condensable had been satisfactory after the circuit to have reached the temperature of saturation in the electric heater. (author)

  1. Nonlinear Optical Spectroscopy in the Time Domain: Studies of Ultrafast Molecular Processes in the Condensed Phase.

    Science.gov (United States)

    Joo, Taiha

    Ultrafast molecular processes in the condensed phase at room temperature are studied in the time domain by four wave mixing spectroscopy. The structure/dynamics of various quantum states can be studied by varying the time ordering of the incident fields, their polarization, their colors, etc. In one, time-resolved coherent Stokes Raman spectroscopy of benzene is investigated at room temperature. The reorientational correlation time of benzene as well as the T_2 time of the nu _1 ring-breathing mode have been measured by using two different polarization geometries. Bohr frequency difference beats have also been resolved between the nu_1 modes of ^ {12}C_6H_6 and ^{12}C_5^{13 }CH_6.. The dephasing dynamics of the nu _1 ring-breathing mode of neat benzene is studied by time-resolved coherent anti-Stokes Raman scattering. Ultrafast time resolution reveals deviation from the conventional exponential decay. The correlation time, tau _{rm c}, and the rms magnitude, Delta, of the Bohr frequency modulation are determined for the process responsible for the vibrational dephasing by Kubo dephasing function analysis. The electronic dephasing of two oxazine dyes in ethylene glycol at room temperature is investigated by photon echo experiments. It was found that at least two stochastic processes are responsible for the observed electronic dephasing. Both fast (homogeneous) and slow (inhomogeneous) dynamics are recovered using Kubo line shape analysis. Moreover, the slow dynamics is found to spectrally diffuse over the inhomogeneous distribution on the time scale around a picosecond. Time-resolved degenerate four wave mixing signal of dyes in a population measurement geometry is reported. The vibrational coherences both in the ground and excited electronic states produced strong oscillations in the signal together with the usual population decay from the excited electronic state. Absolute frequencies and their dephasing times of the vibrational modes at ~590 cm^{-1} are obtained

  2. Solid-phase vibrational redox reactions in coordinated oxides

    International Nuclear Information System (INIS)

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

    1996-01-01

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

  3. Sequential Condensation and Hydrodeoxygenation Reaction of Furfural-Acetone Adduct over Mix Catalysts Ni/SiO2 and Cu/SiO2 in Water

    Directory of Open Access Journals (Sweden)

    Siti Mariyah Ulfa

    2018-05-01

    Full Text Available Sequential condensation and hydrodeoxygenation reaction were perform using autoclave batch reactor in the presence of water as a solvent. The condensation of furfural and acetone was performed using MgO catalyst followed by hydrodeoxygenation using mix catalyst Ni/SiO2 and Cu/SiO2. The catalyst was prepared by wet-impregnation method and analyzed by XRD, SEM-EDX as well as BET surface. Condensation of furfural and acetone in 1:2 mol ratio was carried out by reflux gave 4-(2-furyl-3-buten-2-one and 1,5-bis-(2-furanyl-1,4-pentadien-3-one. The condensation product was then subjected for hydrodeoxygenation using batch reactor, catalyzed by mixed Ni/SiO2 and Cu/SiO2 at 150 and 180 °C for 2 h. The product identified as alkane derivatives with the conversion at 38.83 and 50.35%, respectively. The selectivity of hydrocarbon is 61.39% at 150 °C and 16.55% at 180 °C. Increasing the reaction temperature to 200 °C did not give any products except the recovery of the precursor. It showed that higher temperature enhanced the catalyst activity but the selectivity is controlled by low reaction temperature.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  5. Solid gas reaction phase diagram under high gas pressure

    International Nuclear Information System (INIS)

    Ishizaki, K.

    1992-01-01

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

  6. Experimental phase behavior study of a five-component model gas condensate

    NARCIS (Netherlands)

    Shariati - Sarabi, A.; Straver, E.J.M.; Florusse, L.J.; Peters, C.J.

    2014-01-01

    In this work, the bubble points and dew points of a multicomponent mixture of methane, butane, heptane, decane and tetradecane as a model mixture representative of a gas condensate, have been measured experimentally. Ten samples with approximately the same composition were prepared and their

  7. CFD Modeling of Wall Steam Condensation: Two-Phase Flow Approach versus Homogeneous Flow Approach

    International Nuclear Information System (INIS)

    Mimouni, S.; Mechitoua, N.; Foissac, A.; Hassanaly, M.; Ouraou, M.

    2011-01-01

    The present work is focused on the condensation heat transfer that plays a dominant role in many accident scenarios postulated to occur in the containment of nuclear reactors. The study compares a general multiphase approach implemented in NEPTUNE C FD with a homogeneous model, of widespread use for engineering studies, implemented in Code S aturne. The model implemented in NEPTUNE C FD assumes that liquid droplets form along the wall within nucleation sites. Vapor condensation on droplets makes them grow. Once the droplet diameter reaches a critical value, gravitational forces compensate surface tension force and then droplets slide over the wall and form a liquid film. This approach allows taking into account simultaneously the mechanical drift between the droplet and the gas, the heat and mass transfer on droplets in the core of the flow and the condensation/evaporation phenomena on the walls. As concern the homogeneous approach, the motion of the liquid film due to the gravitational forces is neglected, as well as the volume occupied by the liquid. Both condensation models and compressible procedures are validated and compared to experimental data provided by the TOSQAN ISP47 experiment (IRSN Saclay). Computational results compare favorably with experimental data, particularly for the Helium and steam volume fractions.

  8. Polariton condensation phase diagram in wide-band-gap planar microcavities: GaN versus ZnO

    Science.gov (United States)

    Jamadi, O.; Réveret, F.; Mallet, E.; Disseix, P.; Médard, F.; Mihailovic, M.; Solnyshkov, D.; Malpuech, G.; Leymarie, J.; Lafosse, X.; Bouchoule, S.; Li, F.; Leroux, M.; Semond, F.; Zuniga-Perez, J.

    2016-03-01

    The polariton condensation phase diagram is compared in GaN and ZnO microcavities grown on mesa-patterned silicon substrate. Owing to a common platform, these microcavities share similar photonic properties with large quality factors and low photonic disorder, which makes it possible to determine the optimal spot diameter and to realize a thorough phase diagram study. Both systems have been investigated under the same experimental conditions. The experimental results and the subsequent analysis reveal clearly that longitudinal optical phonons have no influence in the thermodynamic region of the condensation phase diagram, while they allow a strong (slight) decrease of the polariton lasing threshold in the trade-off zone (kinetic region). Phase diagrams are compared with numerical simulations using Boltzmann equations, and are in satisfactory agreement. A lower polariton lasing threshold has been measured at low temperature in the ZnO microcavity, as is expected due to a larger Rabi splitting. This study highlights polariton relaxation mechanisms and their importance in polariton lasing.

  9. Dynamic phase transition in diffusion-limited reactions

    International Nuclear Information System (INIS)

    Tauber, U.C.

    2002-01-01

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

  10. Phase collapse and revival of a 1-mode Bose-Einstein condensate induced by an off-resonant optical probe field and superselection rules

    Science.gov (United States)

    Arruda, L. G. E.; Prataviera, G. A.; de Oliveira, M. C.

    2018-02-01

    Phase collapse and revival for Bose-Einstein condensates are nonlinear phenomena appearing due to atomic collisions. While it has been observed in a general setting involving many modes, for one-mode condensates its occurrence is forbidden by the particle number superselection rule (SSR), which arises because there is no phase reference available. We consider a single mode atomic Bose-Einstein condensate interacting with an off-resonant optical probe field. We show that the condensate phase revival time is dependent on the atom-light interaction, allowing optical control on the atomic collapse and revival dynamics. Incoherent effects over the condensate phase are included by considering a continuous photo-detection over the probe field. We consider conditioned and unconditioned photo-counting events and verify that no extra control upon the condensate is achieved by the probe photo-detection, while further inference of the atomic system statistics is allowed leading to a useful test of the SSR on particle number and its imposition on the kind of physical condensate state.

  11. Water interactions with condensed organic phases: a combined experimental and theoretical study of molecular-level processes

    Science.gov (United States)

    Johansson, Sofia M.; Kong, Xiangrui; Thomson, Erik S.; Papagiannakopoulos, Panos; Pettersson, Jan B. C.; Lovrić, Josip; Toubin, Céline

    2016-04-01

    Water uptake on aerosol particles modifies their chemistry and microphysics with important implications for air quality and climate. A large fraction of the atmospheric aerosol consists of organic aerosol particles or inorganic particles with condensed organic components. Here, we combine laboratory studies using the environmental molecular beam (EMB) method1 with molecular dynamics (MD) simulations to characterize water interactions with organic surfaces in detail. The over-arching aim is to characterize the mechanisms that govern water uptake, in order to guide the development of physics-based models to be used in atmospheric modelling. The EMB method enables molecular level studies of interactions between gases and volatile surfaces at near ambient pressure,1 and the technique may provide information about collision dynamics, surface and bulk accommodation, desorption and diffusion kinetics. Molecular dynamics simulations provide complementary information about the collision dynamics and initial interactions between gas molecules and the condensed phase. Here, we focus on water interactions with condensed alcohol phases that serve as highly simplified proxies for systems in the environment. Gas-surface collisions are in general found to be highly inelastic and result in efficient surface accommodation of water molecules. As a consequence, surface accommodation of water can be safely assumed to be close to unity under typical ambient conditions. Bulk accommodation is inefficient on solid alcohol and the condensed materials appear to produce hydrophobic surface structures, with limited opportunities for adsorbed water to form hydrogen bonds with surface molecules. Accommodation is significantly more efficient on the dynamic liquid alcohol surfaces. The results for n-butanol (BuOH) are particularly intriguing where substantial changes in water accommodation taking place over a 10 K interval below and above the BuOH melting point.2 The governing mechanisms for the

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

    International Nuclear Information System (INIS)

    Strickert, R.G.

    1976-01-01

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

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

    DEFF Research Database (Denmark)

    Østberg, Martin

    1996-01-01

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

  14. Statistical quantization of GUT models and phase diagrams of W condensation for the Universe with finite fermion density

    International Nuclear Information System (INIS)

    Kalashnikov, O.K.; Razumov, L.V.; Perez Rojas, H.

    1990-01-01

    The problems of statistical quantization for grand-unified-theory models are studied using as an example the Weinberg-Salam model with finite fermion density under the conditions of neutral and electric charge conservation. The relativistic R γ gauge with an arbitrary parameter is used and the one-loop effective potential together with its extremum equations are found. We demonstrate (and this is our main result) that the thermodynamic potential obtained from the effective one, after the mass shell for ξ is used, remains gauge dependent if all temperature ranges (not only the leading high-temperature terms) are considered. The contradiction detected within the calculational scheme is eliminated after the redefinition of the model studied is made with the aid of the terms which are proportional to the ''non-Abelian'' chemical potential and equal to zero identically when the unitary gauge is fixed. The phase diagrams of the W condensation are established and all their peculiarities are displayed. We found for the universe with a zero neutral charge density that the W condensate occurs at any small fermion density ρ and appears at first near the point of symmetry restoration. For all ρ≠0 this condensate exists only in the finite-temperature domain and evaporates completely or partially when T goes to zero

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

    Science.gov (United States)

    Gordon, Robert J; Barge, Vishal J

    2007-11-28

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

  16. The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates.

    Science.gov (United States)

    Powers, Anna; Scribano, Yohann; Lauvergnat, David; Mebe, Elsy; Benoit, David M; Bačić, Zlatko

    2018-04-14

    We report a theoretical study of the frequency shift (redshift) of the stretching fundamental transition of an H 2 molecule confined inside the small dodecahedral cage of the structure II clathrate hydrate and its dependence on the condensed-phase environment. In order to determine how much the hydrate water molecules beyond the confining small cage contribute to the vibrational frequency shift, quantum five-dimensional (5D) calculations of the coupled translation-rotation eigenstates are performed for H 2 in the v=0 and v=1 vibrational states inside spherical clathrate hydrate domains of increasing radius and a growing number of water molecules, ranging from 20 for the isolated small cage to over 1900. In these calculations, both H 2 and the water domains are treated as rigid. The 5D intermolecular potential energy surface (PES) of H 2 inside a hydrate domain is assumed to be pairwise additive. The H 2 -H 2 O pair interaction, represented by the 5D (rigid monomer) PES that depends on the vibrational state of H 2 , v=0 or v=1, is derived from the high-quality ab initio full-dimensional (9D) PES of the H 2 -H 2 O complex [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)]. The H 2 vibrational frequency shift calculated for the largest clathrate domain considered, which mimics the condensed-phase environment, is about 10% larger in magnitude than that obtained by taking into account only the small cage. The calculated splittings of the translational fundamental of H 2 change very little with the domain size, unlike the H 2 j = 1 rotational splittings that decrease significantly as the domain size increases. The changes in both the vibrational frequency shift and the j = 1 rotational splitting due to the condensed-phase effects arise predominantly from the H 2 O molecules in the first three complete hydration shells around H 2 .

  17. The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates

    Science.gov (United States)

    Powers, Anna; Scribano, Yohann; Lauvergnat, David; Mebe, Elsy; Benoit, David M.; Bačić, Zlatko

    2018-04-01

    We report a theoretical study of the frequency shift (redshift) of the stretching fundamental transition of an H2 molecule confined inside the small dodecahedral cage of the structure II clathrate hydrate and its dependence on the condensed-phase environment. In order to determine how much the hydrate water molecules beyond the confining small cage contribute to the vibrational frequency shift, quantum five-dimensional (5D) calculations of the coupled translation-rotation eigenstates are performed for H2 in the v =0 and v =1 vibrational states inside spherical clathrate hydrate domains of increasing radius and a growing number of water molecules, ranging from 20 for the isolated small cage to over 1900. In these calculations, both H2 and the water domains are treated as rigid. The 5D intermolecular potential energy surface (PES) of H2 inside a hydrate domain is assumed to be pairwise additive. The H2-H2O pair interaction, represented by the 5D (rigid monomer) PES that depends on the vibrational state of H2, v =0 or v =1 , is derived from the high-quality ab initio full-dimensional (9D) PES of the H2-H2O complex [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)]. The H2 vibrational frequency shift calculated for the largest clathrate domain considered, which mimics the condensed-phase environment, is about 10% larger in magnitude than that obtained by taking into account only the small cage. The calculated splittings of the translational fundamental of H2 change very little with the domain size, unlike the H2 j = 1 rotational splittings that decrease significantly as the domain size increases. The changes in both the vibrational frequency shift and the j = 1 rotational splitting due to the condensed-phase effects arise predominantly from the H2O molecules in the first three complete hydration shells around H2.

  18. Integration of gas phase condensed nanoparticles in YBa_2Cu_3O_7_-_δ multilayers

    International Nuclear Information System (INIS)

    Sparing, Maria

    2012-01-01

    The control and targeted variation of nanoparticles properties is a central challenge in research on particle induced defects in YBa_2Cu_3O_7_-_δ. Using a combined Sputter-PLD system with inert gas condensation particle size and density integrated into the YBCO multilayers were varied independently. The cooling process influences the electrical properties of the multilayers. The effect of HfO2 and FePt nanoparticles on the structural and electrical properties was studied.

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

    DEFF Research Database (Denmark)

    Wang, Yuanyuan

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

  20. Numerical Method based on SIMPLE Algorithm for a Two-Phase Flow with Non-condensable Gas

    International Nuclear Information System (INIS)

    Kim, Jong Tae

    2009-08-01

    In this study, a numerical method based on SIMPLE algorithm for a two-phase flow with non-condensable gas has been developed in order to simulate thermal hydraulics in a containment of a nuclear power plant. As governing equations, it adopts a two-fluid three-field model for the two-phase flows. The three fields include gas, drops, and continuous liquid. The gas field can contains vapor and non-condensable gases such as air and hydrogen. In order to resolve mixing phenomena of gas species, gas transport equations for each species base on the gas mass fractions are solved with gas phase governing equations such as mass, momentum and energy equations. Methods to evaluate the properties of the gas species were implemented in the code. They are constant or polynomial function based a user input and a property library from Chemkin and JANAF table for gas specific heat. Properties for the gas mixture which are dependent on mole fractions of the gas species were evaluated by a mix rule

  1. Vortex-induced phase slip dissipation in a torioidal Bose-Einstein condensate flowing through a barrier

    Energy Technology Data Exchange (ETDEWEB)

    Collins, Lee A [Los Alamos National Laboratory

    2009-01-01

    We study the phase slips superfluid dissipation mechanism with a BEC flowing through a repulsive barrier inside a torus. The barrier is adiabatically raised across the annulus while the condensate is flowing with a finite quantized angular momentum. We found that, at a critical height, a vortex reaches the barrier moving radially from the inner region to eventually circulate along the annulus. At a slightly higher barrier, an anti-vortex also enters into the annulus from the outward region. The vortex and anti-vortex decrease the total angular momentum by leaving behind their respective paths a 2{pi} phase slip. When they collide or orbit along the same loop, the condensate suffers a global 2{pi} phase slip and the total angular momentum decreases by one quantum. The analysis is based on numerical simulations of the dynamical Gross-Pitaevskii equation both in two- and three-dimensions, the latter with the experimental parameters of the torus trap recently created at the NIST institute.

  2. Quantum chemical approach for condensed-phase thermochemistry (V): Development of rigid-body type harmonic solvation model

    Science.gov (United States)

    Tarumi, Moto; Nakai, Hiromi

    2018-05-01

    This letter proposes an approximate treatment of the harmonic solvation model (HSM) assuming the solute to be a rigid body (RB-HSM). The HSM method can appropriately estimate the Gibbs free energy for condensed phases even where an ideal gas model used by standard quantum chemical programs fails. The RB-HSM method eliminates calculations for intra-molecular vibrations in order to reduce the computational costs. Numerical assessments indicated that the RB-HSM method can evaluate entropies and internal energies with the same accuracy as the HSM method but with lower calculation costs.

  3. EncM, a versatile enterocin biosynthetic enzyme involved in Favorskii oxidative rearrangement, aldol condensation, and heterocycle-forming reactions

    Science.gov (United States)

    Xiang, Longkuan; Kalaitzis, John A.; Moore, Bradley S.

    2004-01-01

    The bacteriostatic natural product enterocin from the marine microbe “Streptomyces maritimus” has an unprecedented carbon skeleton that is derived from an aromatic polyketide biosynthetic pathway. Its caged tricyclic, nonaromatic core is derived from a linear poly-β-ketide precursor that formally undergoes a Favorskii-like oxidative rearrangement. In vivo characterization of the gene encM through mutagenesis and heterologous biosynthesis demonstrated that its protein product not only is solely responsible for the oxidative C—C rearrangement, but also facilitates two aldol condensations plus two heterocycle forming reactions. In total, at least five chiral centers and four rings are generated by this multifaceted flavoprotein. Heterologous expression of the enterocin biosynthesis genes encABCDLMN in Streptomyces lividans resulted in the formation of the rearranged metabolite desmethyl-5-deoxyenterocin and the shunt products wailupemycins D-G. Addition of the methyltransferase gene encK, which was previously proposed through mutagenesis to additionally assist EncM in the Favorskii rearrangement, shifted the production to the O-methyl derivative 5-deoxyenterocin. The O-methyltransferase EncK seems to be specific for the pyrone ring of enterocin, because bicyclic polyketides bearing pyrone rings are not methylated in vivo. Expression of encM with different combinations of homologous actinorhodin biosynthesis genes did not result in the production of oxidatively rearranged enterocin-actinorhodin hybrid compounds as anticipated, suggesting that wild-type EncM may be specific for its endogenous type II polyketide synthase or for benzoyl-primed polyketide precursors. PMID:15505225

  4. NUMERICAL TECHNIQUES TO SOLVE CONDENSATIONAL AND DISSOLUTIONAL GROWTH EQUATIONS WHEN GROWTH IS COUPLED TO REVERSIBLE REACTIONS (R823186)

    Science.gov (United States)

    Noniterative, unconditionally stable numerical techniques for solving condensational anddissolutional growth equations are given. Growth solutions are compared to Gear-code solutions forthree cases when growth is coupled to reversible equilibrium chemistry. In all cases, ...

  5. Dynamics of the formation of the condensed phase particles at detonation of high explosives

    CERN Document Server

    Evdokov, O V; Kulipanov, G N; Luckjanchikov, L A; Lyakhov, N Z; Mishnev, S I; Sharafutdinov, M R; Sheromov, M A; Ten, K A; Titov, V M; Tolochko, B P; Zubkov, P I

    2001-01-01

    The article presents the results of the experimental study SAXS on condensed carbon particles that appear at the detonation of a high explosive. It was shown that the SAXS signal rises for 1.5-4 mu s after the detonation front passing. The SAXS signal in trotyl and its alloys with hexogen starts just after the compression of the material in the detonation wave. In octogen, hexogen and PETN, the SAXS signal appears in 0.5 mu s and is much smaller than the signal at the detonation of trotyl and its alloys with hexogen.

  6. Theoretical Studies on Expressions of Condensed-Phase Photoionization Cross Section

    International Nuclear Information System (INIS)

    Ma Xiaoguang; Wang Meishan; Wang Dehua; Qu Zhaojun

    2006-01-01

    A set of general expressions for photoionization cross sections of atoms or molecules embedded in a medium and a dielectric influence function are derived based on Maxwell's equations and the Beer-Lambert's law in this work. The applications are performed for the photoionization process of solid gold both in the Clausius-Mossotti (virtual cavity) model and the Glauber-Lewenstein (real cavity) model firstly. The results show that the present theoretical expressions of photoionization cross section can be used to describe the photoionization process of atoms in condensed matter properly.

  7. Macroscopic self-trapping in Bose-Einstein condensates: Analysis of a dynamical quantum phase transition

    International Nuclear Information System (INIS)

    Julia-Diaz, B.; Dagnino, D.; Martorell, J.; Polls, A.; Lewenstein, M.

    2010-01-01

    We consider a Bose-Einstein condensate in a double-well potential undergoing a dynamical transition from the regime of Josephson oscillations to the regime of self-trapping. We analyze the statistical properties of the ground state (or the highest excited state) of the Hamiltonian in these two regimes for attractive (repulsive) interactions. We demonstrate that it is impossible to describe the transition within the mean-field theory. In contrast, the transition proceeds through a strongly correlated delocalized state, with large quantum fluctuations, and spontaneous breaking of the symmetry.

  8. Two-phase pressurized thermal shock investigations using a 3D two-fluid modeling of stratified flow with condensation

    International Nuclear Information System (INIS)

    Yao, W.; Coste, P.; Bestion, D.; Boucker, M.

    2003-01-01

    In this paper, a local 3D two-fluid model for a turbulent stratified flow with/without condensation, which can be used to predict two-phase pressurized thermal shock, is presented. A modified turbulent K- model is proposed with turbulence production induced by interfacial friction. A model of interfacial friction based on a interfacial sublayer concept and three interfacial heat transfer models, namely, a model based on the small eddies controlled surface renewal concept (HDM, Hughes and Duffey, 1991), a model based on the asymptotic behavior of the Eddy Viscosity (EVM), and a model based on the Interfacial Sublayer concept (ISM) are implemented into a preliminary version of the NEPTUNE code based on the 3D module of the CATHARE code. As a first step to apply the above models to predict the two-phase thermal shock, the models are evaluated by comparison of calculated profiles with several experiments: a turbulent air-water stratified flow without interfacial heat transfer; a turbulent steam-water stratified flow with condensation; turbulence induced by the impact of a water jet in a water pool. The prediction results agree well with the experimental data. In addition, the comparison of three interfacial heat transfer models shows that EVM and ISM gave better prediction results while HDM highly overestimated the interfacial heat transfers compared to the experimental data of a steam water stratified flow

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

    KAUST Repository

    Ma, Ting

    2011-03-09

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

  10. Influence of phase transition on pattern formation during catalytic reactions

    OpenAIRE

    Andrade, Roberto Fernandes Silva; Lima, D.; Cunha, F. B.

    2000-01-01

    p.434–445 We investigate the influence of the order of surface phase transitions on pattern formation during chemical reaction on mono-crystal catalysts. We use a model consisting of two partial differential equations, one of which describes the dynamics of the surface state with the help of a Ginzburg–Landau potential. Second- or first-order transitions are described by decreasing or increasing the relative value of the third-order coefficient of the potential. We concentrate on the stabi...

  11. Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines

    Science.gov (United States)

    Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.

    2017-09-01

    Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.

  12. One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

    KAUST Repository

    Wang, Xinbo

    2015-11-06

    A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction discovered, a new synthetic proposal for Fumitremorgin A and Verruculogen is introduced. Such a protocol could be easily handled and scaled up in an open atmosphere with a wide substrate scope, enabling the construction of a new molecule library.

  13. Interfacial Instability in Two-Phase Flow: Manipulating Coalescence and Condensation

    Data.gov (United States)

    National Aeronautics and Space Administration — Two-phase flow under microgravity conditions presents a number of technical challenges ( and ). Life support and habitation depend on systems that use two-phase flow...

  14. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Failor, R.A.

    1989-01-01

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

  15. Reactions homogenes en phase gazeuse dans les lits fluidises

    Science.gov (United States)

    Laviolette, Jean-Philippe

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

  16. PRR11 regulates late-S to G2/M phase progression and induces premature chromatin condensation (PCC)

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chundong; Zhang, Ying; Li, Yi; Zhu, Huifang; Wang, Yitao; Cai, Wei [Department of Biochemistry and Molecular Biology, Chongqing Medical University, Chongqing 400016 (China); Molecular Medicine and Cancer Research Center, Chongqing Medical University, Chongqing 400016 (China); Zhu, Jiang [Molecular Medicine and Cancer Research Center, Chongqing Medical University, Chongqing 400016 (China); Ozaki, Toshinori [Laboratory of DNA Damage Signaling, Chiba Cancer Center Research Institute, 666-2 Nitona, Chuohku, Chiba 260-8717 (Japan); Bu, Youquan, E-mail: buyqcn@aliyun.com [Department of Biochemistry and Molecular Biology, Chongqing Medical University, Chongqing 400016 (China); Molecular Medicine and Cancer Research Center, Chongqing Medical University, Chongqing 400016 (China)

    2015-03-13

    Recently, we have demonstrated that proline-rich protein 11 (PRR11) is a novel tumor-related gene product likely implicated in the regulation of cell cycle progression as well as lung cancer development. However, its precise role in cell cycle progression remains unclear. In the present study, we have further investigated the expression pattern and functional implication of PRR11 during cell cycle in detail in human lung carcinoma-derived H1299 cells. According to our immunofluorescence study, PRR11 was expressed largely in cytoplasm, the amount of PRR11 started to increase in the late S phase, and was retained until just before mitotic telophase. Consistent with those observations, siRNA-mediated knockdown of PRR11 caused a significant cell cycle arrest in the late S phase. Intriguingly, the treatment with dNTPs further augmented PRR11 silencing-mediated S phase arrest. Moreover, knockdown of PRR11 also resulted in a remarkable retardation of G2/M progression, and PRR11-knockdown cells subsequently underwent G2 phase cell cycle arrest accompanied by obvious mitotic defects such as multipolar spindles and multiple nuclei. In addition, forced expression of PRR11 promoted the premature Chromatin condensation (PCC), and then proliferation of PRR11-expressing cells was massively attenuated and induced apoptosis. Taken together, our current observations strongly suggest that PRR11, which is strictly regulated during cell cycle progression, plays a pivotal role in the regulation of accurate cell cycle progression through the late S phase to mitosis. - Highlights: • PRR11 started to increase in the late S phase and was retained until just before mitotic telophase. • PRR11-knockdown caused a significant cell cycle arrest in the late S phase and G2 phase. • The treatment with dNTPs further augmented PRR11 silencing-mediated S phase arrest. • PRR11-knockdown led to multipolar spindles and multiple nuclei. • Forced expression of PRR11 promoted the PCC and inhibited

  17. PRR11 regulates late-S to G2/M phase progression and induces premature chromatin condensation (PCC)

    International Nuclear Information System (INIS)

    Zhang, Chundong; Zhang, Ying; Li, Yi; Zhu, Huifang; Wang, Yitao; Cai, Wei; Zhu, Jiang; Ozaki, Toshinori; Bu, Youquan

    2015-01-01

    Recently, we have demonstrated that proline-rich protein 11 (PRR11) is a novel tumor-related gene product likely implicated in the regulation of cell cycle progression as well as lung cancer development. However, its precise role in cell cycle progression remains unclear. In the present study, we have further investigated the expression pattern and functional implication of PRR11 during cell cycle in detail in human lung carcinoma-derived H1299 cells. According to our immunofluorescence study, PRR11 was expressed largely in cytoplasm, the amount of PRR11 started to increase in the late S phase, and was retained until just before mitotic telophase. Consistent with those observations, siRNA-mediated knockdown of PRR11 caused a significant cell cycle arrest in the late S phase. Intriguingly, the treatment with dNTPs further augmented PRR11 silencing-mediated S phase arrest. Moreover, knockdown of PRR11 also resulted in a remarkable retardation of G2/M progression, and PRR11-knockdown cells subsequently underwent G2 phase cell cycle arrest accompanied by obvious mitotic defects such as multipolar spindles and multiple nuclei. In addition, forced expression of PRR11 promoted the premature Chromatin condensation (PCC), and then proliferation of PRR11-expressing cells was massively attenuated and induced apoptosis. Taken together, our current observations strongly suggest that PRR11, which is strictly regulated during cell cycle progression, plays a pivotal role in the regulation of accurate cell cycle progression through the late S phase to mitosis. - Highlights: • PRR11 started to increase in the late S phase and was retained until just before mitotic telophase. • PRR11-knockdown caused a significant cell cycle arrest in the late S phase and G2 phase. • The treatment with dNTPs further augmented PRR11 silencing-mediated S phase arrest. • PRR11-knockdown led to multipolar spindles and multiple nuclei. • Forced expression of PRR11 promoted the PCC and inhibited

  18. Bose-Einstein condensation and long-range phase coherence in the many-particle Schroedinger wave function

    International Nuclear Information System (INIS)

    Mayers, J.

    2001-01-01

    The properties of the many-particle Schroedinger wave function Ψ are examined in the presence of Bose-Einstein condensation (BEC). It is shown that it is possible to define, in terms of Ψ, a function ψ(r-vector vertical bar s-vector), which can be regarded as the single-particle wave function of an arbitrary particle for a fixed configuration s-vector of all other particles. It is shown that ψ(r-vector|s-vector) plays an analogous role to the field operator of standard field-theoretical treatments of superfluidity. It is shown that in the presence of a Bose-Einstein condensate fraction f, ψ(r-vector|s-vector) must be nonzero and phase coherent within at least a fraction f of the total volume of the N-particle system for essentially all s-vector. Examination of the form of variational many-particle wave functions shows that in liquid 4 He, ψ(r-vector|s-vector) extends throughout the spaces left between the hard cores of the other atoms at s-vector. By contrast, in the absence of BEC, ψ(r-vector|s-vector) in the ground state must be nonzero only over a localized region of space. It is shown that in order for long-range phase coherence in ψ(r-vector|s-vector) to be maintained in the presence of velocity fields, any circulation must be quantized over macroscopic length scales. Some numerical calculations of the properties and fluctuations of liquid helium are presented. These suggest that the approach outlined in this paper may have significant advantages for the numerical calculations of the properties of Bose-Einstein condensed systems. The properties of ψ(r-vector|s-vector) are used to show that there is no general connection between the static structure factor and the size of the Bose-Einstein condensate fraction in a Bose fluid. It is suggested that the observed connection in liquid 4 He is due to the creation of vacancies in the liquid structure, which are required so that ψ(r-vector vertical bar s-vector) can delocalize, in the presence of hard

  19. Interconversion of pollutants from the gaseous to the condensed phase. Technical progress report - brief summary of recent findings, March 1, 1983-August 31, 1983

    International Nuclear Information System (INIS)

    1983-01-01

    Purpose of the studies were to provide new information on the interconversion of pollutants from the gaseous to the condensed phase. More information were obtained on mechanisms of cluster formation, leading to the production of prenucleation embryos, rates of phase transformation, and the thermochemical properties and photochemical stability of the species involved. Systems studied included nitric acid, ammonia, sulfuric acid, carbonic acid, etc

  20. Population and phase dynamics of F=1 spinor condensates in an external magnetic field

    International Nuclear Information System (INIS)

    Romano, D.R.; Passos, E.J.V. de

    2004-01-01

    We show that the classical dynamics underlying the mean-field description of homogeneous mixtures of spinor F=1 Bose-Einstein condensates in an external magnetic field is integrable as a consequence of number conservation and axial symmetry in spin space. The population dynamics depends only on the quadratic term of the Zeeman energy and on the strength of the spin-dependent term of the atom-atom interaction. We determine the equilibrium populations as function of the ratio of these two quantities and the miscibility of the hyperfine components in the ground state spinors are thoroughly discussed. Outside the equilibrium, the populations are always a periodic function of time where the periodic motion can be a libration or a rotation. Our studies also indicate the absence of metastability

  1. Acute and "chronic" phase reaction-a mother of disease.

    Science.gov (United States)

    Bengmark, Stig

    2004-12-01

    The world is increasingly threatened by a global epidemic of chronic diseases. Almost half of the global morbidity and almost two thirds of global mortality is due to these diseases-approximately 35 million die each year from chronic diseases. And they continue to increase. Increasing evidence suggest that these diseases are associated with lifestyle, stress, lack of physical exercise, over-consumption of calorie-condensed foods rich in saturated fat, sugar and starch, but also under-consumption of antioxidant-rich fruits and vegetables. As a result the function of the innate immune system is severe impaired. This review discusses the changes induced in response to mental and physical stress and their association with the subsequent development of metabolic syndrome, and its association with various chronic diseases. The endothelial cells and their function appears to be of great importance, and the function of their cellular membranes of special importance to the function of the underlying cells; their ability to obtain nutrients and antioxidants and to eliminate waste products. The abdominal adipocytes seen to play a key role, as they have the ability to in stressful situations release much of proinflammatory cytokines, PAI-1 and free fatty acids compared to elsewhere in the body. The load on the liver of these various substances in often of greater magnitude than the liver can handle. Some of the most common chronic diseases and their potential association with acute and "chronic" phase response, and with metabolic syndrome are discussed separately. The need for studies with lifestyle modifications is especially emphasized.

  2. Transport-induced shifts in condensate dew-point and composition in multicomponent systems with chemical reaction

    Science.gov (United States)

    Rosner, D. E.; Nagarajan, R.

    1985-01-01

    Partial heterogeneous condensation phenomena in multicomponent reacting systems are analyzed taking into consideration the chemical element transport phenomena. It is demonstrated that the dew-point surface temperature in chemically reactive systems is not a purely thermodynamic quantity, but is influenced by the multicomponent diffusion and Soret-mass diffusion phenomena. Several distinct dew-points are shown to exist in such systems and, as a result of transport constraints, the 'sharp' locus between two chemically distinct condensates is systematically moved to a difference mainstream composition.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-02-01

    temperature or below. For many spectroscopic measurements, low temperatures have been achieved by co-condensing the actinide vapor in rare gas or inert molecule host matrices. Spectra recorded in matrices are usually considered to be minimally perturbed. Trapping the products from gas-phase reactions that occur when trace quantities of reactants are added to the inert host gas has resulted in the discovery of many new actinide species. Selected aspects of the matrix isolation data were discussed in chapter 17. In the present chapter we review the spectroscopic matrix data in terms of its relationship to gas-phase measurements, and update the description of the new reaction products found in matrices to reflect the developments that have occurred during the past two years. Spectra recorded in matrix environments are usually considered to be minimally perturbed, and this expectation is borne out for many closed shell actinide molecules. However, there is growing evidence that significant perturbations can occur for open shell molecules, resulting in geometric distortions and/or electronic state reordering. Studies of actinide reactions in the gas phase provide an opportunity to probe the relationship between electronic structure and reactivity. Much of this work has focused on the reactions of ionic species, as these may be selected and controlled using various forms of mass spectrometry. As an example of the type of insight derived from reaction studies, it has been established that the reaction barriers for An+ ions are determined by the promotion energies required to achieve the 5fn6d7s configuration. Gas-phase reaction studies also provide fundamental thermodynamic properties such as bond dissociation and ionization energies. In recent years, an increased number of gas-phase ion chemistry studies of bare (atomic) and ligated (molecular) actinide ions have appeared, in which relevant contributions to fundamental actinide chemistry have been made. These studies were initiated

  4. Behavior of the antiferromagnetic phase transition near the fermion condensation quantum phase transition in YbRh{sub 2}Si{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Shaginyan, V.R., E-mail: vrshag@thd.pnpi.spb.r [Petersburg Nuclear Physics Institute, RAS, Gatchina 188300 (Russian Federation); Racah Institute of Physics, Hebrew University, Jerusalem 91904 (Israel); Amusia, M.Ya. [Racah Institute of Physics, Hebrew University, Jerusalem 91904 (Israel); Popov, K.G. [Komi Science Center, Ural Division, RAS, Syktyvkar 167982 (Russian Federation)

    2010-01-11

    Low-temperature specific-heat measurements on YbRh{sub 2}Si{sub 2} at the second order antiferromagnetic (AF) phase transition reveal a sharp peak at T{sub N}=72 mK. The corresponding critical exponent alpha turns out to be alpha=0.38, which differs significantly from that obtained within the framework of the fluctuation theory of second order phase transitions based on the scale invariance, where alphaapprox =0.1. We show that under the application of magnetic field the curve of the second order AF phase transitions passes into a curve of the first order ones at the tricritical point leading to a violation of the critical universality of the fluctuation theory. This change of the phase transition is generated by the fermion condensation quantum phase transition. Near the tricritical point the Landau theory of second order phase transitions is applicable and gives alphaapprox =1/2. We demonstrate that this value of alpha is in good agreement with the specific-heat measurements.

  5. Structure and dynamics of molecular complex He2*(a3Σu+) in condensed phases of helium

    International Nuclear Information System (INIS)

    Kafanov, S.G.; Parshin, A.Ya.; Tadoshchenko, I.A.

    2000-01-01

    The absorption spectra of the helium triplet metastable molecules in the a 3 Σ u + states in the liquid 4 He and 3 He by various pressures and in the 3 He dense gas are studied. The analysis of the spectrum, corresponding to the a 3 Σ u + → c 3 Σ g + transition, proves the conclusion on the availability of a microscopic bubble, surrounding the molecule in the liquid helium. Simple approximation of the wave function of the molecule valent electron is proposed and the bubble parameters under various experimental conditions are determined. The coefficient conditions are determined. The coefficient of the molecular recombination in the liquid 3 He and 4 He by different pressures and in the 3 He cold gas is experimentally determined. The obtained results agree well with the mutual recombination theory. It is shown, that molecular polarization in the helium condensed phases under the magnetic field effect does not lead to their mutual recombination [ru

  6. A new linearized theory of laminar film condensation of two phase annular flow in a capillary pumped loop

    Science.gov (United States)

    Hsu, Y. K.; Swanson, T.; Mcintosh, R.

    1988-01-01

    Future large space based facilities, such as Space Station, will require energy management systems capable of transporting tens of kilowatts of heat over a hundred meters or more. This represents better than an order of magnitude improvement over current technology. Two-phase thermal systems are currently being developed to meet this challenge. Condensation heat transfer plays a very important role in this system. The present study attempts an analytic solution to the set of linearized partial differential equations. The axial velocity and temperature functions were found to be Bessel functions which have oscillatory behavior. This result agrees qualitatively with the experimental evidence from tests at both NASA Goddard Space Flight Center and elsewhere.

  7. Theory of high-T sub c superconductivity based on the fermion-condensation quantum phase transition

    CERN Document Server

    Amusia, M Ya; Shaginyan, V R

    2001-01-01

    A theory of high temperature superconductivity based on the combination of the fermion-condensation quantum phase transition and the conventional theory of superconductivity is presented. This theory describes maximum values of the superconducting gap which can be as big as DELTA sub 1 approx 0.1 epsilon sub F , with epsilon sub F being the Fermi level. It is shown that the critical temperature 2T sub c approx = DELTA sub 1. If there exists the pseudogap above T sub c then 2T* approx = DELTA sub 1 , and T* is the temperature at which the pseudogap vanished. A discontinuity in the specific heat at T sub c is calculated. The transition from conventional superconductors to high-T sub c ones as a function of the doping level is investigated

  8. Phase-equilibria for design of coal-gasification processes: dew points of hot gases containing condensible tars. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Prausnitz, J.M.

    1980-05-01

    This research is concerned with the fundamental physical chemistry and thermodynamics of condensation of tars (dew points) from the vapor phase at advanced temperatures and pressures. Fundamental quantitative understanding of dew points is important for rational design of heat exchangers to recover sensible heat from hot, tar-containing gases that are produced in coal gasification. This report includes essentially six contributions toward establishing the desired understanding: (1) Characterization of Coal Tars for Dew-Point Calculations; (2) Fugacity Coefficients for Dew-Point Calculations in Coal-Gasification Process Design; (3) Vapor Pressures of High-Molecular-Weight Hydrocarbons; (4) Estimation of Vapor Pressures of High-Boiling Fractions in Liquefied Fossil Fuels Containing Heteroatoms Nitrogen or Sulfur; and (5) Vapor Pressures of Heavy Liquid Hydrocarbons by a Group-Contribution Method.

  9. Non-invasive, kinetic measurements of [3H]nitrendipine binding to isolated rat myocytes by condensed phase radioluminescence

    International Nuclear Information System (INIS)

    Tscharner, V. von; Bailey, I.A.

    1983-01-01

    The binding of 3 H-labelled drug molecules to membranes of living cells give rise to photon emission from tryptophan residues at proteinaceous binding sites. This phenomenon, called condensed phase radioluminescence, has been used to measure non-invasively the kinetics of [ 3 H]nitrendipine binding and dissociation on the same samples of cultured beating cardiac myocytes. Signal arose only from bound drug molecules. Binding was monoexponential (tau = 5.5 min) as was dissociation (14.3 min). Preincubating cells with non-radioactive nifedipine reduced the amplitude and rate of [ 3 H]nitrendipine but not of [ 3 H]dihydroalprenolol binding. The potential uses of this phenomenon are discussed. (Auth.)

  10. Defect formation in fluoropolymer films at their condensation from a gas phase

    Science.gov (United States)

    Luchnikov, P. A.

    2018-01-01

    The questions of radiation defects, factors of influence of electronic high-frequency discharge plasma components on the molecular structure and properties of the fluoropolymer vacuum films synthesized on a substrate from a gas phase are considered. It is established that at sedimentation of fluoropolymer coverings from a gas phase in high-frequency discharge plasma in films there are radiation defects in molecular and supramolecular structure because of the influence of active plasma components which significantly influence their main properties.

  11. Communication: On the consistency of approximate quantum dynamics simulation methods for vibrational spectra in the condensed phase.

    Science.gov (United States)

    Rossi, Mariana; Liu, Hanchao; Paesani, Francesco; Bowman, Joel; Ceriotti, Michele

    2014-11-14

    Including quantum mechanical effects on the dynamics of nuclei in the condensed phase is challenging, because the complexity of exact methods grows exponentially with the number of quantum degrees of freedom. Efforts to circumvent these limitations can be traced down to two approaches: methods that treat a small subset of the degrees of freedom with rigorous quantum mechanics, considering the rest of the system as a static or classical environment, and methods that treat the whole system quantum mechanically, but using approximate dynamics. Here, we perform a systematic comparison between these two philosophies for the description of quantum effects in vibrational spectroscopy, taking the Embedded Local Monomer model and a mixed quantum-classical model as representatives of the first family of methods, and centroid molecular dynamics and thermostatted ring polymer molecular dynamics as examples of the latter. We use as benchmarks D2O doped with HOD and pure H2O at three distinct thermodynamic state points (ice Ih at 150 K, and the liquid at 300 K and 600 K), modeled with the simple q-TIP4P/F potential energy and dipole moment surfaces. With few exceptions the different techniques yield IR absorption frequencies that are consistent with one another within a few tens of cm(-1). Comparison with classical molecular dynamics demonstrates the importance of nuclear quantum effects up to the highest temperature, and a detailed discussion of the discrepancies between the various methods let us draw some (circumstantial) conclusions about the impact of the very different approximations that underlie them. Such cross validation between radically different approaches could indicate a way forward to further improve the state of the art in simulations of condensed-phase quantum dynamics.

  12. Dissociative attachment reactions of electrons with gas phase superacids

    International Nuclear Information System (INIS)

    Liu, X.

    1992-01-01

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients β for reactions of electrons with gas phase superacids HCo(PF 3 ) 4 , HRh(PF 3 ) 4 and carbonyl hydride complexes HMn(CO) 5 , HRe(CO) 5 have been determined under thermal conditions over the approximate temperature range 300∼550 K. The superacids react relatively slowly ( max ) with free electrons in a thermal plasma, and the values of β obtained this far do not show a correlation between acidity and β. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF 3 ) 4 was found to be independent of temperature even though the β[HCo(PF 3 ) 4 ] increases with temperature. This proposes that the electron attachment process occurs well before the excited complex dissociates. In addition, the activation energy of HCo(PF 3 ) 4 for electron attachment has been derived from the Arrhenius plots. The carbonyl hydride complexes, HMn(CO) 5 and HRe(CO) 5 , react relatively rapidly (>1/4 of β max ) with free electrons in thermal plasma. This indicates that these reactions cannot be significantly endothermic. Observation of rapid attachment for these non-superacids shows that the Mn-CO and Re-CO bonds are weaker than the Mn-H and Re-H bonds, respectively. Comparisons between the carbonyl and trifluorophosphine cases implies that fast electron capture is related more to the CO ligand than to the transition-metal species

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

    International Nuclear Information System (INIS)

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

    1991-01-01

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

  14. Does increasing pressure always accelerate the condensed material decay initiated through bimolecular reactions? A case of the thermal decomposition of TKX-50 at high pressures.

    Science.gov (United States)

    Lu, Zhipeng; Zeng, Qun; Xue, Xianggui; Zhang, Zengming; Nie, Fude; Zhang, Chaoyang

    2017-08-30

    Performances and behaviors under high temperature-high pressure conditions are fundamentals for many materials. We study in the present work the pressure effect on the thermal decomposition of a new energetic ionic salt (EIS), TKX-50, by confining samples in a diamond anvil cell, using Raman spectroscopy measurements and ab initio simulations. As a result, we find a quadratic increase in decomposition temperature (T d ) of TKX-50 with increasing pressure (P) (T d = 6.28P 2 + 12.94P + 493.33, T d and P in K and GPa, respectively, and R 2 = 0.995) and the decomposition under various pressures initiated by an intermolecular H-transfer reaction (a bimolecular reaction). Surprisingly, this finding is contrary to a general observation about the pressure effect on the decomposition of common energetic materials (EMs) composed of neutral molecules: increasing pressure will impede the decomposition if it starts from a bimolecular reaction. Our results also demonstrate that increasing pressure impedes the H-transfer via the enhanced long-range electrostatic repulsion of H +δ H +δ of neighboring NH 3 OH + , with blue shifts of the intermolecular H-bonds. And the subsequent decomposition of the H-transferred intermediates is also suppressed, because the decomposition proceeds from a bimolecular reaction to a unimolecular one, which is generally prevented by compression. These two factors are the basic root for which the decomposition retarded with increasing pressure of TKX-50. Therefore, our finding breaks through the previously proposed concept that, for the condensed materials, increasing pressure will accelerate the thermal decomposition initiated by bimolecular reactions, and reveals a distinct mechanism of the pressure effect on thermal decomposition. That is to say, increasing pressure does not always promote the condensed material decay initiated through bimolecular reactions. Moreover, such a mechanism may be feasible to other EISs due to the similar intermolecular

  15. Analysis of the test results for the two-phase critical flow with non-condensible gas

    International Nuclear Information System (INIS)

    Chang, S. K.; Chung, C. H.; Park, H. S.; Min, K. H.; Choi, N. H.; Kim, C. H.; Lee, S. H.; Kim, H. C.; Chang, M. H.

    2002-07-01

    The two-phase critical flow test was performed for simulating the pipe break accident of SMART reactor. The requirements of the critical flow test are 7∼20mm pipe break dia., 7∼12MPa stagnation pressure, 0∼60 .deg. C subcooling degree and 0∼0.5kg/s N 2 gas flow rate. The test section is sharp edged pipe type which has the dimension of I.D.=20, L=300mm and I.D.=10.9, L=1000mm. The test conditions are 4, 7, 10 MPa at stagnation pressure, 0, 20, 50 .deg. C of subcooling degree and 0.028∼0.39 kg/s of N 2 injection gas flowrate. The measured data at test section and other components in terms of pressure, temperature and flowrate were collected in DAS computer with maintaining the steady state conditions at least 60 seconds. From the test results, the critical characteristics of the break pipe were analysed and verified the capacity of the test facility. For the verification of the Modified Henry-Fauske model which can predict the two-phase critical flow with non-condensible gas, the code simulation using MARS which contains the option of the Modified Henry -Fauske model was performed. The simulation results of steady-state two-phase critical flow experiments show that they agree with the measured critical flow rates within 6% root-mean-square error

  16. Isomerization and self-condensation reactions subsequent the. beta. -decay of tritiated naphthalene in the presence of liquid and gaseous benzene

    Energy Technology Data Exchange (ETDEWEB)

    Angelini, G.; Keheyan, Y.; Lilla, E.; Perez, G. (Consiglio Nazionale delle Ricerche, Rome (Italy). Ist. di Chimica Nucleare)

    1990-01-01

    Tritiated napththylium ions, generated by spontaneous {beta}-decay of (1,4-{sup 3}H) naphthalene, have been allowed to react with benzene molecules in gaseous and liquid phase. The isomeric phenylnaphthalenes and fluoranthene have been found among the reaction products. The differences between the reactivity pattern of naphthylium ion in the two phases can be explained by the different efficiency of collisional stabilization of the excited reaction intermediates. (orig.).

  17. Dual-comb spectroscopy of molecular electronic transitions in condensed phases

    Science.gov (United States)

    Cho, Byungmoon; Yoon, Tai Hyun; Cho, Minhaeng

    2018-03-01

    Dual-comb spectroscopy (DCS) utilizes two phase-locked optical frequency combs to allow scanless acquisition of spectra using only a single point detector. Although recent DCS measurements demonstrate rapid acquisition of absolutely calibrated spectral lines with unprecedented precision and accuracy, complex phase-locking schemes and multiple coherent averaging present significant challenges for widespread adoption of DCS. Here, we demonstrate Global Positioning System (GPS) disciplined DCS of a molecular electronic transition in solution at around 800 nm, where the absorption spectrum is recovered by using a single time-domain interferogram. We anticipate that this simplified dual-comb technique with absolute time interval measurement and ultrabroad bandwidth will allow adoption of DCS to tackle molecular dynamics investigation through its implementation in time-resolved nonlinear spectroscopic studies and coherent multidimensional spectroscopy of coupled chromophore systems.

  18. Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation.

    Science.gov (United States)

    Charnawskas, Joseph C; Alpert, Peter A; Lambe, Andrew T; Berkemeier, Thomas; O'Brien, Rachel E; Massoli, Paola; Onasch, Timothy B; Shiraiwa, Manabu; Moffet, Ryan C; Gilles, Mary K; Davidovits, Paul; Worsnop, Douglas R; Knopf, Daniel A

    2017-08-24

    Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g ) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

  19. Formation of clusters (ions solvated with products of radiolysis) during irradiation of certain chloralkanes in the condensed phase

    International Nuclear Information System (INIS)

    Sukhov, F.F.; Karatun, A.A.; Slovokhotova, N.A.

    1983-01-01

    Using the infrared spectroscopy method, the radiolysis of the 2-chloropropane and 2-chloro-2-methylpropane was investigated in various phase states and in argon matrix at 15 and 77 K. A conclusion is drawn that the reaction of the radiation dehydrochlorination in the chloralkanes investigated occurs under certain conditions in the vicinity of ions, mostly; as this takes place, unique clusters composed of radiolysis products, i.e. ions solvated with complexes of alkane and hydrogen chloride are being formed. (author)

  20. Predictions of wet natural gases condensation rates via multi-component and multi-phase simulation of supersonic separators

    International Nuclear Information System (INIS)

    Shooshtari, Seyed Heydar Rajaee; Shahsavand, Akbar

    2014-01-01

    Proper correction of water and heavy hydrocarbon dew points of sweet natural gases is essential from various technical and economical standpoints. Supersonic separators (3S) are proved to be capable of achieving these tasks with maximum reliability and minimal expenses. The majority of the previous articles have focused on the flow behavior of pure fluids across a 3S unit. Multicomponent fluid flow inside 3S accompanied with condensation phenomenon will drastically increase the complexity of the simulation process. We tackle this issue by considering a proper combination of fundamental governing equations and phase equilibrium calculations to predict various operating conditions and composition profiles across two multi-component and multi-phase 3S units. Various Iranian sweet gases are used as real case studies to demonstrate the importance of 3S unit practical applications. Simulation results clearly illustrate the effectiveness of 3S units for faithful dehydration of various natural gases, while successfully controlling its dew point, suitable for any practical applications. Conventional HYSYS simulation software is used to validate the simulation results

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

    International Nuclear Information System (INIS)

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

    1981-01-01

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

  2. Hydrogenation/Deoxygenation (H/D Reaction of Furfural-Acetone Condensation Product using Ni/Al2O3-ZrO2 Catalyst

    Directory of Open Access Journals (Sweden)

    Adam Mahfud

    2016-08-01

    Full Text Available The catalytic hydrogenation/deoxygenation (H/D reaction was carried out using Ni/Al2O3-ZrO2 catalyst. The 10% (wt/wt of Ni were impregnated on Al2O3-ZrO2 (10NiAZ by wet impregnation method followed by calcination and reduction. X-Ray diffraction analysis showed that Nideposited on the surface, with specific surface areas (SBET was 48.616 m2/g. Catalyst performance were evaluated for H/D reaction over furfural-acetone condensation products, mixture of 2-(4-furyl-3-buten-2-on and 1,5-bis-(furan-2-yl-pentan-3-one. The reaction was carried out in a batch, performed at 150°C for 8 hours. The H/D reaction gave alkane derivatives C8 and C10 by hydrogenation process followed by ring opening of furan in 15.2% yield. While, oxygenated product C10-C13 were also detected in 17.2% yield. The increasing of pore volume of 10NiAZ might enhance catalyst activity over H/D reaction. The alkene C=C bond was easy to hydrogenated under this condition by the lower bond energy gap.

  3. Method and apparatus for maintaining condensable constituents of a gas in a vapor phase during sample transport

    Science.gov (United States)

    Felix, Larry Gordon; Farthing, William Earl; Irvin, James Hodges; Snyder, Todd Robert

    2010-05-18

    A system for fluid transport at elevated temperatures having a conduit having a fluid inlet end and a fluid outlet end and at least one heating element disposed within the conduit providing direct heating of a fluid flowing through the conduit. The system is particularly suited for preventing condensable constituents of a high temperature fluid from condensing out of the fluid prior to analysis of the fluid. In addition, operation of the system so as to prevent the condensable constituents from condensing out of the fluid surprisingly does not alter the composition of the fluid.

  4. The Effects of a Macromolecular Charring Agent with Gas Phase and Condense Phase Synergistic Flame Retardant Capability on the Properties of PP/IFR Composites

    Science.gov (United States)

    Chen, Hongda; Wang, Jihui; Ding, Anxin; Han, Xia; Sun, Ziheng

    2018-01-01

    In order to improve the efficiency of intumescent flame retardants (IFRs), a novel macromolecular charring agent named poly(ethanediamine-1,3,5-triazine-p-4-amino-2,2,6,6-tetramethylpiperidine) (PETAT) with gas phase and condense phase synergistic flame-retardant capability was synthesized and subsequently dispersed into polypropylene (PP) in combination with ammonium polyphosphate (APP) via a melt blending method. The chemical structure of PETAT was investigated by Fourier transform infrared spectroscopy (FTIR), and 1H nuclear magnetic resonance (NMR) spectroscopy. Thermal properties of the PETAT and IFR systems were tested by thermogravimetric-derivative thermogravimetric analysis (TGA-DTG) and thermogravimetry–Fourier transform infrared spectroscopy (TG-FTIR). The mechanical properties, thermal stability, flame-retardant properties, water resistance, and structures of char residue in flame-retardant composites were characterized using tensile and flexural strength property tests, TGA, limiting oxygen index (LOI) values before and after soaking, underwritten laboratory-94 (UL-94) vertical burning test, cone calorimetric test (CCT), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDXS), and FTIR. The results indicated that PETAT was successfully synthesized, and when the ratio of APP to PETAT was 2:1 with 25 wt % loading, the novel IFR system could reduce the deterioration of tensile strength and enhance the flexural strength of composites. Meanwhile, the flame-retardant composite was able to pass the UL-94 V-0 rating with an LOI value of 30.3%, and the peak of heat release rate (PHRR), total heat release (THR), and material fire hazard values were considerably decreased compared with others. In addition, composites also exhibited excellent water resistance properties compared with traditional IFR composites. SEM-EDXS and FTIR analyses of the char residues, as well as TG-FTIR analyses of IFR were used to investigate the flame

  5. The Effects of a Macromolecular Charring Agent with Gas Phase and Condense Phase Synergistic Flame Retardant Capability on the Properties of PP/IFR Composites

    Directory of Open Access Journals (Sweden)

    Hongda Chen

    2018-01-01

    Full Text Available In order to improve the efficiency of intumescent flame retardants (IFRs, a novel macromolecular charring agent named poly(ethanediamine-1,3,5-triazine-p-4-amino-2,2,6,6-tetramethylpiperidine (PETAT with gas phase and condense phase synergistic flame-retardant capability was synthesized and subsequently dispersed into polypropylene (PP in combination with ammonium polyphosphate (APP via a melt blending method. The chemical structure of PETAT was investigated by Fourier transform infrared spectroscopy (FTIR, and 1H nuclear magnetic resonance (NMR spectroscopy. Thermal properties of the PETAT and IFR systems were tested by thermogravimetric-derivative thermogravimetric analysis (TGA-DTG and thermogravimetry–Fourier transform infrared spectroscopy (TG-FTIR. The mechanical properties, thermal stability, flame-retardant properties, water resistance, and structures of char residue in flame-retardant composites were characterized using tensile and flexural strength property tests, TGA, limiting oxygen index (LOI values before and after soaking, underwritten laboratory-94 (UL-94 vertical burning test, cone calorimetric test (CCT, scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDXS, and FTIR. The results indicated that PETAT was successfully synthesized, and when the ratio of APP to PETAT was 2:1 with 25 wt % loading, the novel IFR system could reduce the deterioration of tensile strength and enhance the flexural strength of composites. Meanwhile, the flame-retardant composite was able to pass the UL-94 V-0 rating with an LOI value of 30.3%, and the peak of heat release rate (PHRR, total heat release (THR, and material fire hazard values were considerably decreased compared with others. In addition, composites also exhibited excellent water resistance properties compared with traditional IFR composites. SEM-EDXS and FTIR analyses of the char residues, as well as TG-FTIR analyses of IFR were used to investigate the flame

  6. The Effects of a Macromolecular Charring Agent with Gas Phase and Condense Phase Synergistic Flame Retardant Capability on the Properties of PP/IFR Composites.

    Science.gov (United States)

    Chen, Hongda; Wang, Jihui; Ni, Aiqing; Ding, Anxin; Han, Xia; Sun, Ziheng

    2018-01-11

    In order to improve the efficiency of intumescent flame retardants (IFRs), a novel macromolecular charring agent named poly(ethanediamine-1,3,5-triazine-p-4-amino-2,2,6,6-tetramethylpiperidine) (PETAT) with gas phase and condense phase synergistic flame-retardant capability was synthesized and subsequently dispersed into polypropylene (PP) in combination with ammonium polyphosphate (APP) via a melt blending method. The chemical structure of PETAT was investigated by Fourier transform infrared spectroscopy (FTIR), and ¹H nuclear magnetic resonance (NMR) spectroscopy. Thermal properties of the PETAT and IFR systems were tested by thermogravimetric-derivative thermogravimetric analysis (TGA-DTG) and thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR). The mechanical properties, thermal stability, flame-retardant properties, water resistance, and structures of char residue in flame-retardant composites were characterized using tensile and flexural strength property tests, TGA, limiting oxygen index (LOI) values before and after soaking, underwritten laboratory-94 (UL-94) vertical burning test, cone calorimetric test (CCT), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDXS), and FTIR. The results indicated that PETAT was successfully synthesized, and when the ratio of APP to PETAT was 2:1 with 25 wt % loading, the novel IFR system could reduce the deterioration of tensile strength and enhance the flexural strength of composites. Meanwhile, the flame-retardant composite was able to pass the UL-94 V-0 rating with an LOI value of 30.3%, and the peak of heat release rate (PHRR), total heat release (THR), and material fire hazard values were considerably decreased compared with others. In addition, composites also exhibited excellent water resistance properties compared with traditional IFR composites. SEM-EDXS and FTIR analyses of the char residues, as well as TG-FTIR analyses of IFR were used to investigate the flame

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

    Directory of Open Access Journals (Sweden)

    Mazzoni A.D.

    2001-01-01

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

  8. A re-assessment of the thermodynamic properties of iodine condensed phases

    International Nuclear Information System (INIS)

    Arblaster, J.W.

    2011-01-01

    Highlights: → In the low temperature region below 298.15 K all previous reviews included highly discrepant experimental data points which should have been rejected. In the present review these data points have been rejected leading to a smooth specific heat curve similar to that obtained for solid bromine. The current values, especially at 298.15 K therefore differ considerably from other reviews but it is suggested are more acceptable. → For temperatures above 298.15 K previous reviews carried out unnecessary corrections to the experimental enthalpy measurements and therefore arrived at distorted values for the thermodynamic properties and since these corrections differed from one review to the next then the situation existed where different sets of thermodynamic tables existed and there was no way to suggest which was the correct one. In the present review the experimental values have been used without correction for calibration and therefore again represent a superior set of tables. → Since iodine is solid at room temperature then the question arises as to whether or not to divide the thermodynamic tables in to low temperature values based on 0 K and high temperature values based on 298.15 K. In this paper the values are based on 0 K only to be consistent with the analogues chlorine and bromine. However if in the opinion of the referees the divide ought to be used in this can be achieved quite easily. - Abstract: Thermodynamic properties of iodine have been calculated to 500 K. Specific heat anomalies accepted for the solid phase in previous reviews have been eliminated and a smooth specific heat curve derived. Corrections previously applied to high temperature solid and liquid enthalpy measurements were shown to be unnecessary.

  9. Zero point energy leakage in condensed phase dynamics: An assessment of quantum simulation methods for liquid water

    Science.gov (United States)

    Habershon, Scott; Manolopoulos, David E.

    2009-12-01

    The approximate quantum mechanical ring polymer molecular dynamics (RPMD) and linearized semiclassical initial value representation (LSC-IVR) methods are compared and contrasted in a study of the dynamics of the flexible q-TIP4P/F water model at room temperature. For this water model, a RPMD simulation gives a diffusion coefficient that is only a few percent larger than the classical diffusion coefficient, whereas a LSC-IVR simulation gives a diffusion coefficient that is three times larger. We attribute this discrepancy to the unphysical leakage of initially quantized zero point energy (ZPE) from the intramolecular to the intermolecular modes of the liquid as the LSC-IVR simulation progresses. In spite of this problem, which is avoided by construction in RPMD, the LSC-IVR may still provide a useful approximation to certain short-time dynamical properties which are not so strongly affected by the ZPE leakage. We illustrate this with an application to the liquid water dipole absorption spectrum, for which the RPMD approximation breaks down at frequencies in the O-H stretching region owing to contamination from the internal modes of the ring polymer. The LSC-IVR does not suffer from this difficulty and it appears to provide quite a promising way to calculate condensed phase vibrational spectra.

  10. Zero point energy leakage in condensed phase dynamics: an assessment of quantum simulation methods for liquid water.

    Science.gov (United States)

    Habershon, Scott; Manolopoulos, David E

    2009-12-28

    The approximate quantum mechanical ring polymer molecular dynamics (RPMD) and linearized semiclassical initial value representation (LSC-IVR) methods are compared and contrasted in a study of the dynamics of the flexible q-TIP4P/F water model at room temperature. For this water model, a RPMD simulation gives a diffusion coefficient that is only a few percent larger than the classical diffusion coefficient, whereas a LSC-IVR simulation gives a diffusion coefficient that is three times larger. We attribute this discrepancy to the unphysical leakage of initially quantized zero point energy (ZPE) from the intramolecular to the intermolecular modes of the liquid as the LSC-IVR simulation progresses. In spite of this problem, which is avoided by construction in RPMD, the LSC-IVR may still provide a useful approximation to certain short-time dynamical properties which are not so strongly affected by the ZPE leakage. We illustrate this with an application to the liquid water dipole absorption spectrum, for which the RPMD approximation breaks down at frequencies in the O-H stretching region owing to contamination from the internal modes of the ring polymer. The LSC-IVR does not suffer from this difficulty and it appears to provide quite a promising way to calculate condensed phase vibrational spectra.

  11. Quantum-phase dynamics of two-component Bose-Einstein condensates: Collapse-revival of macroscopic superposition states

    International Nuclear Information System (INIS)

    Nakano, Masayoshi; Kishi, Ryohei; Ohta, Suguru; Takahashi, Hideaki; Furukawa, Shin-ichi; Yamaguchi, Kizashi

    2005-01-01

    We investigate the long-time dynamics of two-component dilute gas Bose-Einstein condensates with relatively different two-body interactions and Josephson couplings between the two components. Although in certain parameter regimes the quantum state of the system is known to evolve into macroscopic superposition, i.e., Schroedinger cat state, of two states with relative atom number differences between the two components, the Schroedinger cat state is also found to repeat the collapse and revival behavior in the long-time region. The dynamical behavior of the Pegg-Barnett phase difference between the two components is shown to be closely connected with the dynamics of the relative atom number difference for different parameters. The variation in the relative magnitude between the Josephson coupling and intra- and inter-component two-body interaction difference turns out to significantly change not only the size of the Schroedinger cat state but also its collapse-revival period, i.e., the lifetime of the Schroedinger cat state

  12. Condensed phase QM/MM simulations utilizing the exchange core functions to describe exchange repulsions at the QM boundary region

    International Nuclear Information System (INIS)

    Umino, Satoru; Takahashi, Hideaki; Morita, Akihiro

    2016-01-01

    In a recent work, we developed a method [H. Takahashi et al., J. Chem. Phys. 143, 084104 (2015)] referred to as exchange-core function (ECF) approach, to compute exchange repulsion E ex between solute and solvent in the framework of the quantum mechanical (QM)/molecular mechanical (MM) method. The ECF, represented with a Slater function, plays an essential role in determining E ex on the basis of the overlap model. In the work of Takahashi et al. [J. Chem. Phys. 143, 084104 (2015)], it was demonstrated that our approach is successful in computing the hydrogen bond energies of minimal QM/MM systems including a cationic QM solute. We provide in this paper the extension of the ECF approach to the free energy calculation in condensed phase QM/MM systems by combining the ECF and the QM/MM-ER approach [H. Takahashi et al., J. Chem. Phys. 121, 3989 (2004)]. By virtue of the theory of solutions in energy representation, the free energy contribution δμ ex from the exchange repulsion was naturally formulated. We found that the ECF approach in combination with QM/MM-ER gives a substantial improvement on the calculation of the hydration free energy of a hydronium ion. This can be attributed to the fact that the ECF reasonably realizes the contraction of the electron density of the cation due to the deficit of an electron.

  13. Condensed phase QM/MM simulations utilizing the exchange core functions to describe exchange repulsions at the QM boundary region

    Energy Technology Data Exchange (ETDEWEB)

    Umino, Satoru; Takahashi, Hideaki, E-mail: hideaki@m.tohoku.ac.jp; Morita, Akihiro [Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Miyagi 980-8578 (Japan)

    2016-08-28

    In a recent work, we developed a method [H. Takahashi et al., J. Chem. Phys. 143, 084104 (2015)] referred to as exchange-core function (ECF) approach, to compute exchange repulsion E{sub ex} between solute and solvent in the framework of the quantum mechanical (QM)/molecular mechanical (MM) method. The ECF, represented with a Slater function, plays an essential role in determining E{sub ex} on the basis of the overlap model. In the work of Takahashi et al. [J. Chem. Phys. 143, 084104 (2015)], it was demonstrated that our approach is successful in computing the hydrogen bond energies of minimal QM/MM systems including a cationic QM solute. We provide in this paper the extension of the ECF approach to the free energy calculation in condensed phase QM/MM systems by combining the ECF and the QM/MM-ER approach [H. Takahashi et al., J. Chem. Phys. 121, 3989 (2004)]. By virtue of the theory of solutions in energy representation, the free energy contribution δμ{sub ex} from the exchange repulsion was naturally formulated. We found that the ECF approach in combination with QM/MM-ER gives a substantial improvement on the calculation of the hydration free energy of a hydronium ion. This can be attributed to the fact that the ECF reasonably realizes the contraction of the electron density of the cation due to the deficit of an electron.

  14. Ultrasound-assisted green synthesis of pyrroles and pyridazines in water via three-component condensation reactions of arylglyoxals

    Directory of Open Access Journals (Sweden)

    Bagher Eftekhari-Sis

    2013-04-01

    Full Text Available A green and efficient method for the preparation of 5-aryl-4-hydroxy-2-methyl-1H-pyrrole-3-carboxylic acid esters and 6-aryl-3-methylpyridazine-4-carboxylic acid esters via three-component reaction of arylglyoxal hydrates with β-dicarbonyl compounds in the presence of ammonium acetate and hydrazine hydrate using water as solvent under ultrasonic irradiation was reported. The reactions proceeded rapidly and afforded the corresponding pyrroles and pyridazines in good to high yields in very short reaction time.

  15. Theory of terahertz pumping of chemical environments in the condensed phase

    International Nuclear Information System (INIS)

    Mishra, Pankaj Kumar

    2015-12-01

    Newly emerged light-sources allow to generate fully synchronized, ultrashort and highly intense light pulses. With these light pulses, it is possible to initiate a process by a pump pulse and follow the dynamics via probe pulse in the femtosecond timescale. These pump-probe experiments play an important role for studying the chemical and biological processes in real time. Such techniques are also used to generate temperature-jump (T-jump) in ultrashort timescale to study the very fast kinetics of fundamental steps in chemical processes. Because of its biological and chemical relevance, T-jump experiments on liquid water have gained a lot of attention. Rather than acting as a passive environment, the dynamics of water during chemical and biological processes play a fundamental role in the solvation and stabilization of reaction intermediates. To target the O-H stretching mode of water with an infrared (IR) laser is a widely used mechanism to generate the T-jump in nanosecond to femtosecond timescales. With these techniques, T-jump has been limited only to few 10s of K so far. In this thesis, a new mechanism is investigated to generate T-jump up to few 100s of K in sub-ps timescale. The main portion of this thesis concentrates on the response of liquid water to sub-cycle THz pump pulses spectrally centered at 100 cm -1 (∝3 THz). The THz pump pulse with intensity of 5 x 10 12 W/cm 2 transfers a large amount of energy to inter- and intramolecular vibrations of water in sub-ps timescale. After the pump pulse, water reaches to a quasiequilibrium state, which is a gas-like hot liquid. The large energy gain in water causes significant structural modifications and vibrational shifting, which can be probed by timeresolved coherent x-ray scattering and time-resolved IR spectroscopy, respectively. Here, the interaction of THz pulse with water molecules is investigated from clusters to bulk water. We find it to be mainly described via the interaction of electric field with

  16. A route to hydroxylfluorenes: TsOH-mediated condensation reactions of 1,3-diketones with propargylic alcohols

    KAUST Repository

    Yao, Liangfeng; Tan, Davin; Miao, Xiaohe; Huang, Kuo-Wei

    2012-01-01

    An efficient method of preparing hydroxylfluorenes by TsOH-mediated tandem alkylation/rearrangements of propargylic alcohols with 1,3-diketones is described. These reactions are accomplished in moderate to good yields under mild conditions to offer

  17. Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change

    Directory of Open Access Journals (Sweden)

    I. J. George

    2007-08-01

    Full Text Available The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl sebacate (BES particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS and scanning mobility particle sizer (SMPS was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of γ0=1.3 (±0.4, confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity.

  18. DESAIN DAN SINTESIS SENYAWA ACES (ANALOG CURCUMIN SERIES DENGAN METODE SOLID PHASE REACTION SEBAGAI SENYAWA ANTIKANKER POTEN DENGAN MEKANISME MENGHAMBAT PROTEIN NF-kB

    Directory of Open Access Journals (Sweden)

    Monica Sabrina Widiapranolo

    2016-04-01

    Full Text Available Abstract: Analog of curcumin in forms of enone and dienone aromatic is known for their activity as an NF-κB inhibitor. In this study, will be synthesize 2-(4'-N, N-dimethylamino benzilidine cyclohexane-1,3-dione as an analog that predicted has an activity as an NF-κB inhibitor. This research was conducted based on the crossed aldol condensation reaction by reacting 3 mmole pN,N-dimethylamino benzaldehide and 6 mmole cyclohexane-1,3-dione with hydrochloric acid as the catalyst using solid phase reaction method. Based on computational analysis, 2-(4'-N,Ndimethylamino benzilidine cyclohexane-1,3-dione showed a better interaction with NF-κB protein with PLANTSPLP score was -69,7895. The outcome of the reaction was yellow colored powder, no odor and soluble in hydrochloric acid 3N. The yield value was 78.8%. Liquid chromatography showed 100% purity. The melting point range was 237.5-240.3°C. The results of structure elucidation by 1H-NMR, infrared and mass spectroscopy tests indicated the compound was 2-(4-(dimetilaminobenzilidena-4-(3-oksosiklohex-1-enil sikloheksana-1,3-dion. Key words: 2-(4'-N, N-dimethylamino benzilidine cyclohexane-1,3-dione, crossed aldol condensation, solid phase reaction.

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

    DEFF Research Database (Denmark)

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

    2003-01-01

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

  20. Steam generators, turbines, and condensers. Volume six

    International Nuclear Information System (INIS)

    Anon.

    1986-01-01

    Volume six covers steam generators (How steam is generated, steam generation in a PWR, vertical U-tube steam generators, once-through steam generators, how much steam do steam generators make?), turbines (basic turbine principles, impulse turbines, reaction turbines, turbine stages, turbine arrangements, turbine steam flow, steam admission to turbines, turbine seals and supports, turbine oil system, generators), and condensers (need for condensers, basic condenser principles, condenser arrangements, heat transfer in condensers, air removal from condensers, circulating water system, heat loss to the circulating water system, factors affecting condenser performance, condenser auxiliaries)

  1. Acoustic Resonance Reaction Control Thruster (ARCTIC), Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — ORBITEC proposes to develop and demonstrate the innovative Acoustic Resonance Reaction Control Thruster (ARCTIC) to provide rapid and reliable in-space impulse...

  2. Reaction Wheel Disturbance Model Extraction Software, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel disturbances are some of the largest sources of noise on sensitive telescopes. Such wheel-induced mechanical noises are not well characterized....

  3. Reaction Wheel Disturbance Model Extraction Software, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel mechanical noise is one of the largest sources of disturbance forcing on space-based observatories. Such noise arises from mass imbalance, bearing...

  4. Miniature Reaction Wheel for Small Satellite Control, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — The overall goal of this project is to design, develop, demonstrate, and deliver a miniature, high torque, low-vibration reaction wheel for use on small satellites....

  5. Conceptual design of the test facility for the two-phase critical flow with non-condensable gas

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Seok Kyu; Chung, Chang Hwan

    2000-12-01

    The two-phase critical flow test with non-condensible gas is for the simulation of the critical flow phenomena which can be occurred during SB-LOCA on SMART reactor. The requirements of the critical flow test are 7{approx}20mm pipe break dia., 7{approx}12MPa stagnation pressure, 0{approx}60 deg C subcooling degree and 0{approx}0.5kg/s N2 gas flow rate. For the satisfaction of these requirements on the test facility, critical flow rates were calculated with various models. With the selected reference pressure vessel(1.3m{sup 3}), the conceptual design of the test facility was performed. The important components of the test facility are the pressure vessel which has main circulation line, the test section attached to the bottom of the pressure vessel, suppression tank, the N2 gas supply tanks for maintaining the system pressure and N2 gas flow rate at test section and the auxiliary N2 gas converting system. For the measurements of the critical flow rate, flowmeter and level gauge is installed at the upstream of the test section and the pressure vessel, respectively. The realtime pressure control system is installed at the entrance of the pressure vessel for maintaining the system pressure and the N2 gas flow regulating system is also installed at the upstream of the test section. The design of the control and monitoring system for the operation of the test facility and the DAS for acquiring the test data were also performed. The conceptual operating process of the test facility was determined.

  6. Conceptual design of the test facility for the two-phase critical flow with non-condensable gas

    International Nuclear Information System (INIS)

    Chang, Seok Kyu; Chung, Chang Hwan

    2000-12-01

    The two-phase critical flow test with non-condensible gas is for the simulation of the critical flow phenomena which can be occurred during SB-LOCA on SMART reactor. The requirements of the critical flow test are 7∼20mm pipe break dia., 7∼12MPa stagnation pressure, 0∼60 deg C subcooling degree and 0∼0.5kg/s N2 gas flow rate. For the satisfaction of these requirements on the test facility, critical flow rates were calculated with various models. With the selected reference pressure vessel(1.3m 3 ), the conceptual design of the test facility was performed. The important components of the test facility are the pressure vessel which has main circulation line, the test section attached to the bottom of the pressure vessel, suppression tank, the N2 gas supply tanks for maintaining the system pressure and N2 gas flow rate at test section and the auxiliary N2 gas converting system. For the measurements of the critical flow rate, flowmeter and level gauge is installed at the upstream of the test section and the pressure vessel, respectively. The realtime pressure control system is installed at the entrance of the pressure vessel for maintaining the system pressure and the N2 gas flow regulating system is also installed at the upstream of the test section. The design of the control and monitoring system for the operation of the test facility and the DAS for acquiring the test data were also performed. The conceptual operating process of the test facility was determined

  7. Basic design of the test facility for the two-phase critical flow with non-condensable gas

    International Nuclear Information System (INIS)

    Chang, Seok Kyu; Kim, Chang Hwe; Chung, Chang Hwan

    2000-12-01

    The two-phase critical flow test with non-condensible gas is for the simulation of the critical flow phenomena which can be occurred during SB-LOCA on SMART reactor. The basic design of the test facility for the actual installation is performed from the basis of the previous conceptual design according to the test requirements. The 1.3m 3 pressure vessel has the circulation pipeline which contains pump(5m 3 /hr), main heater(150KW) and cooler for heating the working fluid to the test temperature within 6 hours. The N2 gas, water supply line are attached to the upper part and test section, flowmeter and various sensors are installed at the lower part of the pressure vessel. The suppression tank is for the storage and cooling of the discharged water. The N2 gas storage tank provides the system pressure to the pressure vessel during the test. The 0.7m 3 N2 gas injection tank supplies the required N2 gas to the entrance of the test section. Since these N2 supply systems require much amount of gas during short period, multistage valve systems and optimal control logics are needed and applied. For the filling of the N2 gas to the N2 storage tank, 5m 3 LN2 tank and related gas converting system were designed. The operating mode of the test facility can be classified to the starting, steady, main test and cooling modes and the proper monitoring and control logics are developed for each operating mode. The operation of the test facility is performed through the PLC and the acquisition of the test data is done with DAS

  8. Vibrational-rotational excitation: chemical reactions of vibrationally excited molecules

    International Nuclear Information System (INIS)

    Moore, C.B.; Smith, I.W.M.

    1979-03-01

    This review considers a limited number of systems, particularly gas-phase processes. Excited states and their preparation, direct bimolecular reactions, reactions of highly excited molecules, and reactions in condensed phases are discussed. Laser-induced isotope separation applications are mentioned briefly. 109 references

  9. A route to hydroxylfluorenes: TsOH-mediated condensation reactions of 1,3-diketones with propargylic alcohols

    KAUST Repository

    Yao, Liangfeng

    2012-01-01

    An efficient method of preparing hydroxylfluorenes by TsOH-mediated tandem alkylation/rearrangements of propargylic alcohols with 1,3-diketones is described. These reactions are accomplished in moderate to good yields under mild conditions to offer a straightforward and convenient one step synthetic route to hydroxylfluorene derivatives through a plausible mechanism involving a sequence of dehydration, addition, rearrangement and aromatization. This journal is © The Royal Society of Chemistry 2012.

  10. Concise Access to 2-Aroylbenzothiazoles by Redox Condensation Reaction between o-Halonitrobenzenes, Acetophenones, and Elemental Sulfur.

    Science.gov (United States)

    Nguyen, Thanh Binh; Pasturaud, Karine; Ermolenko, Ludmila; Al-Mourabit, Ali

    2015-05-15

    A wide range of 2-aroylbenzothiazoles 3 including some pharmacologically relevant derivatives can be obtained in high yields by simply heating o-halonitrobenzenes 1, acetophenones 2, elemental sulfur, and N-methylmorpholine. This three-component nitro methyl coupling was found to occur in an excellent atom-, step-, and redox-efficient manner in which elemental sulfur played the role of nucleophile building block and redox moderating agent to fulfill electronic requirements of the global reaction.

  11. Pressure induced reactions amongst calcium aluminate hydrate phases

    KAUST Repository

    Moon, Ju-hyuk; Oh, Jae Eun; Balonis, Magdalena; Glasser, Fredrik P.; Clark, Simon M.; Monteiro, Paulo J.M.

    2011-01-01

    The compressibilities of two AFm phases (strätlingite and calcium hemicarboaluminate hydrate) and hydrogarnet were obtained up to 5 GPa by using synchrotron high-pressure X-ray powder diffraction with a diamond anvil cell. The AFm phases show abrupt

  12. A GROMOS-Compatible Force Field for Small Organic Molecules in the Condensed Phase: The 2016H66 Parameter Set.

    Science.gov (United States)

    Horta, Bruno A C; Merz, Pascal T; Fuchs, Patrick F J; Dolenc, Jozica; Riniker, Sereina; Hünenberger, Philippe H

    2016-08-09

    This article reports on the calibration and validation of a new GROMOS-compatible parameter set 2016H66 for small organic molecules in the condensed phase. The calibration is based on 62 organic molecules spanning the chemical functions alcohol, ether, aldehyde, ketone, carboxylic acid, ester, amine, amide, thiol, sulfide, and disulfide, as well as aromatic compounds and nucleic-acid bases. For 57 organic compounds, the calibration targets are the experimental pure-liquid density ρliq and the vaporization enthalpy ΔHvap, as well as the hydration free energy ΔGwat and the solvation free energy ΔGche in cyclohexane, at atmospheric pressure and at (or close to) room temperature. The final root-mean-square deviations (RMSD) for these four quantities over the set of compounds are 32.4 kg m(-3), 3.5 kJ mol(-1), 4.1 kJ mol(-1), and 2.1 kJ mol(-1), respectively, and the corresponding average deviations (AVED) are 1.0 kg m(-3), 0.2 kJ mol(-1), 2.6 kJ mol(-1), and 1.0 kJ mol(-1), respectively. For the five nucleic-acid bases, the parametrization is performed by transferring the final 2016H66 parameters from analogous organic compounds followed by a slight readjustment of the charges to reproduce the experimental water-to-chloroform transfer free energies ΔGtrn. The final RMSD for this quantity over the five bases is 1.7 kJ mol(-1), and the corresponding AVED is 0.8 kJ mol(-1). As an initial validation of the 2016H66 set, seven additional thermodynamic, transport, and dielectric properties are calculated for the 57 organic compounds in the liquid phase. The agreement with experiment in terms of these additional properties is found to be reasonable, with significant deviations typically affecting either a specific chemical function or a specific molecule. This suggests that in most cases, a classical force-field description along with a careful parametrization against ρliq, ΔHvap, ΔGwat, and ΔGche results in a model that appropriately describes the liquid in terms of

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

    Science.gov (United States)

    Csernica, Stephen N.

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

  14. Reactions between Ti3Al-Nb and mixed second phases

    International Nuclear Information System (INIS)

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

    1989-01-01

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

  15. Boilers, evaporators, and condensers

    International Nuclear Information System (INIS)

    Kakac, S.

    1991-01-01

    This book reports on the boilers, evaporators and condensers that are used in power plants including nuclear power plants. Topics included are forced convection for single-phase side heat exchangers, heat exchanger fouling, industrial heat exchanger design, fossil-fuel-fired boilers, once through boilers, thermodynamic designs of fossil fuel-first boilers, evaporators and condensers in refrigeration and air conditioning systems (with respect to reducing CFC's) and nuclear steam generators

  16. Molecular equilibrium with condensation

    International Nuclear Information System (INIS)

    Sharp, C.M.; Huebner, W.F.

    1990-01-01

    Minimization of the Gibbs energy of formation for species of chemical elements and compounds in their gas and condensed phases determines their relative abundances in a mixture in chemical equilibrium. The procedure is more general and more powerful than previous abundance determinations in multiphase astrophysical mixtures. Some results for astrophysical equations of state are presented, and the effects of condensation on opacity are briefly indicated. 18 refs

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

    Science.gov (United States)

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

    2018-03-01

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

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

    International Nuclear Information System (INIS)

    Kleingeld, J.C.

    1984-01-01

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

  19. Gas phase reactions of organic iodine in containment conditions

    International Nuclear Information System (INIS)

    Kaerkalae, T.; Holm, J.; Auvinen, A.; Zilliacus, R.; Kajolinna, T.; Tapper, U.; Gaenneskog, H.; Ekberg, C.

    2010-01-01

    In case of a hypothetical severe accident it is very likely that iodine at least partly deposits on painted walls of a reactor containment building. Iodine may react with painted surfaces to form organic iodine species. These organic species are a possible source of volatile iodine, which may increase the fraction of releasable iodine. Therefore, it is important to study the transport of organic iodine in containment conditions. Another question is, in which form are the organic iodides transported as gaseous molecules or as aerosol particles resulting from organic iodides reacting with radiolysis products. To answer this last question methyl iodide was fed into the EXSI facility in an air mixture. In some experiments the flow contained also humidity. The reactions took place in a quartz tube heated either to 50 deg. C, 90 deg. C or 120 deg. C. UV-light was used as a source of radiation to produce ozone from oxygen. A separate generator was also applied to reach higher ozone concentrations. Nucleated aerosol particles were collected on plane filters and gaseous iodine species were trapped in trapping bottles. Aerosol mass flow rate and size distribution as well as speciation of gaseous reaction products were measured with several on-line instruments. Collected aerosol particles were analysed with SEM. It was found that the formation of aerosol particles was very fast when ozone and methyl iodide were present in the facility. Even a very low concentration of ozone produced high number concentration of particles. The measured aerosol mass concentration increased with increasing temperature and ozone concentration. Because the particle diameter was quite small (<180 nm), their settling velocity is low. Therefore, iodine containing aerosols may exist in containment atmosphere for a long period of time. Part of methyl iodide was always transported through the facility regardless of experimental conditions. All ozone was consumed in the reactions when only UV-light was

  20. Condensed Matter Cluster Reactions in LENR Power Cells for a Radical New Type of Space Power Source

    Science.gov (United States)

    Yang, Xiaoling; Miley, George H.; Hora, Heinz

    2009-03-01

    This paper reviews previous theoretical and experimental study on the possibility of nuclear events in multilayer thin film electrodes (Lipson et al., 2004 and 2005; Miley et al., 2007), including the correlation between excess heat and transmutations (Miley and Shrestha, 2003) and the cluster theory that predicts it. As a result of this added understanding of cluster reactions, a new class of electrodes is under development at the University of Illinois. These electrodes are designed to enhance cluster formation and subsequent reactions. Two approaches are under development. The first employs improved loading-unloading techniques, intending to obtain a higher volumetric density of sites favoring cluster formation. The second is designed to create nanostructures on the electrode where the cluster state is formed by electroless deposition of palladium on nickel micro structures. Power units employing these electrodes should offer unique advantages for space applications. This is a fundamental new nuclear energy source that is environmentally compatible with a minimum of radiation involvement, high specific power, very long lifetime, and scalable from micro power to kilowatts.

  1. Condensed Matter Cluster Reactions in LENR Power Cells for a Radical New Type of Space Power Source

    International Nuclear Information System (INIS)

    Yang Xiaoling; Miley, George H.; Hora, Heinz

    2009-01-01

    This paper reviews previous theoretical and experimental study on the possibility of nuclear events in multilayer thin film electrodes (Lipson et al., 2004 and 2005; Miley et al., 2007), including the correlation between excess heat and transmutations (Miley and Shrestha, 2003) and the cluster theory that predicts it. As a result of this added understanding of cluster reactions, a new class of electrodes is under development at the University of Illinois. These electrodes are designed to enhance cluster formation and subsequent reactions. Two approaches are under development. The first employs improved loading-unloading techniques, intending to obtain a higher volumetric density of sites favoring cluster formation. The second is designed to create nanostructures on the electrode where the cluster state is formed by electroless deposition of palladium on nickel micro structures. Power units employing these electrodes should offer unique advantages for space applications. This is a fundamental new nuclear energy source that is environmentally compatible with a minimum of radiation involvement, high specific power, very long lifetime, and scalable from micro power to kilowatts.

  2. Water Condensation

    DEFF Research Database (Denmark)

    Jensen, Kasper Risgaard; Fojan, Peter; Jensen, Rasmus Lund

    2014-01-01

    The condensation of water is a phenomenon occurring in multiple situations in everyday life, e.g., when fog is formed or when dew forms on the grass or on windows. This means that this phenomenon plays an important role within the different fields of science including meteorology, building physics......, and chemistry. In this review we address condensation models and simulations with the main focus on heterogeneous condensation of water. The condensation process is, at first, described from a thermodynamic viewpoint where the nucleation step is described by the classical nucleation theory. Further, we address...

  3. 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

  4. Spectroscopic and theoretical study of the "azo"-dye E124 in condensate phase: evidence of a dominant hydrazo form.

    Science.gov (United States)

    Almeida, Mariana R; Stephani, Rodrigo; Dos Santos, Hélio F; de Oliveira, Luiz Fernando C

    2010-01-14

    Spectroscopic techniques, including Raman, IR, UV/vis, and NMR were used to characterize the samples of the azo dye Ponceau 4R (also known as E124, New Coccine; Cochineal Red; C.I. no. 16255; Food Red No. 102), which is 1,3-naphthalenedisulfonic acid, 7-hydroxy-8-[(4-sulfo-1-naphthalenyl) azo] trisodium salt in aqueous solution and solid state. In addition, first principle calculations were carried out for the azo (OH) and hydrazo (NH) tautomers in order to assist in the assignment of the experimental data. The two intense bands observed in the UV/vis spectrum, centered at 332 and 507 nm, can be compared to the calculated values at 296 and 474 nm for azo and 315 and 500 nm for hydrazo isomer, with the latter in closer agreement to the experiment. The Raman spectrum is quite sensitive to tautomeric equilibrium; in solid state and aqueous solution, three bands were observed around 1574, 1515, and 1364 cm(-1), assigned to mixed modes including deltaNH + betaCH + nuCC, deltaNH + nuC horizontal lineO + nuC horizontal lineN + betaCH and nuCC vibrations, respectively. These assignments are predicted only for the NH species centered at 1606, 1554, and 1375 cm(-1). The calculated Raman spectrum for the azo (OH) tautomer showed two strong bands at 1468 (nuN = N + deltaOH) and 1324 cm(-1) (nuCC + nuC-N), which were not obtained experimentally. The (13)C NMR spectrum showed a very characteristic peak at 192 ppm assigned to the carbon bound to oxygen in the naphthol ring; the predicted values were 165 ppm for OH and 187 for NH isomer, supporting once again the predominance of NH species in solution. Therefore, all of the experimental and theoretical results strongly suggest the food dye Ponceau 4R or E124 has a major contribution of the hydrazo structure instead of the azo form as the most abundant in condensate phase.

  5. Iron Oxide-Supported Copper Oxide Nanoparticles (Nanocat-Fe-CuO): Magnetically Recyclable Catalysts for the Synthesis of Pyrazole Derivatives, 4-Methoxyaniline, and Ullmann-type Condensation Reactions

    Science.gov (United States)

    An efficient and benign protocol is reported for the synthesis of 4-methoxyaniline, medicinally important pyrazole derivatives, and Ullmann-type condensation reaction using magnetically separable and reusable magnetite-supported copper (nanocat-Fe-CuO) nanoparticles under mild co...

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

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed

    2014-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-06-15

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

  8. Anomalous tunneling of collective excitations and effects of superflow in the polar phase of a spin-1 spinor Bose-Einstein condensate

    International Nuclear Information System (INIS)

    Watabe, Shohei; Ohashi, Yoji; Kato, Yusuke

    2011-01-01

    We investigate tunneling properties of collective modes in the polar phase of a spin-1 spinor Bose-Einstein condensate (BEC). This spinor BEC state has two kinds of gapless modes (i.e., Bogoliubov and spin-wave). Within the framework of mean-field theory at T=0, we show that these Goldstone modes exhibit perfect transmission in the low-energy limit. Their anomalous tunneling behavior still holds in the presence of superflow, except in the critical current state. In the critical current state, while the tunneling of Bogoliubov mode is accompanied by finite reflection, the spin wave still exhibits perfect transmission, unless the strengths of spin-dependent and spin-independent interactions take the same value. We discuss the relation between perfect transmission of a spin wave and underlying superfluidity through a comparison of wave functions of the spin wave and the condensate.

  9. Pressure induced reactions amongst calcium aluminate hydrate phases

    KAUST Repository

    Moon, Ju-hyuk

    2011-06-01

    The compressibilities of two AFm phases (strätlingite and calcium hemicarboaluminate hydrate) and hydrogarnet were obtained up to 5 GPa by using synchrotron high-pressure X-ray powder diffraction with a diamond anvil cell. The AFm phases show abrupt volume contraction regardless of the molecular size of the pressure-transmitting media. This volume discontinuity could be associated to a structural transition or to the movement of the weakly bound interlayer water molecules in the AFm structure. The experimental results seem to indicate that the pressure-induced dehydration is the dominant mechanism especially with hygroscopic pressure medium. The Birch-Murnaghan equation of state was used to compute the bulk modulus of the minerals. Due to the discontinuity in the pressure-volume diagram, a two stage bulk modulus of each AFm phase was calculated. The abnormal volume compressibility for the AFm phases caused a significant change to their bulk modulus. The reliability of this experiment is verified by comparing the bulk modulus of hydrogarnet with previous studies. © 2011 Elsevier Ltd. All rights reserved.

  10. The influence of phase transfer catalyst structure on reaction selectivity

    International Nuclear Information System (INIS)

    Demlov, Eh.V.

    1995-01-01

    A concise review is given of systematic studies which are concerned with the tuning of regio, frequentio-, chemo-, and diastereoselectivity by the structure or type of phase transfer catalyst. Use of MEI as an alkylating agent is described. Refs. 36, figs. 11

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

    International Nuclear Information System (INIS)

    Joergensen, S.I.

    1985-01-01

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

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

    Science.gov (United States)

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

    2014-12-02

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

  13. Gas-phase reactions at combustion and gasification

    International Nuclear Information System (INIS)

    Hupa, M.; Kilpinen, P.; Chowdhury, K.; Brink, A.; Mueller, C.

    1995-01-01

    Formation and destruction of gaseous nitrogen pollutants at combustion (NO x , N 2 O) and gasification (NH 3 , HCN) are studied based on detailed chemical kinetic modelling and experiments in laboratory reactors. During 1994 the following topics have been studied: (a) nitrogen reactions in pressurized combustion processes (in co-operation with the LIEKKI projects 202 and 204), (b) NO x reduction by staging techniques in CO 2 , rich combustion processes, (c) HCN reactions at pyrolysis, (d) formation of soot precursors in a blast furnace (in co-operation with the SULA project 103) (e) incorporation of better NO x description into furnace models, (in co-operation with the LIEKKI project Y01). NH 3 conversion to N 2 in gasification product gases, (in co-operation with the LIEKKI project 203). In this report, some results of the items (a-c) will be presented. The results of items (d-f) are described in the reports by the co-operation projects. (author)

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

    International Nuclear Information System (INIS)

    Fagerstroem, K.

    1993-01-01

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

  15. Synthesis of TiO2 Nanoparticles from Ilmenite Through the Mechanism of Vapor-Phase Reaction Process by Thermal Plasma Technology

    Science.gov (United States)

    Samal, Sneha

    2017-11-01

    Synthesis of nanoparticles of TiO2 was carried out by non-transferred arc thermal plasma reactor using ilmenite as the precursor material. The powder ilmenite was vaporized at high temperature in plasma flame and converted to a gaseous state of ions in the metastable phase. On cooling, chamber condensation process takes place on recombination of ions for the formation of nanoparticles. The top-to-bottom approach induces the disintegration of complex ilmenite phases into simpler compounds of iron oxide and titanium dioxide phases. The vapor-phase reaction mechanism was carried out in thermal plasma zone for the synthesis of nanoparticles from ilmenite compound in a plasma reactor. The easy separation of iron particles from TiO2 was taken place in the plasma chamber with deposition of light TiO2 particles at the top of the cooling chamber and iron particles at the bottom. The dissociation and combination process of mechanism and synthesis are studied briefly in this article. The product TiO2 nanoparticle shows the purity with a major phase of rutile content. TiO2 nanoparticles produced in vapor-phase reaction process shows more photo-induced capacity.

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  17. Steam condenser

    International Nuclear Information System (INIS)

    Masuda, Fujio

    1980-01-01

    Purpose: To enable safe steam condensation by providing steam condensation blades at the end of a pipe. Constitution: When high temperature high pressure steam flows into a vent pipe having an opening under water in a pool or an exhaust pipe or the like for a main steam eacape safety valve, non-condensable gas filled beforehand in the steam exhaust pipe is compressed, and discharged into the water in the pool. The non-condensable gas thus discharged from the steam exhaust pipe is introduced into the interior of the hollow steam condensing blades, is then suitably expanded, and thereafter exhausted from a number of exhaust holes into the water in the pool. In this manner, the non-condensable gas thus discharged is not directly introduced into the water in the pool, but is suitable expanded in the space of the steam condensing blades to suppress extreme over-compression and over-expansion of the gas so as to prevent unstable pressure vibration. (Yoshihara, H.)

  18. Enhanced Hydrothermal Stability and Catalytic Activity of La x Zr y O z Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Ruiz, Juan A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Cooper, Alan R. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Li, Guosheng [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States; Albrecht, Karl O. [Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States

    2017-08-24

    Common ketonization catalysts such as ZrO2, CeO2, CexZryOz, and TiO2-based catalysts have been reported to lose surface area, undergo phase-transformation, and lose catalytic activity when utilized in the condensed aqueous phase. In this work, we synthesized and tested a series of LaxZryOz mixed metal oxides with different La:Zr atomic ratios with the goal of enhancing the catalytic activity and stability for the ketonization of acetic acid in condensed aqueous media at 568 K. We synthesized a hydrothermally stable LaxZryOz mixed-metal oxide catalyst with enhanced ketonization activities 360 and 40 times more active than La2O3 and ZrO2, respectively. Catalyst characterization techniques suggest that the formation of a hydrothermally stable catalyst which is isomorphic with tetragonal-ZrO2 under hydrothermal reaction conditions.

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

    Science.gov (United States)

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

    2016-09-14

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

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

    International Nuclear Information System (INIS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

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

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

    Science.gov (United States)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

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

  2. Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

    Science.gov (United States)

    Franczuk, Barbara; Danikiewicz, Witold

    2018-03-01

    Ion-molecule reactions of Me2S2 with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction ( m/z 47), SN2 ( m/z 79), and E2 elimination - addition sequence of reactions ( m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent SN2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results. [Figure not available: see fulltext.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

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

    Science.gov (United States)

    Wurtz, Jean David; Lee, Chiu Fan

    2018-02-01

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

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

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

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

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

    NARCIS (Netherlands)

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

    2015-01-01

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

  7. A study on the performance of condensation heat transfer for various working fluid of two-phase closed thermosyphons with various helical grooves

    International Nuclear Information System (INIS)

    Han, Kyu Il; Cho, Dong Hyun

    2005-01-01

    This study concerns the performance of condensing heat transfer in two-phase closed thermosyphons with various helical grooves. Distilled water, methanol, ethanol have been used as the working fluid. In the present work, a copper tube of the length of 1200mm and 14.28mm of inside diameter is used as the container of the thermosyphon. Each of the evaporator and the condenser section has a length of 550mm, while the remaining part of the thermosyphon tube is adiabatic section. A experimental study was carried out for analyzing the performances of having 50, 60, 70, 80, 90 helical grooves. A plain thermosyphon having the same inner and outer diameter as the grooved thermosyphons is also tested for the comparison. The type of working fluid and the numbers of grooves of the thermosyphons with various helical grooves have been used as the experimental parameters. The experimental results have been assessed and compared with existing theories. The results show that the type of working fluids are very important factors for the operation of thermosyphons. And the maximum enhancement (i.e. the ratio of the heat transfer coefficients the helical thermosyphons to plain thermosyphons) is 1.5∼2 for condensation

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

    Directory of Open Access Journals (Sweden)

    Yang Gao

    2014-01-01

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

  9. Orthogonality Catastrophe as a prerequisite for the irreversible decay of the global relative phase of a two-component Bose-Einstein condensate

    Science.gov (United States)

    Birman, Joseph L.; Kuklov, A. B.

    2001-05-01

    The concept of the orthogonality catastrophe (OC), which has been introduced previously for one component condensate ( A.B. Kuklov, J.L. Birman, PRA 63), 013609 (2001), is applied to the two-component condensate. The evolution of the global relative phase, which is created by the rf-pulse, is studied under the condition of no exchange of bosons between the components after the pulse. It is shown that the normal component does not induce the OC. Instead, it produces a reversible thermal dephasing, which competes with the quantum phase diffusion (QPD) effect (E.M.Wright, et al, PRL 77), 2158(1996). The thermal dephasing results from the thermal ensemble averaging, and the corresponding dephasing rate is controlled by the two-body interaction and temperature as well as by the closeness to the intrinsic su(2) symmetry, so that no dephasing exists in the case of the exact symmetry (A.B. Kuklov, J.L. Birman, PRL 85), 5488 (2000). The reversible nature of the thermal dephasing as well as of the QPD can be revealed in the atomic echo effect. The role of external noise in erasing the phase memory is discussed as well.

  10. Experimental facility with two-phase flow and with high concentration of non-condensable gases for research and development of emergency cooling system of advanced nuclear reactors

    International Nuclear Information System (INIS)

    Macedo, Luiz Alberto; Baptista Filho, Benedito Dias

    2006-01-01

    The development of emergency cooling passive systems of advanced nuclear reactors requires the research of some relative processes to natural circulation, in two-phase flow conditions involving condensation processes in the presence of non-condensable gases. This work describes the main characteristics of the experimental facility called Bancada de Circulacao Natural (BCN), designed for natural circulation experiments in a system with a hot source, electric heater, a cold source, heat exchanger, operating with two-phase flow and with high concentration of noncondensable gas, air. The operational tests, the data acquisition system and the first experimental results in natural circulation are presented. The experiments are transitory in natural circulation considering power steps. The distribution of temperatures and the behavior of the flow and of the pressure are analyzed. The experimental facility, the instrumentation and the data acquisition system demonstrated to be adapted for the purposes of research of emergency cooling passive systems, operating with two-phase flow and with high concentration of noncondensable gases. (author)

  11. Rydberg phases of Hydrogen and low energy nuclear reactions

    Science.gov (United States)

    Olafsson, Sveinn; Holmlid, Leif

    2016-03-01

    For over the last 26 years the science of cold fusion/LENR has been researched around the world with slow pace of progress. Modest quantity of excess heat and signatures of nuclear transmutation and helium production have been confirmed in experiments and theoretical work has only resulted in a large flora of inadequate theoretical scenarios. Here we review current state of research in Rydberg matter of Hydrogen that is showing strong signature of nuclear processes. In the presentation experimental behavior of Rydberg matter of hydrogen is described. An extensive collaboration effort of surface physics, catalysis, atomic physics, solid state physics, nuclear physics and quantum information is need to tackle the surprising experimental results that have so far been obtained. Rydberg matter of Hydrogen is the only known state of matter that is able to bring huge collection of protons to so short distances and for so long time that tunneling becomes a reasonable process for making low energy nuclear reactions. Nuclear quantum entanglement can also become realistic process at theses conditions.

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

    International Nuclear Information System (INIS)

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

    1996-01-01

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

  13. Design and performance of a mechanically pumped two-phase loop to support the evaporation-condensation experiments on the TZ1

    Directory of Open Access Journals (Sweden)

    Z.R. Wang

    2017-09-01

    Full Text Available The mechanically pumped two-phase loop (MPTL has the advantages of long distance heat transport, high heat density and good temperature control. On TZ1, the MPTL technology is adopted to support a series experiments of evaporation and condensation. The main objective is to provide accurate (±0.5 ℃ temperature control from −5 ℃ to 40 ℃ and remove 80 W heat from the experimental setup. In this paper, the requirements, system design, hardware and performance of the MPTL are introduced.

  14. Random-lattice models and simulation algorithms for the phase equilibria in two-dimensional condensed systems of particles with coupled internal and translational degrees of freedom

    DEFF Research Database (Denmark)

    Nielsen, Morten; Miao, Ling; Ipsen, John Hjorth

    1996-01-01

    In this work we concentrate on phase equilibria in two-dimensional condensed systems of particles where both translational and internal degrees of freedom are present and coupled through microscopic interactions, with a focus on the manner of the macroscopic coupling between the two types...... where the spin degrees of freedom are slaved by the translational degrees of freedom and develop a first-order singularity in the order-disorder transition that accompanies the lattice-melting transition. The internal degeneracy of the spin states in model III implies that the spin order...

  15. Phase separation of a Lennard-Jones fluid interacting with a long, condensed polymer chain: implications for the nuclear body formation near chromosomes.

    Science.gov (United States)

    Oh, Inrok; Choi, Saehyun; Jung, YounJoon; Kim, Jun Soo

    2015-08-28

    Phase separation in a biological cell nucleus occurs in a heterogeneous environment filled with a high density of chromatins and thus it is inevitably influenced by interactions with chromatins. As a model system of nuclear body formation in a cell nucleus filled with chromatins, we simulate the phase separation of a low-density Lennard-Jones (LJ) fluid interacting with a long, condensed polymer chain. The influence of the density variation of LJ particles above and below the phase boundary and the role of attractive interactions between LJ particles and polymer segments are investigated at a fixed value of strong self-interaction between LJ particles. For a density of LJ particles above the phase boundary, phase separation occurs and a dense domain of LJ particles forms irrespective of interactions with the condensed polymer chain whereas its localization relative to the polymer chain is determined by the LJ-polymer attraction strength. Especially, in the case of moderately weak attractions, the domain forms separately from the polymer chain and subsequently associates with the polymer chain. When the density is below the phase boundary, however, the formation of a dense domain is possible only when the LJ-polymer attraction is strong enough, for which the domain grows in direct contact with the interacting polymer chain. In this work, different growth behaviors of LJ particles result from the differences in the density of LJ particles and in the LJ-polymer interaction, and this work suggests that the distinct formation of activity-dependent and activity-independent nuclear bodies (NBs) in a cell nucleus may originate from the differences in the concentrations of body-specific NB components and in their interaction with chromatins.

  16. SLAC synchronous condenser

    International Nuclear Information System (INIS)

    Corvin, C.

    1995-06-01

    A synchronous condenser is a synchronous machine that generates reactive power that leads real power by 90 degrees in phase. The leading reactive power generated by the condenser offsets or cancels the normal lagging reactive power consumed by inductive and nonlinear loads at the accelerator complex. The quality of SLAC's utility power is improved with the addition of the condenser. The inertia of the condenser's 35,000 pound rotor damps and smoothes voltage excursions on two 12 kilovolt master substation buses, improving voltage regulation site wide. The condenser absorbs high frequency transients and noise in effect ''scrubbing'' the electric system power at its primary distribution source. In addition, the condenser produces a substantial savings in power costs. Federal and investor owned utilities that supply electric power to SLAC levy a monthly penalty for lagging reactive power delivered to the site. For the 1993 fiscal year this totaled over $285,000 in added costs for the year. By generating leading reactive power on site, thereby reducing total lagging reactive power requirements, a substantial savings in electric utility bills is achieved. Actual savings of $150,000 or more a year are possible depending on experimental operations

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

    International Nuclear Information System (INIS)

    Benner, C.L.

    1985-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1967-07-01

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

  19. Pion condensation and neutron star dynamics

    International Nuclear Information System (INIS)

    Kaempfer, B.

    1983-01-01

    The question of formation of pion condensate via a phase transition in nuclear matter, especially in the core of neutron stars is reviewed. The possible mechanisms and the theoretical restrictions of pion condensation are summarized. The effects of ultradense equation of state and density jumps on the possible condensation phase transition are investigated. The possibilities of observation of condensation process are described. (D.Gy.)

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

    Science.gov (United States)

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

    2016-11-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-05

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Leyrit, P

    1999-06-28

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

  3. Condensed matter physics

    International Nuclear Information System (INIS)

    Anon.

    1985-01-01

    The condensed matter physics research in the Physics Department of Risoe National Laboratory is predominantly experimental utilising diffraction of neutrons and x-rays. The research topics range from studies of structure, excitations and phase transitions in model systems to studies of ion transport, texture and recrystallization kinetics with a more applied nature. (author)

  4. Driving CO2 to a Quasi-Condensed Phase at the Interface between a Nanoparticle Surface and a Metal-Organic Framework at 1 bar and 298 K.

    Science.gov (United States)

    Lee, Hiang Kwee; Lee, Yih Hong; Morabito, Joseph V; Liu, Yejing; Koh, Charlynn Sher Lin; Phang, In Yee; Pedireddy, Srikanth; Han, Xuemei; Chou, Lien-Yang; Tsung, Chia-Kuang; Ling, Xing Yi

    2017-08-23

    We demonstrate a molecular-level observation of driving CO 2 molecules into a quasi-condensed phase on the solid surface of metal nanoparticles (NP) under ambient conditions of 1 bar and 298 K. This is achieved via a CO 2 accumulation in the interface between a metal-organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. Using real-time surface-enhanced Raman scattering spectroscopy, a >18-fold enhancement of surface coverage of CO 2 is observed at the interface. The high surface concentration leads CO 2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO 2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO 2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (>10 5 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO 2 conversion and ambient solid-gas operation.

  5. The influence of N-7 guanine modifications on the strength of Watson-Crick base pairing and guanine N-1 acidity: Comparison of gas-phase and condensed-phase trends

    Czech Academy of Sciences Publication Activity Database

    Burda, J. V.; Šponer, Jiří; Hrabáková, J.; Zeizinger, M.; Leszczynski, J.

    2003-01-01

    Roč. 107, č. 22 (2003), s. 5349-5356 ISSN 1520-6106 R&D Projects: GA MŠk ME 517; GA MŠk LN00A016 Grant - others:Wellcome Trust(GB) GR067507MF; ONR(US) N00034-03-1-0116; National Science Foundation(US) CREST 9805465 Institutional research plan: CEZ:AV0Z5004920 Keywords : Watson-Crick base pairing * guanines * gas-phase and condensed-phase trends Subject RIV: BO - Biophysics Impact factor: 3.679, year: 2003

  6. Simple phenomenological model for phase transitions in confined geometry. 2. Capillary condensation/evaporation in cylindrical mesopores.

    Science.gov (United States)

    Pellenq, Roland J-M; Coasne, Benoit; Denoyel, Renaud O; Coussy, O

    2009-02-03

    A simple phenomenological model that describes capillary condensation and evaporation of pure fluids confined in cylindrical mesopores is presented. Following the work of Celestini (Celestini, F. Phys. Lett. A 1997, 228, 84), the free energy density of the system is derived using interfacial tensions and a corrective term that accounts for the interaction coupling between the vapor/adsorbed liquid and the adsorbed liquid/adsorbent interfaces. This corrective term is shown to be consistent with the Gibbs adsorption isotherm and assessed by standard adsorption tests. This model reveals that capillary condensation and evaporation are metastable and equilibrium processes, respectively, hence exhibiting the existence of a hysteresis loop inadsorption/desorption isotherm that is well-known in experiment. We extend the phenomenological model of Celestini to give a quantitative description of adsorption on the pore wall and hysteresis width evolution with temperature and confinement. Direct quantitative comparison is made with experimental data for confined argon. Used as a characterizing tool, this integrated model allows in a single fit of an experimental adsorption/desorption isotherm assessing essential characterization data such as the specific surface area, pore volume, and mean pore size.

  7. Condensed matter physics

    CERN Document Server

    Marder, Michael P

    2010-01-01

    This Second Edition presents an updated review of the whole field of condensed matter physics. It consolidates new and classic topics from disparate sources, teaching not only about the effective masses of electrons in semiconductor crystals and band theory, but also about quasicrystals, dynamics of phase separation, why rubber is more floppy than steel, granular materials, quantum dots, Berry phases, the quantum Hall effect, and Luttinger liquids.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-05-01

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

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

    Science.gov (United States)

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

    2018-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-14

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

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  12. 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.

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

    NARCIS (Netherlands)

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

    2015-01-01

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

  14. Phase space conduits for reaction in multidimensional systems : HCN isomerization in three dimensions

    NARCIS (Netherlands)

    Waalkens, Holger; Burbanks, Andrew; Wiggins, Stephen

    2004-01-01

    The three-dimensional hydrogen cyanide/isocyanide isomerization problem is taken as an example to present a general theory for computing the phase space structures which govern classical reaction dynamics in systems with an arbitrary (finite) number of degrees of freedom. The theory, which is

  15. Analysis of coupled mass transfer and sol-gel reaction in a two-phase system

    NARCIS (Netherlands)

    Castelijns, H.J.; Huinink, H.P.; Pel, L.; Zitha, P.L.J.

    2006-01-01

    The coupled mass transfer and chemical reactions of a gel-forming compound in a two-phase system were studied in detail. Tetra-methyl-ortho-silicate (TMOS) is often used as a precursor in sol-gel chemistry to produce silica gels in aqueous systems. TMOS can also be mixed with many hydrocarbons

  16. Process Intensification. Continuous Two-Phase Catalytic Reactions in a Table-Top Centrifugal Contact Separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Schuur, Boelo; van Zwol, Floris; Haak, Robert M.; Minnaard, Adriaan J.; Feringa, Ben L.; Heeres, Hero J.; de Vries, Johannes G.; Prunier, ML

    2009-01-01

    Production of fine chemicals is mostly performed in batch reactors. Use of continuous processes has many advantages which may reduce the cost of production. We have developed the use of centrifugal contact separators (CCSs) for continuous two-phase catalytic reactions. This equipment has previously

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

    NARCIS (Netherlands)

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

    2001-01-01

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

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

    Science.gov (United States)

    Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey

    2015-04-01

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

  19. Uranium fluoride chemistry. Part 1. The gas phase reaction of uranium hexafluoride with alcohols

    International Nuclear Information System (INIS)

    Schnautz, N.G.; Venter, P.J.

    1992-01-01

    The reaction between uranium hexafluoride (UF 6 ) and simple alcohols in the gas phase was observed to proceed by way of three possible reaction pathways involving dehydration, deoxygenative fluorination, and ether formation. These reactions can best be explained by assuming that alcohols first react with UF 6 to afford the alkoxy uranium pentafluoride intermediate ROUF 5 , which reacts further to give the dehydration, deoxygenative fluorination, and ether products. In each of the above three reaction pathways, UF 6 is transformed to UOF 4 , which being as reactive toward alcohols as UF 6 , reacts further with the alcohol in question to finally afford the unreactive uranyl fluoride (UO 2 F 2 ). 6 refs., 2 tabs

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

    Science.gov (United States)

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

    2011-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-10

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

  2. Polariton condensates

    International Nuclear Information System (INIS)

    Snoke, David; Littlewood, Peter

    2010-01-01

    Most students of physics know about the special properties of Bose-Einstein condensates (BECs) as demonstrated in the two best-known examples: superfluid helium-4, first reported in 1938, and condensates of trapped atomic gases, first observed in 1995. (See the article by Wolfgang Ketterle in PHYSICS TODAY, December 1999, page 30.) Many also know that superfluid 3 He and superconducting metals contain BECs of fermion pairs. An underlying principle of all those condensed-matter systems, known as quantum fluids, is that an even number of fermions with half-integer spin can be combined to make a composite boson with integer spin. Such composite bosons, like all bosons, have the property that below some critical temperature--roughly the temperature at which the thermal de Broglie wavelength becomes comparable to the distance between the bosons--the total free energy is minimized by having a macroscopic number of bosons enter a single quantum state and form a macroscopic, coherent matter wave. Remarkably, the effect of interparticle repulsion is to lead to quantum mechanical exchange interactions that make that state robust, since the exchange interactions add coherently.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-01-01

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

  4. The geometric phase in quantum systems foundations, mathematical concepts, and applications in molecular and condensed matter physics

    CERN Document Server

    Böhm, Arno; Koizumi, Hiroyasu; Niu, Qian; Zwanziger, Joseph

    2003-01-01

    Aimed at graduate physics and chemistry students, this is the first comprehensive monograph covering the concept of the geometric phase in quantum physics from its mathematical foundations to its physical applications and experimental manifestations It contains all the premises of the adiabatic Berry phase as well as the exact Anandan-Aharonov phase It discusses quantum systems in a classical time-independent environment (time dependent Hamiltonians) and quantum systems in a changing environment (gauge theory of molecular physics) The mathematical methods used are a combination of differential geometry and the theory of linear operators in Hilbert Space As a result, the monograph demonstrates how non-trivial gauge theories naturally arise and how the consequences can be experimentally observed Readers benefit by gaining a deep understanding of the long-ignored gauge theoretic effects of quantum mechanics and how to measure them

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

    Science.gov (United States)

    Peng, Zhou; McLuckey, Scott A.

    2015-01-01

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

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

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

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

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

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

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

  8. Transport diphasique de gaz et de condensat. Aspects techniques et économiques Technical and Economic Aspects of Two-Phase Pipelining of Gas and Condensate

    Directory of Open Access Journals (Sweden)

    Bourgeois T.

    2006-11-01

    Full Text Available L'évacuation diphasique de la production d'un gisement de gaz à condensat présente des avantages importants, en particulier sur le plan économique. Les caractéristiques des écoulements diphasiques sont exposées, avec les conséquences principales sur la définition d'un schéma d'exploitation. Une comparaison économique est ensuite présentée, pour illustrer la réduction des investissements qui peut être apportée par l'évacuation diphasique de la production. Enfin, les recherches françaises sur les écoulements diphasiques dans les conduites pétrolières sont brièvement décrites, ainsi qu'un exemple de calcul sur une conduite de gaz à condensat en exploitation diphasique. The two-phase pipelining of a wet gas field production presents many advantages, especially from an economic point of view. The characteristics of two-phase flow are described, together with their main consequences on the operational scheme. Then an economic comparison is made to illustrate the reduction in investment costs that can by achieved with two-phase pipelining. Research in France on two-phase flow in gas and condensate pipelines is briefly described, and an example is given of the designing of a wet-gas pipeline currently being operated in the two-phase mode.

  9. From cation to oxide: hydroxylation and condensation of aqueous complexes

    International Nuclear Information System (INIS)

    Jolivet, J.P.

    1997-01-01

    Hydroxylation, condensation and precipitation of metal cations in aqueous solution are briefly reviewed. Hydroxylation of aqueous complexes essentially depends on the format charge (oxidation state), the size and the pH of the medium. It is the step allowing the condensation reaction. Depending on the nature of complexes (aqua-hydroxo, oxo-hydroxo), the. mechanism of condensation is different, olation or ox-olation respectively. The first one leads to poly-cations or hydroxides more or less stable against dehydration. The second one leads to poly-anions or oxides. Oligomeric species (poly-cations, poly-anions) are form from charged monomer complexes while the formation of solid phases requires non-charged precursors. Because of their high lability, charged oligomers are never the precursors of solids phases. The main routes for the formation of solid phases from solution are studied with two important and representative elements, Al and Si. For Al 3+ ions, different methods (base addition in solution, thermo-hydrolysis, hydrothermal synthesis) are discussed in relation to the crystal structure of the solid phase obtained. For silicic species condensing by ox-olation, the role of acid or base catalysis on the morphology of gels is studied. The influence of complexing ligands on the processes and on the characteristics of solids (morphology of particles, basic salts and polymetallic oxides formation) is studied. (author)

  10. Refrigeration. Heat Transfer. Part I: Evaporators and Condensers

    DEFF Research Database (Denmark)

    Knudsen, Hans-Jørgen Høgaard

    2002-01-01

    The note gives an introduction to heat transfer with phase shift. Pool Boiling, Flow Boiling, Condensation.......The note gives an introduction to heat transfer with phase shift. Pool Boiling, Flow Boiling, Condensation....

  11. Classification of phase transitions of finite Bose-Einstein condensates in power law traps by Fisher zeros

    NARCIS (Netherlands)

    Mülken, O.; Borrmann, P.; Harting, J.D.R.; Stamerjohanns, H.

    2001-01-01

    We present a detailed description of a classification scheme for phase transitions in finite systems based on the distribution of Fisher zeros of the canonical partition function in the complex temperature plane. We apply this scheme to finite Bose systems in power-law traps within a semi-analytic

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

    NARCIS (Netherlands)

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

    2016-01-01

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

  13. Condensed elementary particle matter

    International Nuclear Information System (INIS)

    Kajantie, K.

    1996-01-01

    Quark matter is a special case of condensed elementary particle matter, matter governed by the laws of particle physics. The talk discusses how far one can get in the study of particle matter by reducing the problem to computations based on the action. As an example the computation of the phase diagram of electroweak matter is presented. It is quite possible that ultimately an antireductionist attitude will prevail: experiments will reveal unpredicted phenomena not obviously reducible to the study of the action. (orig.)

  14. On the role of the activation procedure of supported hydrotalcites for base catalyzed reactions: Glycerol to glycerol carbonate and self-condensation of acetone

    NARCIS (Netherlands)

    Alvarez, M.G.; Frey, A.M.; Bitter, J.H.; Segarra, A.M.; Jong, de K.P.; Medina, F.

    2013-01-01

    Bulk and carbon nanofiber supported MgAl hydrotalcites have been investigated as solid base catalysts for the synthesis of glycerol carbonate and dicarbonate and for the self-condensation of acetone. The supported materials exhibited a 300 times higher activity compared to bulk activated

  15. Continuous-flow hydration–condensation reaction: Synthesis of α,β-unsaturated ketones from alkynes and aldehydes by using a heterogeneous solid acid catalyst

    Directory of Open Access Journals (Sweden)

    Magnus Rueping

    2011-12-01

    Full Text Available A simple, practical and efficient continuous-flow hydration–condensation protocol was developed for the synthesis of α,β-unsaturated ketones starting from alkynes and aldehydes by employing a heterogeneous catalyst in a flow microwave. The procedure presents a straightforward and convenient access to valuable differently substituted chalcones and can be applied on multigram scale.

  16. Condensation of exciton polaritons

    International Nuclear Information System (INIS)

    Kasprzak, J.

    2006-10-01

    Because of their unique property of bringing pure quantum effects into the real world scale, phase transitions towards condensed phases - like Bose-Einstein condensation (BEC), superfluidity, and superconductivity - have always fascinated scientists. The BEC, appearing upon cooling a gas of bosons below a critical temperature, has been given a striking demonstration in dilute atomic gases of rubidium atoms at temperatures below 200 nK. By confining photons in a semiconductor micro-cavity, and strongly coupling them to electronic excitations, one may create polaritons. These bosonic quasi-particles are 10 9 times lighter than rubidium atoms, thus theoretically allowing a BEC at standard cryogenic temperatures. Here we detail a comprehensive set of experiments giving compelling evidence for a BEC of polaritons. Above a critical density, we observe massive occupation of the ground state, developing from a thermalized and saturated distribution of the polariton population at (16-20) K. We demonstrate as well the existence of a critical temperature for this transition. The spontaneous onset of a coherent state is manifested by the increase of temporal coherence, the build-up of long-range spatial coherence and the reduction of the thermal noise observed in second order coherence experiments. The marked linear polarization of the emission from the condensate is also measured. All of these findings indicate the spontaneous onset of a macroscopic quantum phase. (author)

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

    Science.gov (United States)

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

    2010-03-01

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

  18. Optimization of phase analysis of refractory alloys in the gas-ion-reaction chamber

    International Nuclear Information System (INIS)

    Blumenkamp, H.J.; Hoven, H.; Koizlik, K.; Nickel, H.

    1980-04-01

    Reactor components outside the core which are under high thermal and mechanical stresses are made from refractory alloys. For basic research and for quality control, these materials are investigated by metallography, which is an independent group of characterization procedures as well as basis for many other methods. An important way of increasing the information about a material yielded by metallography is the expansions of phase contrast, in particular the phase contrasting in the gas-ion-reaction chamber. In this paper, the experimental procedure is described and the process of optimizing the procedure with respect to the Ni- and Fe-based refractory alloys examined in the IRW is discussed. (orig.) [de

  19. Irradiation of fish fillets: Relation of vapor phase reactions to storage quality

    Science.gov (United States)

    Spinelli, J.; Dollar, A.M.; Wedemeyer, G.A.; Gallagher, E.C.

    1969-01-01

    Fish fillets irradiated under air, nitrogen, oxygen, or carbon dioxide atmospheres developed rancidlike flavors when they were stored at refrigerated temperatures. Packing and irradiating under vacuum or helium prevented development of off-flavors during storage.Significant quantities of nitrate and oxidizing substances were formed when oxygen, nitrogen, or air were present in the vapor or liquid phases contained in a Pyrex glass model system exposed to ionizing radiation supplied by a 60Co source. It was demonstrated that the delayed flavor changes that occur in stored fish fillets result from the reaction of vapor phase radiolysis products and the fish tissue substrates.

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

    Science.gov (United States)

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

    2014-03-06

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

  1. Molecular dynamics study of kinetic boundary condition at an interface between a polyatomic vapor and its condensed phase

    OpenAIRE

    Ishiyama, Tatsuya; Yano, Takeru; Fujikawa, Shigeo

    2004-01-01

    The kinetic boundary condition for the Boltzmann equation at an interface between a polyatomic vapor and its liquid phase is investigated by the numerical method of molecular dynamics, with particular emphasis on the functional form of the evaporation part of the boundary condition, including the evaporation coefficient. The present study is an extension of a previous one for argon [Ishiyama, Yano, and Fujikawa, Phys. Fluids 16, 2899 (2004)] to water and methanol, typical examples of polyatom...

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

    International Nuclear Information System (INIS)

    Noest, A.J.

    1983-01-01

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

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  4. Procedure for the preparation of catalysts for application in catalytic gas phase reactions

    International Nuclear Information System (INIS)

    1976-01-01

    The invention describes the preparation of catalysts to be used in catalytic reactions in the gaseous phase. The catalytic material is disposed at the surface of a ceramic or carbon substrate (av. particle size 0.1 μ - 0.5 cm, surface area smaller than 20 m 2 /g) by bombardment of the catalytic material (Pt, Rh, Pd, Ru, Os, Ir) with energetic ions (Ne, Ar, Kr, Xe) in the vicinity of the substrate in medium vacuum

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  6. Two-phase, mass-transport model for direct methanol fuel cells with effect of non-equilibrium evaporation and condensation

    Science.gov (United States)

    Yang, W. W.; Zhao, T. S.

    A two-phase, mass-transport model for liquid-feed direct methanol fuel cells (DMFCs) is developed by taking into account the effect of non-equilibrium evaporation and condensation of methanol and water. The comparison between the present model and other models indicates that the present model yields more reasonable predictions of cell performance. Particularly, it is shown that the models that invoke a thermodynamic-equilibrium assumption between phases will overestimate mass-transport rates of methanol and water, thereby resulting in an inaccurate prediction of cell performance. The parametric study using the present model reveals that the gas coverage at the flow channel-diffusion-layer interface is directly related to the gas-void fraction inside the anode porous region; increasing the gas-void fraction will increase the mass-transfer resistance of methanol and thus lower cell performance. The effects of the geometric dimensions of the cell structure, such as channel width and rib width, on cell performance are also investigated with the model developed in this work.

  7. Field-induced phase transition in a metalorganic spin-dimer system-a potential model system to study Bose-Einstein condensation of magnons

    International Nuclear Information System (INIS)

    Tsui, Y.; Bruehl, A.; Removic-Langer, K.; Pashchenko, V.; Wolf, B.; Donath, G.; Pikul, A.; Kretz, T.; Lerner, H.-W.; Wagner, M.; Salguero, A.; Saha-Dasgupta, T.; Rahaman, B.; Valenti, R.; Lang, M.

    2007-01-01

    We report on the results obtained from studying electron spin resonance, magnetic susceptibility, specific heat and thermal expansion experiments on a metalorganic spin-dimer system, C 36 H 48 Cu 2 F 6 N 8 O 12 S 2 (TK91). According to the first principle Density Functional Theory calculations, the compound represents a 3D-coupled dimer system with intradimer coupling J 1 /k B ∼ 10K and interdimer couplings J 2 /k B ∼J 3 /k B ∼ 1K. The measurements have been performed on both pressed powder and single-crystal samples in external magnetic fields up to 12T and at low temperatures down to ∼ 0.2K. Susceptibility measurements reveal a spin-gap behavior consistent with the theoretical results. Furthermore, clear indications of a field-induced phase transition have been observed. A similar field-induced phase transition was also detected in an inorganic compound TlCuCl 3 and was interpreted as Bose-Einstein condensation (BEC) of magnons. The possibility of changing both the intradimer and interdimer couplings in TK91 by chemical substitutions makes the system a potentially good system to study BEC of magnons

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

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

    International Nuclear Information System (INIS)

    Hiraoka, Kenzo

    1977-01-01

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

  10. Polyoxyethylene/styrene - a model system for studying reaction-induced phase separation (RIPS)

    International Nuclear Information System (INIS)

    Sutton, D.; Stanford, J.L.; Ryan, A.J.

    2003-01-01

    Full text: Reaction-induced, phase-separation has been studied in polymer blends. A model crystalline-amorphous system consisted of semi-crystalline polyoxyethylene (POE) dissolved in the monomer styrene, which was employed as a reactive solvent to ease processing. When the styrene was polymerised to polystyrene (PS) in the mould, phase-separation and phase-inversion are induced, and a polymer blend was formed. POE was selected with a molar mass, Mn = 8578 g mol -1 and a polydispersity of 1.19 as determined using GPC. The polymerisation of styrene was initiated using 1 wt-% benzoin methyl ether (BME) and 0.2 wt-% 2,2'-azobisisobutyronitrile (AIBN) under ultra-violet (UV) light. The polymerisation kinetics were determined by monitoring the reduction in the intensity of the C=C stretching vibration band at 1631 cm -1 in the Raman spectrum of styrene. The onset times for the liquid-solid (L-S) phase-separation and crystallisation of POE from styrene/PS were observed using simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). Onset times for L-S phase-separation determined from the SAXS data were combined with the styrene polymerisation kinetics to plot the L-S phase-separation data onto a ternary phase diagram for the reactive system POE/styrene/PS at 45 and 50 deg C

  11. Kinetics of mineral condensation in the solar nebula

    International Nuclear Information System (INIS)

    Grove, T.L.

    1987-01-01

    A natural extension of the type of gas-mineral-melt condensation experiments is to study the gas-mineral-melt reaction process by controlling the reaction times of appropriate gas compositions with silicate materials. In a condensing and vaporizing gas-solid system, important processes that could influence the composition of and speciation in the gas phase are the kinetics of vaporization of components from silicate crystals and melts. The high vacuum attainable in the space station would provide an environment for studying these processes at gas pressures much lower than those obtainable in experimental devices operated at terrestrial conditions in which the gas phase and mineral or melt would be allowed to come to exchange equilibrium. Further experiments would be performed at variable gas flow rates to simulate disequilibrium vapor fractionation. In this type of experiment it is desirable to analyze directly the species in the gas phase in equilibrium with the condensed silicate material. This analytical method would provide a direct determination of the species present in the gas phase. Currently, the notion of gas speciation is based on calculations from thermodynamic data. The proposed experiments require similar furnace designs and use similar experimental starting compositions, pressures, and temperatures as those described by Mysen

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

    Science.gov (United States)

    Gamez-Garcia, Victoria G; Galano, Annia

    2017-10-05

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

  13. Models of coherent exciton condensation

    International Nuclear Information System (INIS)

    Littlewood, P B; Eastham, P R; Keeling, J M J; Marchetti, F M; Simons, B D; Szymanska, M H

    2004-01-01

    That excitons in solids might condense into a phase-coherent ground state was proposed about 40 years ago, and has been attracting experimental and theoretical attention ever since. Although experimental confirmation has been hard to come by, the concepts released by this phenomenon have been widely influential. This tutorial review discusses general aspects of the theory of exciton and polariton condensates, focusing on the reasons for coherence in the ground state wavefunction, the BCS to Bose crossover(s) for excitons and for polaritons, and the relationship of the coherent condensates to standard lasers

  14. Models of coherent exciton condensation

    Energy Technology Data Exchange (ETDEWEB)

    Littlewood, P B [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Eastham, P R [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Keeling, J M J [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Marchetti, F M [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Simons, B D [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Szymanska, M H [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom)

    2004-09-08

    That excitons in solids might condense into a phase-coherent ground state was proposed about 40 years ago, and has been attracting experimental and theoretical attention ever since. Although experimental confirmation has been hard to come by, the concepts released by this phenomenon have been widely influential. This tutorial review discusses general aspects of the theory of exciton and polariton condensates, focusing on the reasons for coherence in the ground state wavefunction, the BCS to Bose crossover(s) for excitons and for polaritons, and the relationship of the coherent condensates to standard lasers.

  15. Thermochemistry of methoxythiophenes: Measurement of their enthalpies of vaporization and estimation of their enthalpies of formation in the condensed phase

    International Nuclear Information System (INIS)

    Temprado, Manuel; Notario, Rafael; Roux, María Victoria; Verevkin, Sergey P.

    2014-01-01

    Highlights: • The enthalpies of vaporization of 2- and 3-methoxythiophenes have been measured by the transpiration method. • We have estimated the enthalpies of formation of methoxythiophenes in liquid phase. • The optimized geometries of methoxythiophenes have been tabulated and compared with the experimental crystal structures. - Abstract: Enthalpies of vaporization of 2- and 3-methoxythiophenes (48.32 ± 0.30 and 48.54 ± 0.22 kJ · mol −1 , respectively) have been measured by the transpiration method using nitrogen as the carrying and protecting stream. Combustion experiments leading to enthalpies of formation in the liquid phase, Δ f H 0 m (l), for both isomers failed due to rapid darkening of freshly distilled samples even under a protecting atmosphere. However, combination of experimental vaporization enthalpies with values of the gaseous enthalpies of formation, Δ f H 0 m (g), obtained by quantum-chemical calculations from our previous work Notario et al. (2012) [24] permits establishing estimated Δ f H 0 m (l) values of −(68.3 ± 4.2) and −(80.1 ± 4.2) kJ · mol −1 , for 2- and 3-methoxythiophene, respectively

  16. Final Technical Report for Quantum Embedding for Correlated Electronic Structure in Large Systems and the Condensed Phase

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Garnet Kin-Lic [Princeton Univ., NJ (United States)

    2017-04-30

    This is the final technical report. We briefly describe some selected results below. Developments in density matrix embedding. DMET is a quantum embedding theory that we introduced at the beginning of the last funding period, around 2012-2013. Since the first DMET papers, which demonstrated proof-of- principle calculations on the Hubbard model and hydrogen rings, we have carried out a number of different developments, including: Extending the DMET technology to compute broken symmetry phases, including magnetic phases and super- conductivity (Pub. 13); Calibrating the accuracy of DMET and its cluster size convergence against other methods, and formulation of a dynamical cluster analog (Pubs. 4, 10) (see Fig. 1); Implementing DMET for ab-initio molecular calculations, and exploring different self-consistency criteria (Pubs. 9, 14); Using embedding to defi ne quantum classical interfaces Pub. 2; Formulating DMET for spectral functions (Pub. 7) (see Fig. 1); Extending DMET to coupled fermion-boson problems (Pub. 12). Together with these embedding developments, we have also implemented a wide variety of impurity solvers within our DMET framework, including DMRG (Pub. 3), AFQMC (Pub. 10), and coupled cluster theory (CC) (Pub. 9).

  17. 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)

  18. Multistate electron transfer dynamics in the condensed phase: Exact calculations from the reduced hierarchy equations of motion approach

    International Nuclear Information System (INIS)

    Tanaka, Midori; Tanimura, Yoshitaka

    2010-01-01

    Multiple displaced oscillators coupled to an Ohmic heat bath are used to describe electron transfer (ET) in a dissipative environment. By performing a canonical transformation, the model is reduced to a multilevel system coupled to a heat bath with the Brownian spectral distribution. A reduced hierarchy equations of motion approach is introduced for numerically rigorous simulation of the dynamics of the three-level system with various oscillator configurations, for different nonadiabatic coupling strengths and damping rates, and at different temperatures. The time evolution of the reduced density matrix elements illustrates the interplay of coherences between the electronic and vibrational states. The ET reaction rates, defined as a flux-flux correlation function, are calculated using the linear response of the system to an external perturbation as a function of activation energy. The results exhibit an asymmetric inverted parabolic profile in a small activation regime due to the presence of the intermediate state between the reactant and product states and a slowly decaying profile in a large activation energy regime, which arises from the quantum coherent transitions.

  19. Condensed Matter Nuclear Science

    Science.gov (United States)

    Biberian, Jean-Paul

    2006-02-01

    1. General. A tribute to gene Mallove - the "Genie" reactor / K. Wallace and R. Stringham. An update of LENR for ICCF-11 (short course, 10/31/04) / E. Storms. New physical effects in metal deuterides / P. L. Hagelstein ... [et al.]. Reproducibility, controllability, and optimization of LENR experiments / D. J. Nagel -- 2. Experiments. Electrochemistry. Evidence of electromagnetic radiation from Ni-H systems / S. Focardi ... [et al.]. Superwave reality / I. Dardik. Excess heat in electrolysis experiments at energetics technologies / I. Dardik ... [et al.]. "Excess heat" during electrolysis in platinum/K[symbol]CO[symbol]/nickel light water system / J. Tian ... [et al.]. Innovative procedure for the, in situ, measurement of the resistive thermal coefficient of H(D)/Pd during electrolysis; cross-comparison of new elements detected in the Th-Hg-Pd-D(H) electrolytic cells / F. Celani ... [et al.]. Emergence of a high-temperature superconductivity in hydrogen cycled Pd compounds as an evidence for superstoihiometric H/D sites / A. Lipson ... [et al.]. Plasma electrolysis. Calorimetry of energy-efficient glow discharge - apparatus design and calibration / T. B. Benson and T. O. Passell. Generation of heat and products during plasma electrolysis / T. Mizuno ... [et al.]. Glow discharge. Excess heat production in Pd/D during periodic pulse discharge current in various conditions / A. B. Karabut. Beam experiments. Accelerator experiments and theoretical models for the electron screening effect in metallic environments / A. Huke, K. Czerski, and P. Heide. Evidence for a target-material dependence of the neutron-proton branching ratio in d+d reactions for deuteron energies below 20keV / A. Huke ... [et al.]. Experiments on condensed matter nuclear events in Kobe University / T. Minari ... [et al.]. Electron screening constraints for the cold fusion / K. Czerski, P. Heide, and A. Huke. Cavitation. Low mass 1.6 MHz sonofusion reactor / R. Stringham. Particle detection. Research

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

    International Nuclear Information System (INIS)

    Boulaud, Denis

    1977-01-01

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

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

    Science.gov (United States)

    Prentice, Boone M; McLuckey, Scott A

    2013-02-01

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

  2. Isotope effects and the temperature dependences of the hyperfine coupling constants of muoniated sec-butyl radicals in condensed phases.

    Science.gov (United States)

    Fleming, Donald G; Bridges, Michael D; Arseneau, Donald J; Chen, Ya Kun; Wang, Yan Alexander

    2011-04-07

    Reported here is the first μSR study of the muon (A(μ)) and proton (A(p)) β-hyperfine coupling constants (Hfcc) of muoniated sec-butyl radicals, formed by muonium (Mu) addition to 1-butene and to cis- and trans-2-butene. The data are compared with in vacuo spin-unrestricted MP2 and hybrid DFT/B3YLP calculations reported in the previous paper (I), which played an important part in the interpretation of the data. The T-dependences of both the (reduced) muon, A(μ)′(T), and proton, A(p)(T), Hfcc are surprisingly well explained by a simple model, in which the calculated Hfcc from paper I at energy minima of 0 and near ±120° are thermally averaged, assuming an energy dependence given by a basic 2-fold torsional potential. Fitted torsional barriers to A(μ)′(T) from this model are similar (~3 kJ/mol) for all muoniated butyl radicals, suggesting that these are dominated by ZPE effects arising from the C−Mu bond, but for A(p)(T) exhibit wide variations depending on environment. For the cis- and trans-2-butyl radicals formed from 2-butene, A(μ)′(T) exhibits clear discontinuities at bulk butene melting points, evidence for molecular interactions enhancing these muon Hfcc in the environment of the solid state, similar to that found in earlier reports for muoniated tert-butyl. In contrast, for Mu−sec-butyl formed from 1-butene, there is no such discontinuity. The muon hfcc for the trans-2-butyl radical are seemingly very well predicted by B3LYP calculations in the solid phase, but for sec-butyl from 1-butene, showing the absence of further interactions, much better agreement is found with the MP2 calculations across the whole temperature range. Examples of large proton Hfcc near 0 K are also reported, due to eclipsed C−H bonds, in like manner to C−Mu, which then also exhibit clear discontinuities in A(p)(T) at bulk melting points. The data suggest that the good agreement found between theory and experiment from the B3LYP calculations for eclipsed bonds in

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

    International Nuclear Information System (INIS)

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

    2004-01-01

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

  4. Manipulation of a Bose-Einstein condensate by a time-averaged orbiting potential using phase jumps of the rotating field

    NARCIS (Netherlands)

    Cleary, P.W.; Hijmans, T.W.; Walraven, J.T.M.

    2010-01-01

    We report on the manipulation of the center-of-mass motion ("sloshing") of a Bose-Einstein condensate in a time-averaged orbiting potential (TOP) trap. We start with a condensate at rest in the center of a static trapping potential. When suddenly replacing the static trap with a TOP trap centered

  5. Identification of secondary phases formed during unsaturated reaction of UO2 with EJ-13 water

    International Nuclear Information System (INIS)

    Bates, J.K.; Tani, B.S.; Veleckis, E.

    1989-01-01

    A set of experiments, wherein UO 2 has been contacted by dripping water, has been conducted over a period of 182.5 weeks. The experiments are being conducted to develop procedures to study spent fuel reaction under unsaturated conditions that are expected to exist over the lifetime of the proposed Yucca Mountain repository site. One half of the experiments have been terminated, while one half are ongoing. Analyses of solutions that have dripped from the reacted UO 2 have been performed for all experiments, while the reacted UO 2 surfaces have been examined for the terminated experiments. A pulse of uranium release from the UO 2 solid, combined with the formation of schoepite on the surface of the UO 2 , was observed between 39 and 96 weeks of reaction. Thereafter, the uranium release decreased and a second set of secondary phases was observed. The latter phases incorporated cations from the EJ-13 water and included boltwoodite, uranophane, sklodowskite, compreignacite, and schoepite. The experiments are continuing to monitor whether additional changes in solution chemistry or secondary phase formation occurs. 6 refs., 2 figs., 2 tabs

  6. Antimicrobial activity of silica coated silicon nano-tubes (SCSNT) and silica coated silicon nano-particles (SCSNP) synthesized by gas phase condensation.

    Science.gov (United States)

    Tank, Chiti; Raman, Sujatha; Karan, Sujoy; Gosavi, Suresh; Lalla, Niranjan P; Sathe, Vasant; Berndt, Richard; Gade, W N; Bhoraskar, S V; Mathe, Vikas L

    2013-06-01

    Silica-coated, silicon nanotubes (SCSNTs) and silica-coated, silicon nanoparticles (SCSNPs) have been synthesized by catalyst-free single-step gas phase condensation using the arc plasma process. Transmission electron microscopy and scanning tunneling microscopy showed that SCSNTs exhibited a wall thickness of less than 1 nm, with an average diameter of 14 nm and a length of several 100 nm. Both nano-structures had a high specific surface area. The present study has demonstrated cheaper, resistance-free and effective antibacterial activity in silica-coated silicon nano-structures, each for two Gram-positive and Gram-negative bacteria. The minimum inhibitory concentration (MIC) was estimated, using the optical densitometric technique, and by determining colony-forming units. The MIC was found to range in the order of micrograms, which is comparable to the reported MIC of metal oxides for these bacteria. SCSNTs were found to be more effective in limiting the growth of multidrug-resistant Staphylococcus aureus over SCSNPs at 10 μg/ml (IC 50 = 100 μg/ml).

  7. Dynamics of inhomogeneous chiral condensates

    Science.gov (United States)

    Carlomagno, Juan Pablo; Krein, Gastão; Kroff, Daniel; Peixoto, Thiago

    2018-01-01

    We study the dynamics of the formation of inhomogeneous chirally broken phases in the final stages of a heavy-ion collision, with particular interest on the time scales involved in the formation process. The study is conducted within the framework of a Ginzburg-Landau time evolution, driven by a free energy functional motivated by the Nambu-Jona-Lasinio model. Expansion of the medium is modeled by one-dimensional Bjorken flow and its effect on the formation of inhomogeneous condensates is investigated. We also use a free energy functional from a nonlocal Nambu-Jona-Lasinio model which predicts metastable phases that lead to long-lived inhomogeneous condensates before reaching an equilibrium phase with homogeneous condensates.

  8. Geometric phase and quantum interference in photosynthetic reaction center: Regulation of electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yuming, E-mail: ymsun@ytu.edu.cn; Su, Yuehua; Dai, Zhenhong; Wang, WeiTian

    2016-10-20

    Photosynthesis is driven by electron transfer in reaction centers in which the functional unit is composed of several simple molecules C{sub 2}-symmetrically arranged into two branches. In view of quantum mechanism, both branches are possible pathways traversed by the transferred electron. Due to different evolution of spin state along two pathways in transmembrane electric potential (TEP), quantum state of the transferred electron at the bridged site acquires a geometric phase difference dependent on TEP, the most efficient electron transport takes place in a specific range of TEP beyond which electron transfer is dramatically suppressed. What’s more, reaction center acts like elaborately designed quantum device preparing polarized spin dependent on TEP for the transferred electron to regulate the reduction potential at bridged site. In brief, electron transfer generates the TEP, reversely, TEP modulates the efficiency of electron transfer. This may be an important approach to maintaining an appreciable pH environment in photosynthesis.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-08-01

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

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

    CERN Document Server

    Kraft, M

    2003-01-01

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

  11. In-Space technology experiments program. A high efficiency thermal interface (using condensation heat transfer) between a 2-phase fluid loop and heatpipe radiator: Experiment definition phase

    Science.gov (United States)

    Pohner, John A.; Dempsey, Brian P.; Herold, Leroy M.

    1990-01-01

    Space Station elements and advanced military spacecraft will require rejection of tens of kilowatts of waste heat. Large space radiators and two-phase heat transport loops will be required. To minimize radiator size and weight, it is critical to minimize the temperature drop between the heat source and sink. Under an Air Force contract, a unique, high-performance heat exchanger is developed for coupling the radiator to the transport loop. Since fluid flow through the heat exchanger is driven by capillary forces which are easily dominated by gravity forces in ground testing, it is necessary to perform microgravity thermal testing to verify the design. This contract consists of an experiment definition phase leading to a preliminary design and cost estimate for a shuttle-based flight experiment of this heat exchanger design. This program will utilize modified hardware from a ground test program for the heat exchanger.

  12. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  13. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    International Nuclear Information System (INIS)

    Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso

    2012-01-01

    Highlights: ► Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. ► Gas chromatography and computational potential energy surfaces were performed. ► A mechanism in steps looked like the most probable mechanism. ► A spin–orbit coupling appeared at the singlet and triple diradical open structures. ► A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463–503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10 13 s −1 , respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G ∗∗ level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin–orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

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

    Science.gov (United States)

    Fang, Gu; Chen, Chih-chi

    2015-07-01

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

  15. Reaction

    African Journals Online (AJOL)

    abp

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

  16. Illustrating the Utility of X-Ray Crystallography for Structure Elucidation through a Tandem Aldol Condensation/Diels-Alder Reaction Sequence

    Science.gov (United States)

    Hoang, Giang T.; Kubo, Tomohiro; Young, Victor G., Jr.; Kautzky, Jacob A.; Wissinger, Jane E.

    2015-01-01

    Two introductory organic chemistry laboratory experiments are described based on the Diels-Alder reaction of 2,3,4,5-tetraphenylcyclopentadienone, which is synthesized prior to or in a one-pot reaction, with styrene. Students are presented with three possible products, the "endo" and "exo" diastereomers and the decarbonylated…

  17. Conditioning of radioactive ash residue in a wave of solid-phase exothermal reactions

    International Nuclear Information System (INIS)

    Karlina, O.K.; Varlakova, G.A.; Ozhovan, M.I.; Tivanskij, V.M.; Dmitriev, S.A.

    2001-01-01

    The abilities for utilization of exothermic reaction heat in solid phase for conditioning the ash residue produced as a result of solid radioactive waste burning are analyzed. It is shown that the process of ash residue making monolithic with obtaining the glass-like finish product containing 50-60 mass % of ash residue which meets the requirements for solidified radioactive wastes may be realized without energy supplying from external heat sources. The conditioning is realized in a special crucible furnace-container designed not only for the process conducting but also for subsequent storage or disposal of the finish product [ru

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

    Science.gov (United States)

    Minakata, Daisuke; Crittenden, John

    2011-04-15

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

  19. Fermion condensation and gapped domain walls in topological orders

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Yidun [Department of Physics and Center for Field Theory and Particle Physics, Fudan University,Shanghai 200433 (China); Collaborative Innovation Center of Advanced Microstructures, Nanjing University,Nanjing 210093 (China); Perimeter Institute for Theoretical Physics,Waterloo N2L 2Y5, Ontario (Canada); Wang, Chenjie [Perimeter Institute for Theoretical Physics,Waterloo N2L 2Y5, Ontario (Canada)

    2017-03-31

    We study fermion condensation in bosonic topological orders in two spatial dimensions. Fermion condensation may be realized as gapped domain walls between bosonic and fermionic topological orders, which may be thought of as real-space phase transitions from bosonic to fermionic topological orders. This picture generalizes the previous idea of understanding boson condensation as gapped domain walls between bosonic topological orders. While simple-current fermion condensation was considered before, we systematically study general fermion condensation and show that it obeys a Hierarchy Principle: a general fermion condensation can always be decomposed into a boson condensation followed by a minimal fermion condensation. The latter involves only a single self-fermion that is its own anti-particle and that has unit quantum dimension. We develop the rules of minimal fermion condensation, which together with the known rules of boson condensation, provides a full set of rules for general fermion condensation.

  20. Continuous condensation in nanogrooves

    Science.gov (United States)

    Malijevský, Alexandr

    2018-05-01

    We consider condensation in a capillary groove of width L and depth D , formed by walls that are completely wet (contact angle θ =0 ), which is in a contact with a gas reservoir of the chemical potential μ . On a mesoscopic level, the condensation process can be described in terms of the midpoint height ℓ of a meniscus formed at the liquid-gas interface. For macroscopically deep grooves (D →∞ ), and in the presence of long-range (dispersion) forces, the condensation corresponds to a second-order phase transition, such that ℓ ˜(μcc-μ ) -1 /4 as μ →μcc - where μc c is the chemical potential pertinent to capillary condensation in a slit pore of width L . For finite values of D , the transition becomes rounded and the groove becomes filled with liquid at a chemical potential higher than μc c with a difference of the order of D-3. For sufficiently deep grooves, the meniscus growth initially follows the power law ℓ ˜(μcc-μ ) -1 /4 , but this behavior eventually crosses over to ℓ ˜D -(μ-μc c) -1 /3 above μc c, with a gap between the two regimes shown to be δ ¯μ ˜D-3 . Right at μ =μc c , when the groove is only partially filled with liquid, the height of the meniscus scales as ℓ*˜(D3L) 1 /4 . Moreover, the chemical potential (or pressure) at which the groove is half-filled with liquid exhibits a nonmonotonic dependence on D with a maximum at D ≈3 L /2 and coincides with μc c when L ≈D . Finally, we show that condensation in finite grooves can be mapped on the condensation in capillary slits formed by two asymmetric (competing) walls a distance D apart with potential strengths depending on L . All these predictions, based on mesoscopic arguments, are confirmed by fully microscopic Rosenfeld's density functional theory with a reasonable agreement down to surprisingly small values of both L and D .

  1. Asymmetric condensed dark matter

    Energy Technology Data Exchange (ETDEWEB)

    Aguirre, Anthony; Diez-Tejedor, Alberto, E-mail: aguirre@scipp.ucsc.edu, E-mail: alberto.diez@fisica.ugto.mx [Santa Cruz Institute for Particle Physics and Department of Physics, University of California, Santa Cruz, CA, 95064 (United States)

    2016-04-01

    We explore the viability of a boson dark matter candidate with an asymmetry between the number densities of particles and antiparticles. A simple thermal field theory analysis confirms that, under certain general conditions, this component would develop a Bose-Einstein condensate in the early universe that, for appropriate model parameters, could survive the ensuing cosmological evolution until now. The condensation of a dark matter component in equilibrium with the thermal plasma is a relativistic process, hence the amount of matter dictated by the charge asymmetry is complemented by a hot relic density frozen out at the time of decoupling. Contrary to the case of ordinary WIMPs, dark matter particles in a condensate must be lighter than a few tens of eV so that the density from thermal relics is not too large. Big-Bang nucleosynthesis constrains the temperature of decoupling to the scale of the QCD phase transition or above. This requires large dark matter-to-photon ratios and very weak interactions with standard model particles.

  2. Saccadic reaction times to audiovisual stimuli show effects of oscillatory phase reset.

    Directory of Open Access Journals (Sweden)

    Adele Diederich

    Full Text Available Initiating an eye movement towards a suddenly appearing visual target is faster when an accessory auditory stimulus occurs in close spatiotemporal vicinity. Such facilitation of saccadic reaction time (SRT is well-documented, but the exact neural mechanisms underlying the crossmodal effect remain to be elucidated. From EEG/MEG studies it has been hypothesized that coupled oscillatory activity in primary sensory cortices regulates multisensory processing. Specifically, it is assumed that the phase of an ongoing neural oscillation is shifted due to the occurrence of a sensory stimulus so that, across trials, phase values become highly consistent (phase reset. If one can identify the phase an oscillation is reset to, it is possible to predict when temporal windows of high and low excitability will occur. However, in behavioral experiments the pre-stimulus phase will be different on successive repetitions of the experimental trial, and average performance over many trials will show no signs of the modulation. Here we circumvent this problem by repeatedly presenting an auditory accessory stimulus followed by a visual target stimulus with a temporal delay varied in steps of 2 ms. Performing a discrete time series analysis on SRT as a function of the delay, we provide statistical evidence for the existence of distinct peak spectral components in the power spectrum. These frequencies, although varying across participants, fall within the beta and gamma range (20 to 40 Hz of neural oscillatory activity observed in neurophysiological studies of multisensory integration. Some evidence for high-theta/alpha activity was found as well. Our results are consistent with the phase reset hypothesis and demonstrate that it is amenable to testing by purely psychophysical methods. Thus, any theory of multisensory processes that connects specific brain states with patterns of saccadic responses should be able to account for traces of oscillatory activity in observable

  3. The condensed matter physics

    International Nuclear Information System (INIS)

    Sapoval, B.

    1988-01-01

    The 1988 progress report of the laboratory of the Condensed Matter Physics (Polytechnic School, France), is presented. The Laboratory activities are related to the physics of semiconductors and disordered phases. The electrical and optical properties of the semiconductors, mixed conductor, superionic conductors and ceramics, are studied. Moreover, the interfaces of those systems and the sol-gel inorganic polymerization phenomena, are investigated. The most important results obtained, concern the following investigations: the electrochemical field effect transistor, the cathodoluminescence, the low energy secondary electrons emission, the fluctuations of a two-dimensional diffused junction and the aerogels [fr

  4. Dual approaches for defects condensation

    Energy Technology Data Exchange (ETDEWEB)

    Rougemont, Romulo; Grigorio, Leonardo de Souza; Wotzasek, Clovis [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil); Guimaraes, Marcelo Santos [Universidade do Estado do Rio de Janeiro (UERJ), RJ (Brazil)

    2009-07-01

    Full text. Due to the fact that the QCD running coupling constant becomes larger as we go into the low energy (or large distance) limit of the theory, a perturbative treatment of its infrared (IR) region is impossible. In particular, a formal mathematical demonstration of color confinement and a complete physical understanding of the exact mechanism that confines quarks and gluons are two missing points in our current knowledge of the IR-QCD. It was known that due to the Meissner effect of expulsion of magnetic fields in a electric condensate that usual superconductors should confine magnetic monopoles. That point led to the conjecture that the QCD vacuum could be a condensate of chromomagnetic monopoles, a dual superconductor (DSC). Such a chromomagnetic condensate should be responsible for the dual Meissner effect which is expected to lead to the confinement of color charges immersed in this medium. In dual superconductor models of color confinement, magnetic monopoles appear as topological defects in points of the space where the abelian projection becomes singular. Also, condensation of other kinds of defects such as vortices in superfluids and line-like defects in solids are responsible for a great variety of phase transitions, which once more proves the relevance of the subject. In the present work we review two methods that allow us to approach the condensation of defects: the Kleinert Mechanism (KM) and the Julia-Toulouse Mechanism (JTM). We show that in the limit where the vortex gauge field goes to zero, which we identify as the signature of the condensation of defects in the dual picture, these are two equivalent dual prescriptions for obtaining an effective theory for a phase where defects are condensed, starting from the fundamental theory defined in the normal phase where defects are diluted. (author)

  5. Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry

    Science.gov (United States)

    Colizza, Kevin; Yevdokimov, Alexander; McLennan, Lindsay; Smith, James L.; Oxley, Jimmie C.

    2018-01-01

    Our efforts to lower the detection limits of hexamethylene triperoxide diamine (HMTD) have uncovered previously unreported gas-phase reactions of primary and secondary amines with one of the six methylene carbons. The reaction occurs primarily in the atmospheric pressure chemical ionization (APCI) source and is similar to the behavior of alcohols with HMTD [1]. However, unlike alcohols, the amine reaction conserves the hydrogen peroxide on the intact product. Furthermore, with or without amines, HMTD is oxidized to tetramethylene diperoxide diamine dialdehyde (TMDDD) in a temperature-dependent fashion in the APCI source. Synthesized TMDDD forms very strong adducts (not products) to ammonium and amine ions in the electrospray ionization (ESI) source. Attempts to improve HMTD detection by generating TMDDD in the APCI source with post-column addition of amines were not successful. Signal intensity of the solvent related HMTD product in methanol, [HMTD+MeOH2-H2O2]+ (m/z 207.0975), was understandably related to the amount of methanol in the HMTD environment as it elutes into the source. With conditions optimized for this product, the detection of 100 pg on column was accomplished with a robust analysis of 300 pg (1.44 pmol) routinely performed on the Orbitrap mass spectrometers. [Figure not available: see fulltext.

  6. Universal Themes of Bose-Einstein Condensation

    Science.gov (United States)

    Proukakis, Nick P.; Snoke, David W.; Littlewood, Peter B.

    2017-04-01

    Foreword; List of contributors; Preface; Part I. Introduction: 1. Universality and Bose-Einstein condensation: perspectives on recent work D. W. Snoke, N. P. Proukakis, T. Giamarchi and P. B. Littlewood; 2. A history of Bose-Einstein condensation of atomic hydrogen T. Greytak and D. Kleppner; 3. Twenty years of atomic quantum gases: 1995-2015 W. Ketterle; 4. Introduction to polariton condensation P. B. Littlewood and A. Edelman; Part II. General Topics: Editorial notes; 5. The question of spontaneous symmetry breaking in condensates D. W. Snoke and A. J. Daley; 6. Effects of interactions on Bose-Einstein condensation R. P. Smith; 7. Formation of Bose-Einstein condensates M. J. Davis, T. M. Wright, T. Gasenzer, S. A. Gardiner and N. P. Proukakis; 8. Quenches, relaxation and pre-thermalization in an isolated quantum system T. Langen and J. Schmiedmayer; 9. Ultracold gases with intrinsic scale invariance C. Chin; 10. Berezinskii-Kosterlitz-Thouless phase of a driven-dissipative condensate N. Y. Kim, W. H. Nitsche and Y. Yamamoto; 11. Superfluidity and phase correlations of driven dissipative condensates J. Keeling, L. M. Sieberer, E. Altman, L. Chen, S. Diehl and J. Toner; 12. BEC to BCS crossover from superconductors to polaritons A. Edelman and P. B. Littlewood; Part III. Condensates in Atomic Physics: Editorial notes; 13. Probing and controlling strongly correlated quantum many-body systems using ultracold quantum gases I. Bloch; 14. Preparing and probing chern bands with cold atoms N. Goldman, N. R. Cooper and J. Dalibard; 15. Bose-Einstein condensates in artificial gauge fields L. J. LeBlanc and I. B. Spielman; 16. Second sound in ultracold atomic gases L. Pitaevskii and S. Stringari; 17. Quantum turbulence in atomic Bose-Einstein condensates N. G. Parker, A. J. Allen, C. F. Barenghi and N. P. Proukakis; 18. Spinor-dipolar aspects of Bose-Einstein condensation M. Ueda; Part IV. Condensates in Condensed Matter Physics: Editorial notes; 19. Bose

  7. Condensation model for the ESBWR passive condensers

    International Nuclear Information System (INIS)

    Revankar, S. T.; Zhou, W.; Wolf, B.; Oh, S.

    2012-01-01

    In the General Electric's Economic simplified boiling water reactor (GE-ESBWR) the passive containment cooling system (PCCS) plays a major role in containment pressure control in case of an loss of coolant accident. The PCCS condenser must be able to remove sufficient energy from the reactor containment to prevent containment from exceeding its design pressure following a design basis accident. There are three PCCS condensation modes depending on the containment pressurization due to coolant discharge; complete condensation, cyclic venting and flow through mode. The present work reviews the models and presents model predictive capability along with comparison with existing data from separate effects test. The condensation models in thermal hydraulics code RELAP5 are also assessed to examine its application to various flow modes of condensation. The default model in the code predicts complete condensation well, and basically is Nusselt solution. The UCB model predicts through flow well. None of condensation model in RELAP5 predict complete condensation, cyclic venting, and through flow condensation consistently. New condensation correlations are given that accurately predict all three modes of PCCS condensation. (authors)

  8. Mixed fermion-photon condensate in strongly coupled quantum electrodynamics

    International Nuclear Information System (INIS)

    Gusynin, V.P.; Kushnir, V.A.

    1989-01-01

    The existence of a new mixed fermion-photon condensate breaking chiral symmetry in strongly coupled phase of quantum electrodynamics is shown. An analytical expression for the renormalized condensate is obtained. 20 refs.; 2 figs

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

    Science.gov (United States)

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

    2016-02-15

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

  10. Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

    International Nuclear Information System (INIS)

    Del Ben, Mauro; Hutter, Jürg; VandeVondele, Joost

    2015-01-01

    The forces acting on the atoms as well as the stress tensor are crucial ingredients for calculating the structural and dynamical properties of systems in the condensed phase. Here, these derivatives of the total energy are evaluated for the second-order Møller-Plesset perturbation energy (MP2) in the framework of the resolution of identity Gaussian and plane waves method, in a way that is fully consistent with how the total energy is computed. This consistency is non-trivial, given the different ways employed to compute Coulomb, exchange, and canonical four center integrals, and allows, for example, for energy conserving dynamics in various ensembles. Based on this formalism, a massively parallel algorithm has been developed for finite and extended system. The designed parallel algorithm displays, with respect to the system size, cubic, quartic, and quintic requirements, respectively, for the memory, communication, and computation. All these requirements are reduced with an increasing number of processes, and the measured performance shows excellent parallel scalability and efficiency up to thousands of nodes. Additionally, the computationally more demanding quintic scaling steps can be accelerated by employing graphics processing units (GPU’s) showing, for large systems, a gain of almost a factor two compared to the standard central processing unit-only case. In this way, the evaluation of the derivatives of the RI-MP2 energy can be performed within a few minutes for systems containing hundreds of atoms and thousands of basis functions. With good time to solution, the implementation thus opens the possibility to perform molecular dynamics (MD) simulations in various ensembles (microcanonical ensemble and isobaric-isothermal ensemble) at the MP2 level of theory. Geometry optimization, full cell relaxation, and energy conserving MD simulations have been performed for a variety of molecular crystals including NH 3 , CO 2 , formic acid, and benzene

  11. Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

    Science.gov (United States)

    Del Ben, Mauro; Hutter, Jürg; VandeVondele, Joost

    2015-09-01

    The forces acting on the atoms as well as the stress tensor are crucial ingredients for calculating the structural and dynamical properties of systems in the condensed phase. Here, these derivatives of the total energy are evaluated for the second-order Møller-Plesset perturbation energy (MP2) in the framework of the resolution of identity Gaussian and plane waves method, in a way that is fully consistent with how the total energy is computed. This consistency is non-trivial, given the different ways employed to compute Coulomb, exchange, and canonical four center integrals, and allows, for example, for energy conserving dynamics in various ensembles. Based on this formalism, a massively parallel algorithm has been developed for finite and extended system. The designed parallel algorithm displays, with respect to the system size, cubic, quartic, and quintic requirements, respectively, for the memory, communication, and computation. All these requirements are reduced with an increasing number of processes, and the measured performance shows excellent parallel scalability and efficiency up to thousands of nodes. Additionally, the computationally more demanding quintic scaling steps can be accelerated by employing graphics processing units (GPU's) showing, for large systems, a gain of almost a factor two compared to the standard central processing unit-only case. In this way, the evaluation of the derivatives of the RI-MP2 energy can be performed within a few minutes for systems containing hundreds of atoms and thousands of basis functions. With good time to solution, the implementation thus opens the possibility to perform molecular dynamics (MD) simulations in various ensembles (microcanonical ensemble and isobaric-isothermal ensemble) at the MP2 level of theory. Geometry optimization, full cell relaxation, and energy conserving MD simulations have been performed for a variety of molecular crystals including NH3, CO2, formic acid, and benzene.

  12. Density Functional Theory Study of Competitive Reaction Pathways of Ti+ with Fluorinated Acetone in the Gas Phase

    International Nuclear Information System (INIS)

    Hong, Kiryong; Kim, Tae Kyu

    2012-01-01

    We investigate the doublet and quartet potential energy surfaces associated with the gas-phase reaction between Ti + and CF 3 COCH 3 for two plausible reaction pathways, TiF 2 + and TiO + formation pathways by using the density functional theory (DFT) method. The molecular structures of intermediates and transition states involved in these reaction pathways are optimized at the DFT level by using the PBE0 functional. All transition states are identified by using the intrinsic reaction coordinate (IRC) method, and the resulting reaction coordinates describe how Ti + activates CF 3 COCH 3 and produces TiF 2 + and TiO + as products. On the basis of presented results, we propose the most favorable reaction pathway in the reaction between Ti + and CF 3 COCH 3

  13. A Fluorogenic Aromatic Nucleophilic Substitution Reaction for Demonstrating Normal-Phase Chromatography and Isolation of Nitrobenzoxadiazole Chromophores

    Science.gov (United States)

    Key, Jessie A.; Li, Matthew D.; Cairo, Christopher W.

    2011-01-01

    Normal-phase chromatography is an essential technique for monitoring chemical reactions, identifying the presence of specific components, as well as the purification of organic compounds. An experiment to facilitate the instruction and understanding of the concepts behind normal-phase chromatography at the introductory and intermediate…

  14. Proposal for new experimental tests of the Bose-Einstein condensation mechanism for low-energy nuclear reaction and transmutation processes in deuterium loaded micro- and nano-scale cavities

    International Nuclear Information System (INIS)

    Yeong, E. Kim; Koltick, David S.; Reifenberger, Ronald G.; Zubarev, Alexander L.

    2006-01-01

    Most of experimental results of low-energy nuclear reaction (LENR) reported so far cannot be reproduced on demand. There have been persistent. experimental results indicating that the LENR und transmutation processes in condensed matter (LENRTPCM) are surface phenomena rather than bulk phenomena. Recently, proposed Bose-Einstein condensation (BEC) mechanism may provide a suitable theoretical description of the surface phenomena. New experiments are proposed and described for testing the BEC mechanism for LENR and transmutation processes in micro- and nano-scale traps. (1) We propose the use of micro-or nano-porous conducting materials as a cathode in electrolysis experiments with heavy water with or without Li in order to stabilize the active surface spots and to enhance the effect for the purpose of improving the reproducibility of excess heat generation and nuclear emission. (2) We propose new experimental tests of the BEC mechanism by measuring the pressure and temperature dependence of LENR events using deuterium gas and those deuterated metals with or without Li. If the LENRTPCM are surface phenomena, the proposed use of micro-/nano-scale porous materials is expected to enhance and scale up the LENRTPCM effects by many orders of magnitude, and thus may lead to better reproducibility and theoretical understanding of the phenomena. (authors)

  15. Proposal for new experimental tests of the Bose-Einstein condensation mechanism for low-energy nuclear reaction and transmutation processes in deuterium loaded micro- and nano-scale cavities

    Energy Technology Data Exchange (ETDEWEB)

    Yeong, E. Kim; Koltick, David S.; Reifenberger, Ronald G.; Zubarev, Alexander L. [Department of Phsysics, Purdue University, West Lafayette, IN 47907 (United States)

    2006-07-01

    Most of experimental results of low-energy nuclear reaction (LENR) reported so far cannot be reproduced on demand. There have been persistent. experimental results indicating that the LENR und transmutation processes in condensed matter (LENRTPCM) are surface phenomena rather than bulk phenomena. Recently, proposed Bose-Einstein condensation (BEC) mechanism may provide a suitable theoretical description of the surface phenomena. New experiments are proposed and described for testing the BEC mechanism for LENR and transmutation processes in micro- and nano-scale traps. (1) We propose the use of micro-or nano-porous conducting materials as a cathode in electrolysis experiments with heavy water with or without Li in order to stabilize the active surface spots and to enhance the effect for the purpose of improving the reproducibility of excess heat generation and nuclear emission. (2) We propose new experimental tests of the BEC mechanism by measuring the pressure and temperature dependence of LENR events using deuterium gas and those deuterated metals with or without Li. If the LENRTPCM are surface phenomena, the proposed use of micro-/nano-scale porous materials is expected to enhance and scale up the LENRTPCM effects by many orders of magnitude, and thus may lead to better reproducibility and theoretical understanding of the phenomena. (authors)

  16. Proposal for New Experimental Tests of the Bose-Einstein Condensation Mechanism for Low-Energy Nuclear Reaction and Transmutation Processes in Deuterium Loaded - and Nano-Scale Cavities

    Science.gov (United States)

    Kim, Yeong E.; Koltick, David S.; Reifenberger, Ronald G.; Zubarev, Alexander L.

    2006-02-01

    Most of experimental results of low-energy nuclear reaction (LENR) reported so far cannot be reproduced on demand. There have been persistent experimental results indicating that the LENR and transmutation processes in condensed matters (LENRTPCM) are surface phenomena rather than bulk phenomena. Recently proposed Bose-Einstein condensation (BEC) mechanism may provide a suitable theoretical description of the surface phenomena. New experiments are proposed and described for testing the BEC mechanism for LENR and transmutation processes in micro- and nano-scale traps. (1) We propose the use of micro- or nano-porous conducting materials as a cathode in electrolysis experiments with heavy water with or without Li in order to stabilize the active surface spots and to enhance the effect for the purpose of improving the reproducibility of excess heat generation and nuclear emission. (2) We propose new experimental tests of the BEC mechanism by measuring the pressure and temperature dependence of LENR events using deuterium gas and these deuterated metals with or without Li. If the LENRTPCM are surface phenomena, the proposed use of micro-/nano-scale porous materials is expected to enhance and scale up the LENRTPCM effects by many order of magnitude, and thus may lead to better reproductivity and theoretical understanding of the phenomena.

  17. Enhanced Condensation Heat Transfer

    Science.gov (United States)

    Rose, John Winston

    The paper gives some personal observations on various aspects of enhanced condensation heat transfer. The topics discussed are external condensation (horizontal low-finned tubes and wire-wrapped tubes), internal condensation (microfin tubes and microchannels) and Marangoni condensation of binary mixtures.

  18. Reactions of charged and neutral recoil particles following nuclear transformations. Progress report No. 11, September 1976--August 1977

    International Nuclear Information System (INIS)

    Ache, H.J.

    1977-09-01

    The status of the following programs is reported: study of the stereochemistry of halogen atom reactions produced via (n,γ) nuclear reactions with diastereomeric molecules in the condensed phase; decay-induced labelling of compounds of biochemical interest; reactions of energetic tritium species in graphite; and positron lifetime measurements in γ-irradiated organic solids

  19. Microwave discharge electrodeless lamps (MDEL). Part IV. Novel self-ignition system incorporating metallic microwave condensing cones to activate MDELs in photochemical reactions.

    Science.gov (United States)

    Horikoshi, Satoshi; Tsuchida, Akihiro; Sakai, Hideki; Abe, Masahiko; Sato, Susumu; Serpone, Nick

    2009-11-01

    A metallic condensing cone that concentrates microwave radiation (equivalent to an optical lens) has been developed and used as part of a system to activate a microwave discharge electrodeless lamp (MDEL) in the oxidative treatment of wastewaters by aiding the novel self-ignition of the lamp on irradiation at low microwave power levels. This approach to self-ignition can potentially lead to considerable energy savings in such treatments. System performance was examined for the ignition power of microwaves of such MDEL devices in water, whose usefulness was assessed by investigating the photolytic transformation of aqueous solutions of representatives of three classes of contaminants: chlorinated phenols, herbicides and endocrine disruptors, specifically 4-chlorophenol (4-CP), 2,4-dichlorophenoxyacetic acid (2,4-D) and 4,4'-isopropylidenediphenol (bisphenol-A; BPA), respectively, taken as model wastewaters in air-equilibrated, in oxygen-saturated and in TiO2-containing aqueous media. The results are discussed in terms of the dynamics of the photo-induced degradation processes.

  20. Strangeness condensation and ''clearing'' of the vacuum

    International Nuclear Information System (INIS)

    Brown, G.E.; Kubodera, Kuniharu; Rho, M.; State Univ. of New York, Stony Brook

    1987-01-01

    We show that a substantial amount of strange quark-antiquark pair condensates in the nucleon required by the πN sigma term implies that kaons could condense in nuclear matter at a density about three times that of normal nuclear matter. This phenomenon can be understood as the ''cleansing'' of qanti q condensates from the QCD vacuum by a dense nuclear matter, resulting in a (partial) restoration of the chiral symmetry explicitly broken in the vacuum. It is suggested that the condensation signals a new phase distinct from that of quark plasma and that of ordinary dense hadronic matter. (orig.)

  1. Critical behavior in reaction-diffusion systems exhibiting absorbing phase transition

    CERN Document Server

    Ódor, G

    2003-01-01

    Phase transitions of reaction-diffusion systems with site occupation restriction and with particle creation that requires n>1 parents and where explicit diffusion of single particles (A) exists are reviewed. Arguments based on mean-field approximation and simulations are given which support novel kind of non-equilibrium criticality. These are in contradiction with the implications of a suggested phenomenological, multiplicative noise Langevin equation approach and with some of recent numerical analysis. Simulation results for the one and two dimensional binary spreading 2A -> 4A, 4A -> 2A model display a new type of mean-field criticality characterized by alpha=1/3 and beta=1/2 critical exponents suggested in cond-mat/0210615.

  2. Low Energy Nuclear Reaction Aircraft- 2013 ARMD Seedling Fund Phase I Project

    Science.gov (United States)

    Wells, Douglas P.; McDonald, Robert; Campbell, Robbie; Chase, Adam; Daniel, Jason; Darling, Michael; Green, Clayton; MacGregor, Collin; Sudak, Peter; Sykes, Harrison; hide

    2014-01-01

    This report serves as the final written documentation for the Aeronautic Research Mission Directorate (ARMD) Seedling Fund's Low Energy Nuclear Reaction (LENR) Aircraft Phase I project. The findings presented include propulsion system concepts, synergistic missions, and aircraft concepts. LENR is a form of nuclear energy that potentially has over 4,000 times the energy density of chemical energy sources. It is not expected to have any harmful emissions or radiation which makes it extremely appealing. There is a lot of interest in LENR, but there are no proven theories. This report does not explore the feasibility of LENR. Instead, it assumes that a working system is available. A design space exploration shows that LENR can enable long range and high speed missions. Six propulsion concepts, six missions, and four aircraft concepts are presented. This report also includes discussion of several issues and concerns that were uncovered during the study and potential research areas to infuse LENR aircraft into NASA's aeronautics research.

  3. Nanocrystalline AL2 O2 powders produced by laser induced gas phase reactions

    International Nuclear Information System (INIS)

    Borsella, E.; Botti, S.; Martelli, S.; Zappa, G.; Giorgi, R.; Turt, S.

    1993-01-01

    Nanocrystalline Al 2 O 3 powders were successfully synthesized by a CO 2 laser-driven gas-phase reaction involving trimethylaluminium (Al(CH 3 ) 3 ) and nitrous-oxide (N 2 O). Ethylene (C 2 H 4 ) was added as gas sensitizer. The as-synthesized powder particles showed a considerable carbon contamination and an amorphous-like structure. After thermal treatment at 1200-1400 degrees C, the powder was transformed to hexagonal a-Al 2 O 3 with very low carbon contamination as confirmed by X-ray diffraction, X-ray photo-electron spectroscopy and chemical analysis. The calcinated powders resulted to be spherical single crystal nanoparticles with a mean size of 15-20 nm, as determined by X-ray diffraction, electron microscopy and B.E.T. specific surface measurements. The laser synthesized Al 2 O 3 particles are well suited dispersoids for intermetallic alloy technology

  4. Fermion masses through four-fermion condensates

    Energy Technology Data Exchange (ETDEWEB)

    Ayyar, Venkitesh [Department of Physics, Duke University,Science Drive, Durham, NC 27708 (United States); Chandrasekharan, Shailesh [Department of Physics, Duke University,Science Drive, Durham, NC 27708 (United States); Center for High Energy Physics, Indian Institute of Science,C.V. Raman Avenue, Bangalore, 560012 (India)

    2016-10-12

    Fermion masses can be generated through four-fermion condensates when symmetries prevent fermion bilinear condensates from forming. This less explored mechanism of fermion mass generation is responsible for making four reduced staggered lattice fermions massive at strong couplings in a lattice model with a local four-fermion coupling. The model has a massless fermion phase at weak couplings and a massive fermion phase at strong couplings. In particular there is no spontaneous symmetry breaking of any lattice symmetries in both these phases. Recently it was discovered that in three space-time dimensions there is a direct second order phase transition between the two phases. Here we study the same model in four space-time dimensions and find results consistent with the existence of a narrow intermediate phase with fermion bilinear condensates, that separates the two asymptotic phases by continuous phase transitions.

  5. Investigation into the determination of trimethylarsine in natural gas and its partitioning into gas and condensate phases using (cryotrapping)/gas chromatography coupled to inductively coupled plasma mass spectrometry and liquid/solid sorption techniques

    International Nuclear Information System (INIS)

    Krupp, E.M.; Johnson, C.; Rechsteiner, C.; Moir, M.; Leong, D.; Feldmann, J.

    2007-01-01

    Speciation of trialkylated arsenic compunds in natural gas, pressurized and stable condensate samples from the same gas well was performed using (Cryotrapping) Gas Chromatography-Inductively Coupled Plasma Mass Spectrometry. The major species in all phases investigated was found to be trimethylarsine with a highest concentration of 17.8 ng/L (As) in the gas phase and 33.2 μg/L (As) in the stable condensate phase. The highest amount of trimethylarsine (121 μg/L (As)) was found in the pressurized condensate, along with trace amounts of non-identified higher alkylated arsines. Volatile arsenic species in natural gas and its related products cause concern with regards to environment, safety, occupational health and gas processing. Therefore, interest lies in a fast and simple field method for the determination of volatile arsenicals. Here, we use simple liquid and solid sorption techniques, namely absorption in silver nitrate solution and adsorption on silver nitrate impregnated silica gel tubes followed by total arsenic determination as a promising tool for field monitoring of volatile arsenicals in natural gas and gas condensates. Preliminary results obtained for the sorption-based methods show that around 70% of the arsenic is determined with these methods in comparison to volatile arsenic determination using GC-ICP-MS. Furthermore, an inter-laboratory- and inter-method comparison was performed using silver nitrate impregnated silica tubes on 14 different gas samples with concentrations varying from below 1 to 1000 μg As/m 3 natural gas. The results obtained from the two laboratories differ in a range of 10 to 60%, but agree within the order of magnitude, which is satisfactory for our purposes

  6. HPLC, NMR and MALDI-TOF MS Analysis of Condensed Tannins from Lithocarpus glaber Leaves with Potent Free Radical Scavenging Activity

    OpenAIRE

    Zhang, Liang Liang; Lin, Yi Ming

    2008-01-01

    Using acid-catalyzed degradation in the presence of cysteamine, the condensed tannins from Lithocarpus glaber leaves were characterized, following thiolysis, by means of reversed-phase HPLC, 13C-NMR and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) analyses. The thiolysis reaction products showed the presence of the procyanidin (PC) and prodelphinidin (PD) structures. The 13C-NMR spectrum revealed that the condensed tannins were comprised of PD (7...

  7. Vapor phase reactions in polymerization plasma for divinylsiloxane-bis-benzocyclobutene film deposition

    International Nuclear Information System (INIS)

    Kinoshita, Keizo; Nakano, Akinori; Kawahara, Jun; Kunimi, Nobutaka; Hayashi, Yoshihiro; Kiso, Osamu; Saito, Naoaki; Nakamura, Keiji; Kikkawa, Takamaro

    2006-01-01

    Vapor phase reactions in plasma polymerization of divinylsiloxane-bis-benzocyclobutene (DVS-BCB) low-k film depositions on 300 mm wafers were studied using mass spectrometry, in situ Fourier transform infrared, and a surface wave probe. Polymerization via Diels-Alder cycloaddition reaction was identified by the detection of the benzocyclohexene group. Hydrogen addition and methyl group desorption were also detected in DVS-BCB monomer and related large molecules. The dielectric constant k of plasma polymerized DVS-BCB with a plasma source power range up to 250 W was close to ∼2.7 of thermally polymerized DVS-BCB, and increased gradually over 250 W. The electron density at 250 W was about 1.5x10 10 cm -3 . The increase of the k value at higher power was explained by the decrease of both large molecular species via multistep dissociation and incorporation of silica components into the polymer. It was found that the reduction of electron density as well as precursor residence time is important for the plasma polymerization process to prevent the excess dissociation of the precursor

  8. The physics of exciton-polariton condensates

    CERN Document Server

    Lagoudakis, Konstantinos

    2013-01-01

    In 2006 researchers created the first polariton Bose-Einstein condensate at 19K in the solid state. Being inherently open quantum systems, polariton condensates open a window into the unpredictable world of physics beyond the “fifth state of matter”: the limited lifetime of polaritons renders polariton condensates out-of-equilibrium and provides a fertile test-bed for non-equilibrium physics. This book presents an experimental investigation into exciting features arising from this non-equilibrium behavior. Through careful experimentation, the author demonstrates the ability of polaritons to synchronize and create a single energy delocalized condensate. Under certain disorder and excitation conditions the complete opposite case of coexisting spatially overlapping condensates may be observed. The author provides the first demonstration of quantized vortices in polariton condensates and the first observation of fractional vortices with full phase and amplitude characterization. Finally, this book investigate...

  9. Performance of a passive emergency heat removal system of advanced reactors in two-phase flow and with high concentration of non-condensable; Atuacao de um sistema passivo de remocao de calor de emergencia de reatores avancados em escoamento bifasico e com alta concentracao de nao-condensaveis

    Energy Technology Data Exchange (ETDEWEB)

    Macedo, Luiz Alberto

    2008-07-01

    The research and the development of passive emergency cooling systems are necessary for the new generation of thermo-nuclear systems. Some basic information on the operation of these systems require the research of some relative processes to the natural circulation, mainly in conditions of two-phase flow involving processes of condensation in the presence of non-condensable gases, because many found situations are new. The experimental facility called Bancada de Circulacao Natural (BCN) was used for the realization of tests with diverse concentrations of non-condensable and power levels. The non-condensable gas present in the circuit decreases the rate of heat transfer for the secondary of the heat exchanger, determining low efficiency of the heat exchanger. High concentration of non-condensable in the vapor condensation, determines negative pressure, and cause the inversion of the flow in the circuit. The initial concentration of non-condensable and the geometry of the circuit, in the inlet of the heat exchanger, determines the establishment of transitory with two-phase flow. The BCN was performed with the computational code of Analysis of Accidents and Thermal-Hydraulics RELAP5/MOD 3.3 and, the calculated values had been compared with the experimental data, presenting good agreement for small non-condensable concentrations. The values calculated for high concentrations of non-condensable had been satisfactory after the circuit to have reached the temperature of saturation in the electric heater. (author)

  10. Phase equilibria basic principles, applications, experimental techniques

    CERN Document Server

    Reisman, Arnold

    2013-01-01

    Phase Equilibria: Basic Principles, Applications, Experimental Techniques presents an analytical treatment in the study of the theories and principles of phase equilibria. The book is organized to afford a deep and thorough understanding of such subjects as the method of species model systems; condensed phase-vapor phase equilibria and vapor transport reactions; zone refining techniques; and nonstoichiometry. Physicists, physical chemists, engineers, and materials scientists will find the book a good reference material.

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

    KAUST Repository

    Hong, Jongsup

    2015-08-01

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

  12. Born-Kothari Condensation for Fermions

    Directory of Open Access Journals (Sweden)

    Arnab Ghosh

    2017-09-01

    Full Text Available In the spirit of Bose–Einstein condensation, we present a detailed account of the statistical description of the condensation phenomena for a Fermi–Dirac gas following the works of Born and Kothari. For bosons, while the condensed phase below a certain critical temperature, permits macroscopic occupation at the lowest energy single particle state, for fermions, due to Pauli exclusion principle, the condensed phase occurs only in the form of a single occupancy dense modes at the highest energy state. In spite of these rudimentary differences, our recent findings [Ghosh and Ray, 2017] identify the foregoing phenomenon as condensation-like coherence among fermions in an analogous way to Bose–Einstein condensate which is collectively described by a coherent matter wave. To reach the above conclusion, we employ the close relationship between the statistical methods of bosonic and fermionic fields pioneered by Cahill and Glauber. In addition to our previous results, we described in this mini-review that the highest momentum (energy for individual fermions, prerequisite for the condensation process, can be specified in terms of the natural length and energy scales of the problem. The existence of such condensed phases, which are of obvious significance in the context of elementary particles, have also been scrutinized.

  13. Advances in high pressure research in condensed matter: proceedings of the international conference on condensed matter under high pressures

    International Nuclear Information System (INIS)

    Sikka, S.K.; Gupta, Satish C.; Godwal, B.K.

    1997-01-01

    The use of pressure as a thermodynamic variable for studying condensed matter has become very important in recent years. Its main effect is to reduce the volume of a substance. Thus, in some sense, it mimics the phenomena taking place during the cohesion of solids like pressure ionization, modifications in electronic properties and phase changes etc. Some of the phase changes under pressure lead to synthesis of new materials. The recent discovery of high T c superconductivity in YBa 2 Cu 3 O 7 may be indirectly attributed to the pressure effect. In applied fields like simulation of reactor accident, design of inertial confinement fusion schemes and for understanding the rock mechanical effects of shock propagation in earth due to underground nuclear explosions, the pressure versus volume relations of condensed matter are a vital input. This volume containing the proceedings of the International Conference on Condensed Matter Under High Pressure covers various aspects of high pressure pertaining to equations of state, phase transitions, electronic, optical and transport properties of solids, atomic and molecular studies, shock induced reactions, energetic materials, materials synthesis, mineral physics, geophysical and planetary sciences, biological applications and food processing and advances in experimental techniques and numerical simulations. Papers relevant to INIS are indexed separately

  14. The phase transport and reactions of γ-irradiated aqueous-ionic liquids

    International Nuclear Information System (INIS)

    Howett, S.; Joseph, J.; Noel, J.J.; Wren, J.C.

    2010-01-01

    A novel technology based on the transfer of chemical species across water/ionic liquid interfaces via specific complexation reactions is currently being considered for the separation and sequestration of metal ion contaminants from radioactive waste effluents in the nuclear fuel cycle. An ideal solvent for these applications should have a high intrinsic selectivity for a targeted metal or group of metals (e.g., trans-Pu actinides, lanthanides, or other fission products), an efficient switching mechanism (between complexation and decomplexation), and a high immiscibility with aqueous solutions. These characteristics must be maintained in the chemical, radiation, and mass transport environments present during the separation process. Ionic liquids (ILs) have an almost negligible vapour pressure and high thermal stability. Their ability to dissolve a wide range of substrate molecules and potential to be highly resilient in radiation fields make ILs particularly promising media. The separation efficiency of the biphasic system will depend on many parameters, including the aqueous oxidation state of the targeted metal ion, and the thermodynamics and kinetics of interfacial transport and metal-ligand complex formation at the water/IL interface or in the IL phase. The most uncertain and unstudied area for these applications is the effect of ionizing radiation on the stability and separation efficiency of the biphasic system. The present study investigates the effect of γ-radiation on gas/IL and water/IL interfacial stability and mass transfer with trihexyltetradecylphosphonium bis(trifluoromethyl-sulfonyl)imide, a phosphonium-based IL. The IL, in contact with either gas or water, was irradiated at a dose rate of 6.4 kGy·h -1 . Gas-phase samples were analyzed by gas chromatography-mass spectrometry (GC-MS) and the changes in the IL and aqueous phases were monitored by conductivity measurements and Raman spectroscopy. In this paper we discuss these observations and their

  15. 125IdUrd-induced chromosome fragments, assayed by premature chromosome condensation, and DNA double-strand breaks have similar repair kinetics in G1-phase CHO-cells

    International Nuclear Information System (INIS)

    Iliakis, George; Pantelias, G.E.; Okayasu, Ryuichi; Seaner, Robert

    1987-01-01

    The effect of 125 I-decay on cell lethality, and induction of chromosome and DNA damage, was studied in synchronous non-cycling, G 1 -phase CHO-cells. Neutral filter elution was used to assay repair of DNA double-strand breaks (dsbs), and premature chromosome condensation was used to assay repair of chromosome fragments and induction of ring chromosomes. The results indicate very little repair at the cell survival level (repair of PLD). At the DNA level an efficient repair of DNA dsbs was observed, with kinetics similar to those observed after exposure to X-rays. At the chromosome level a fast repair of prematurely condensed chromosome fragments was observed, with a concomitant increase in the number of ring chromosomes induced. The repair kinetics of chromosome fragments and DNA dsbs were very similar, suggesting that DNA dsbs may underlie chromosome fragmentation. (author)

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

    DEFF Research Database (Denmark)

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

    2012-01-01

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

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

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  18. Performance of evaporative condensers

    Energy Technology Data Exchange (ETDEWEB)

    Ettouney, Hisham M.; El-Dessouky, Hisham T.; Bouhamra, Walid; Al-Azmi, Bader

    2001-07-01

    Experimental investigation is conducted to study the performance of evaporative condensers/coolers. The analysis includes development of correlations for the external heat transfer coefficient and the system efficiency. The evaporative condenser includes two finned-tube heat exchangers. The system is designed to allow for operation of a single condenser, two condensers in parallel, and two condensers in series. The analysis is performed as a function of the water-to-air mass flow rate ratio (L/G) and the steam temperature. Also, comparison is made between the performance of the evaporative condenser and same device as an air-cooled condenser. Analysis of the collected data shows that the system efficiency increases at lower L/G ratios and higher steam temperatures. The system efficiency for various configurations for the evaporative condenser varies between 97% and 99%. Lower efficiencies are obtained for the air-cooled condenser, with values between 88% and 92%. The highest efficiency is found for the two condensers in series, followed by two condensers in parallel and then the single condenser. The parallel condenser configuration can handle a larger amount of inlet steam and can provide the required system efficiency and degree of subcooling. The correlation for the system efficiency gives a simple tool for preliminary system design. The correlation developed for the external heat transfer coefficient is found to be consistent with the available literature data. (Author)

  19. Vortices in a rotating dark matter condensate

    International Nuclear Information System (INIS)

    Yu, Rotha P; Morgan, Michael J

    2002-01-01

    We examine vortices in a self-gravitating dark matter Bose-Einstein condensate (BEC), consisting of ultra-low mass scalar bosons that arise during a late-time cosmological phase transition. Rotation of the dark matter BEC imprints a background phase gradient on the condensate, which establishes a harmonic trap potential for vortices. A numerical simulation of vortex dynamics shows that the vortex number density, n v ∝ r -1 , resulting in a flat velocity profile for the dark matter condensate. (letter to the editor)

  20. The Effect of Capillary Number on a Condensate Blockage in Gas Condensate Reservoirs

    OpenAIRE

    Saifon DAUNGKAEW; Alain C GRINGARTEN

    2004-01-01

    In the petroleum industry, gas condensate reservoirs are becoming more common as exploration targets. However, there is a lack of knowledge of the reservoir behaviour mainly due to its complexity in the near wellbore region, where two phases, i.e. reservoir gas and condensate coexist when the wellbore pressure drops below the dew point pressure. The condensation process causes a reduction of the gas productivity (1). It has been reported in the literature that there is an increasing gas mobil...

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

    Science.gov (United States)

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

    2018-05-01

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

  2. Scattering of atoms on a Bose-Einstein condensate

    International Nuclear Information System (INIS)

    Poulsen, Uffe V.; Moelmer, Klaus

    2003-01-01

    We study the scattering properties of a Bose-Einstein condensate held in a finite depth well when the incoming particles are identical to the ones in the condensate. We calculate phase shifts and corresponding transmission and reflection coefficients, and we show that the transmission times can be negative, i.e., the atomic wave packet seemingly leaves the condensate before it arrives

  3. Interference of an array of independent Bose-Einstein condensates

    International Nuclear Information System (INIS)

    Hadzibabic, Zoran; Stock, Sabine; Battelier, Baptiste; Bretin, Vincent; Dalibard, Jean

    2004-01-01

    We have observed high-contrast matter wave interference between 30 Bose-Einstein condensates with uncorrelated phases. Interferences were observed after the independent condensates were released from a one-dimensional optical lattice and allowed to overlap. This phenomenon is explained with a simple theoretical model, which generalizes the analysis of the interference of two condensates

  4. Reactions of charged and neutral recoil particles following nuclear transformations. Progress report No. 10

    International Nuclear Information System (INIS)

    Ache, H.J.

    1976-09-01

    The status of the following programs is reported: study of the stereochemistry of halogen atom reactions produced via (n,γ) nuclear reactions with diastereomeric molecules in the condensed phase; decay-induced labelling of compounds of biochemical interest; and chemistry of positronium

  5. Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

    Science.gov (United States)

    Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

    2003-09-17

    We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

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

    Science.gov (United States)

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

    2012-03-29

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

  7. Demonstration of Nautilus Centripetal Capillary Condenser Technology

    Science.gov (United States)

    Wheeler, RIchard; Tang, Linh; Wambolt, Spencer; Golliher, Eric; Agui, Juan

    2016-01-01

    This paper describes the results of a proof of concept effort for development of a Nautilus Centripetal Capillary Condenser (NCCC or NC3) used for microgravity compatible water recovery from moist air with integral passive phase separation. Removal of liquid condensate from the air stream exiting a condenser is readily performed here on Earth. In order to perform this function in space however, without gravity or mechanical action, other tactics including utilization of inertial, drag and capillary forces are required. Within the NC3, liquid water forms via condensation on cold condenser surfaces as humid air passes along multiple spiral channels, each in its own plane, all together forming a stacked plate assembly. Non-mechanical inertial forces are employed to transfer condensate, as it forms, via centripetal action to the outer perimeter of each channel. A V-shaped groove, constructed on this outer edge of the spiral channel, increases local capillary forces thereby retaining the liquid. Air drag then pulls the liquid along to a collection region near the center of the device. Dry air produced by each parallel spiral channel is combined in a common orthogonal, out-of-plane conduit passing down the axial center of the stacked device. Similarly, the parallel condensate streams are combined and removed from the condenser/separator through yet another out-of-plane axial conduit. NC3 is an integration of conventional finned condenser operation, combined with static phase separation and capillary transport phenomena. A Mars' transit mission would be a logical application for this technology where gravity is absent and the use of vibrating, energy-intensive, motor-driven centrifugal separators is undesired. Here a vapor stream from either the Heat Melt Compactor or the Carbon dioxide Reduction Assembly, for example, would be dried to a dew point of 10 deg using a passive NC3 condenser/separator with the precious water condensate recycled to the water bus.

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

    Energy Technology Data Exchange (ETDEWEB)

    Leyrit, P.

    1999-06-28

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

  9. Resonance phase and sings of P-odd and P-even effects, observable in the reactions with neutrons

    International Nuclear Information System (INIS)

    Smotritskij, L.M.

    2002-01-01

    It is shown that introduction of the resonance phase for two quasistationary states with a similar spin and counter parity makes it possible to correlate the sing dependence of both the P-odd and P-even effects, experimentally observed in the reactions with neutrons. The common description of such effects enables determination of the theory unknown (free) parameters from the experiment [ru

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

    KAUST Repository

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

    2015-01-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors

  11. Condensation of steam

    International Nuclear Information System (INIS)

    Prisyazhniuk, V.A.

    2002-01-01

    An equation for nucleation kinetics in steam condensation has been derived, the equation taking into account the concurrent and independent functioning of two nucleation mechanisms: the homogeneous one and the heterogeneous one. The equation is a most general-purpose one and includes all the previously known condensation models as special cases. It is shown how the equation can be used in analyzing the process of steam condensation in the condenser of an industrial steam-turbine plant, and in working out new ways of raising the efficiency of the condenser, as well as of the steam-turbine plant as a whole. (orig.)

  12. Low pressure lithium condensation

    International Nuclear Information System (INIS)

    Wadkins, R.P.; Oh, C.H.

    1985-01-01

    A low pressure experiment to evaluate the laminar film condensation coefficients of lithium was conducted. Some thirty-six different heat transfer tests were made at system pressures ranging from 1.3 to 26 Pa. Boiled lithium was condensed on the inside of a 7.6-cm (ID), 409 stainless-steel pipe. Condensed lithium was allowed to reflux back to the pool boiling region below the condensing section. Fourteen chromel/alumel thermocouples were attached in various regions of the condensing section. The thermocouples were initially calibrated with errors of less than one degree Celsius

  13. Enhancing gas-phase reaction in a plasma using high intensity and high power ultrasonic acoustic waves

    DEFF Research Database (Denmark)

    2010-01-01

    is absorbed into said plasma (104), and where a sound pressure level of said generated ultrasonic high intensity and high power acoustic waves (102) is at least substantially 140 dB and where an acoustic power of said generated ultrasonic high intensity and high power acoustic waves (102); is at least...... substantially 100 W. In this way, a high sound intensity and power are obtained that efficiently enhances a gas-phase reaction in the plasma, which enhances the plasma process, e.g. enabling more efficient ozone or hydrogen generation using plasma in relation to reaction speed and/or obtained concentration......This invention relates to enhancing a gas-phase reaction in a plasma comprising: creating plasma (104) by at least one plasma source (106), and wherein that the method further comprises: generating ultrasonic high intensity and high power acoustic waves (102) having a predetermined amount...

  14. Gas-phase reactions of glycine, alanine, valine and their N-methyl derivatives with the nitrosonium ion, NO+.

    Science.gov (United States)

    Freitas, M A; O'Hair, R A; Schmidt, J A; Tichy, S E; Plashko, B E; Williams, T D

    1996-10-01

    The gas-phase reactions of the nitrosonium ion, NO+ with the amino acids glycine, alanine and valine and their N-methyl derivatives were investigated under chemical ionization mass spectrometric (CIMS) conditions. Two products were observed in all cases: the formation of the iminium ion and the formation of an [M-H]+ ion. The latter product is consistent with a reaction channel involving hydride abstraction by NO+, and was confirmed by (i) examining the Ar+CI mass spectra of the same amino acids under similar source conditions and (ii) examining the unimolecular fragmentation reactions of the [M + H]+ ions of the N-nitroso-N-methyl derivatives of each of the amino acids in a tandem mass spectrometer. Further insights into the reaction of glycine with NO+ were obtained by performing ab initio calculations (at the MP2/6-31G* parallel HF/6-31G* level). These results indicate that four reactions are thermodynamically viable for glycine: (i) hydride abstraction; (ii) iminium ion formation (with concomitant loss of HONO and CO); (iii) diazonium ion formation; and (iv) diazonium ion formation followed by loss of N2. Possible reasons why reactions (iii) and (iv) are not observed are discussed, and comparisons with solution reactivity and the gas-phase reactivity of NO+ are also made.

  15. Modelling of condensation phenomena

    International Nuclear Information System (INIS)

    Jeong, Jae Jun; Chang, Won Pyo

    1996-07-01

    Condensation occurs when vapor is cooled sufficiently below the saturation temperature to induce the nucleation of droplets. Such nucleation may occur homogeneously within the vapor or heterogeneously on entrained particular matter. Heterogeneous nucleation may occur on the walls of the system, where the temperature is below the saturation temperature. There are two forms of heterogeneous condensation, drop-wise and film-wise. Another form of condensation occurs when vapor directly contacts to subcooled liquid. In nuclear power plant systems, all forms of condensation may occur during normal operation or accident conditions. In this work the modelling of condensation is surveyed, including the Nusselts' laminar film condensation theory in 1916, Rohsenow's turbulent film condensation model in 1950s, and Chen's models in 1987. Major attention is paid on the film condensation models among various research results because of its importance in engineering applications. It is found that theory, experiment, and empirical correlations for film condensation are well established, but research for drop-wise and direct-contact condensation are not sufficient yet. Condensation models in the best-estimate system codes such as RELAP5/MOD3 and CATHARE2 are also investigated. 3 tabs., 11 figs., 36 refs. (Author)

  16. Study of ions - molecules reactions in the gas phase with collision reaction cell devices: Applications to the direct resolution of spectroscopic interferences in ICP-MS

    International Nuclear Information System (INIS)

    Favre, G.

    2008-12-01

    Inductively Coupled Plasma Mass Spectrometry emerged as the most widespread mass spectrometry technique in inorganic analytical chemistry for determining the concentration of a given isotope or an isotope ratio. The problem of spectroscopic interferences, inherent to this technique, finds a solution through the use of reaction cell devices. An in situ interference removal is feasible with the addition of a well selected gas in the cell. The understanding of the chemistry of ions-molecules interactions in the gas phase is however fundamental to optimize the efficiency of such devices. An accurate knowledge of experimental conditions in the reaction zone according to instrumental parameters appears crucial in order to interpret observed reactivities. This preliminary study is then used for the resolution of two nuclear field characteristic interferences. (author)

  17. Bose-Einstein condensates form in heuristics learned by ciliates deciding to signal 'social' commitments.

    Science.gov (United States)

    Clark, Kevin B

    2010-03-01

    Fringe quantum biology theories often adopt the concept of Bose-Einstein condensation when explaining how consciousness, emotion, perception, learning, and reasoning emerge from operations of intact animal nervous systems and other computational media. However, controversial empirical evidence and mathematical formalism concerning decoherence rates of bioprocesses keep these frameworks from satisfactorily accounting for the physical nature of cognitive-like events. This study, inspired by the discovery that preferential attachment rules computed by complex technological networks obey Bose-Einstein statistics, is the first rigorous attempt to examine whether analogues of Bose-Einstein condensation precipitate learned decision making in live biological systems as bioenergetics optimization predicts. By exploiting the ciliate Spirostomum ambiguum's capacity to learn and store behavioral strategies advertising mating availability into heuristics of topologically invariant computational networks, three distinct phases of strategy use were found to map onto statistical distributions described by Bose-Einstein, Fermi-Dirac, and classical Maxwell-Boltzmann behavior. Ciliates that sensitized or habituated signaling patterns to emit brief periods of either deceptive 'harder-to-get' or altruistic 'easier-to-get' serial escape reactions began testing condensed on initially perceived fittest 'courting' solutions. When these ciliates switched from their first strategy choices, Bose-Einstein condensation of strategy use abruptly dissipated into a Maxwell-Boltzmann computational phase no longer dominated by a single fittest strategy. Recursive trial-and-error strategy searches annealed strategy use back into a condensed phase consistent with performance optimization. 'Social' decisions performed by ciliates showing no nonassociative learning were largely governed by Fermi-Dirac statistics, resulting in degenerate distributions of strategy choices. These findings corroborate

  18. Sensitivity analysis and economic optimization studies of inverted five-spot gas cycling in gas condensate reservoir

    OpenAIRE

    Shams Bilal; Yao Jun; Zhang Kai; Zhang Lei

    2017-01-01

    Gas condensate reservoirs usually exhibit complex flow behaviors because of propagation response of pressure drop from the wellbore into the reservoir. When reservoir pressure drops below the dew point in two phase flow of gas and condensate, the accumulation of large condensate amount occurs in the gas condensate reservoirs. Usually, the saturation of condensate accumulation in volumetric gas condensate reservoirs is lower than the critical condensate saturation that causes trapping of large...

  19. Proceedings: Condenser technology conference

    International Nuclear Information System (INIS)

    Tsou, J.L.; Mussalli, Y.G.

    1991-08-01

    Seam surface condenser and associated systems performance strongly affects availability and heat rate in nuclear and fossil power plants. Thirty-six papers presented at a 1990 conference discuss research results, industry experience, and case histories of condenser problems and solutions. This report contains papers on life extension, performance improvement, corrosion and failure analysis, fouling prevention, and recommendation for future R ampersand D. The information represents recent work on condenser problems and solutions to improve the procurement, operation, and maintenance functions of power plant personnel. Several key points follow: A nuclear and a fossil power plant report show that replacing titanium tube bundles improves condenser availability and performance. One paper reports 10 years of experience with enhanced heat transfer tubes in utility condensers. The newly developed enhanced condenser tubes could further improve condensing heat transfer. A new resistance summation method improves the accuracy of condenser performance prediction, especially for stainless steel and titanium tubed condensers. Several papers describe improved condenser fouling monitoring techniques, including a review of zebra mussel issues

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

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

    Science.gov (United States)

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

    2012-02-01

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

  2. Thermodynamic entanglement of magnonic condensates

    Science.gov (United States)

    Yuan, H. Y.; Yung, Man-Hong

    2018-02-01

    Over the past decade, significant progress has been achieved to create Bose-Einstein condensates (BECs) of magnetic excitations, i.e., magnons, at room temperature, which is a novel quantum many-body system with a strong spin-spin correlation, and contains potential applications in magnonic spintronics. For quantum information science, the magnonic condensates can become an attractive source of quantum entanglement, which plays a central role in most of the quantum information processing tasks. Here we theoretically study the entanglement properties of a magnon gas above and below the condensation temperature. We show that the thermodynamic entanglement of the spins is a manifestation of the off-diagonal long-range order; the entanglement of the condensate does not vanish, even if the spins are separated by an infinitely long distance, which is fundamentally distinct from the normal magnetic ordering below the Curie temperature. In addition, the phase-transition point occurs when the derivative of the entanglement changes abruptly. These results provide a theoretical foundation for a future investigation of the magnon BEC in terms of quantum entanglement.

  3. A study of phase and morphology changes occurring as a result of galvanic reactions with FeO nanocrystals

    Science.gov (United States)

    Onserio, Benard Obae

    Recently, iron oxide nanoparticles have attracted great attention from various research groups. This is due to their potential applications in various fields such as biomedicine, environmental remediation, storage media, catalysis, and as anode materials for lithium-ion batteries. The objective of this study is to develop a synthesis of hollow Fe3O4 nanoparticles via galvanic reaction between FeO nanocrystals and oxidizing agents in which a nanoscale Kirkendall effect occurs. The objective is based on prior results in which it was demonstrated that Cu2+ oxidized MnO nanocrystals to yield hollow Mn3O4 nanoparticles. The analogous process starting from FeO is expected to be even more thermodynamically favorable. Despite efforts to obtain FeO nanocrystals, the magnetite Fe3O 4 phase was obtained. With this sample, attempts were made towards galvanic reactions in the presence of Cu2+. The initial result of the reaction of Fe3O4 nanocrystals with Cu2+ was unexpected, and FeO was obtained; however, the result could not be reproduced. Later efforts focused on attempting to understand the galvanic reaction that took place leading to the formation of FeO. Thus reaction of Fe3O 4 with oleylamine, silver (I), and ascorbic acid were studied. Data for the phase and morphological changes of the iron oxides will be presented.

  4. Intramolecular kinetic isotope effect in gas-phase proton-transfer reactions

    International Nuclear Information System (INIS)

    Wellman, K.M.; Victoriano, M.E.; Isolani, P.C.; Riveros, J.M.

    1979-01-01

    The k/sub H//k/sub D/ isotope effects were determined by ICR for the reaction of substituted toluenes with several alkoxides. The results showed a definite trend for k/sub H//k/sub D/ starting as a normal isotope effect for appreciably exothermic reaction (> 3 kcal mol -1 ) and proceeding smoothly toward an inverse isotope effect as the reaction approached thermoneutrality or becomes endothermic. These observations were explained by a reaction which involved a double minima potential with a central energy barrier

  5. Biomolecular condensates: organizers of cellular biochemistry.

    Science.gov (United States)

    Banani, Salman F; Lee, Hyun O; Hyman, Anthony A; Rosen, Michael K

    2017-05-01

    Biomolecular condensates are micron-scale compartments in eukaryotic cells that lack surrounding membranes but function to concentrate proteins and nucleic acids. These condensates are involved in diverse processes, including RNA metabolism, ribosome biogenesis, the DNA damage response and signal transduction. Recent studies have shown that liquid-liquid phase separation driven by multivalent macromolecular interactions is an important organizing principle for biomolecular condensates. With this physical framework, it is now possible to explain how the assembly, composition, physical properties and biochemical and cellular functions of these important structures are regulated.

  6. Bose-Einstein condensation in real space

    International Nuclear Information System (INIS)

    Valencia, J.J.; Llano, M. de; Solis, M.A.

    2004-01-01

    We show how Bose-Einstein condensation (BEC) occurs not only in momentum space but also in coordinate (or real) space. Analogies between the isotherms of a van der Waals classical gas of extended (or finite-diameter) identical atoms and the point (or zero-diameter) particles of an ideal BE gas allow concluding that, in contrast with the classical case, the volume per particle vanishes in the pure BE condensate phase precisely because the boson diameters are zero. Thus a BE condensate forms in real space without exhibiting a liquid branch as does the classical gas. (Author)

  7. Capillary condensation between disks in two dimensions

    DEFF Research Database (Denmark)

    Gil, Tamir; Ipsen, John Hjorth

    1997-01-01

    Capillary condensation between two two-dimensional wetted circular substrates (disks) is studied by an effective free energy description of the wetting interface. The interfacial free-energy potential is developed on the basis of the theory for the wetting of a single disk, where interfacial...... capillary fluctuations play a dominant role. A simple approximative analytical expression of the interfacial free energy is developed and is validated numerically. The capillary condensation is characterized by the analysis of the coverage of the condensed phase, its stability, and asymptotic behaviors...

  8. Turbulence and heat transfer in condensate in drying cylinders at high g-forces. Phase 2; Turbulens och vaermeoeverfoering i kondensat i torkcylindrar vid hoega g-krafter. Fas 2

    Energy Technology Data Exchange (ETDEWEB)

    Stenstroem, Stig; Ingvarsson, David [Lund Inst. of Tech. (Sweden). Dept. of Chemical Engineering

    2006-02-15

    During paper drying a condensate layer is formed on the inside surface of the rotating cylinder which acts as resistance for heat transfer through the cylinder. The heat transfer resistance in the condensate layer is mainly dependant on the layer thickness and the turbulence in the layer. Consequently the resistance increases with higher cylinder speeds due to increased centrifugal forces and thus reduced turbulence in the layer. In order to minimize the influence of condensate on the heat transfer process the cylinder used in Phase 1 has been equipped with axial grooves. The aim of the project has been to study the water movement in the cylinder and to investigate how the drying capacity is influenced by condensate accumulating in the grooves rather than moving along the smooth surface of a paper dryer cylinder. This knowledge should be considered preferably before construction of cylinders for new machines. For existing machines with smooth cylinders the importance of axial vertical flanges for improved heat transfer has been investigated. In addition the capacity of stationary siphons has been evaluated. The results are of importance for the manufacturers of paper machines as well as the producing newsprint and printing paper companies. According to the results from the experiments the water flows mainly in the grooves, assuming that the number of grooves and that the dimensions of the grooves are adjusted to the water load. Then the surfaces between the grooves can be considered as completely dry unlike in a smooth cylinder where the surfaces more or less are covered with a thin layer of condensate. Furthermore the centrifugal force helps the water to flow down into the grooves. Consequently a high water flow will rely on a high cylinder speed in order to keep the water flowing into the axial grooves. The computer simulations show that the drying capacity increases with up to 46 % in dryer cylinders provided with axial grooves compared to smooth cylinders

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

    Science.gov (United States)

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

    2012-07-05

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

  10. Condensate cleaning systems

    International Nuclear Information System (INIS)

    Yamamoto, Michiyoshi; Oosumi, Katsumi; Takashima, Yoshie; Mitani, Shinji.

    1982-01-01

    Purpose: To decrease the frequency for the backwash and regeneration operations due to the increase in the differential pressure resulted from claddings captured in a mixed floor type desalter, and decrease the amount of radioactive liquid wastes of claddings from the condensate systems by removing claddings with electromagnetic filters. Constitution: In an existent plant, a valves is disposed between a condensate pump and a mixed floor type desalter. A pipeway is branched from a condensate pipe between the condensate pipe and the valve, through which condensates are transferred by a pump to an electromagnetic filter such as of a high gradient type electromagntic filter to remove claddings, then returned to a condensate pipe between the valve and the mixed floor type desalter and, thereafter, are removed with ionic components in the mixed floor type desalter and fed to the reactor. (Yoshino, Y.)

  11. Purification method for condensate

    International Nuclear Information System (INIS)

    Shimoda, Akiyoshi.

    1996-01-01

    Condensates generated in secondary coolant circuits of a PWR type reactor are filtered using a hollow thread separation membranes comprising aromatic polyether ketone. Preferably, condensates after passing through a turbine are filtered at a place between a condensator and a steam generator at high temperature as close as a temperature of the steam generator. As the hollow thread membrane, partially crystalline membrane comprising aromatic polyether ketone is used. When it is used at high temperature, the crystallinity is preferably not less than 15wt%. Since a hollow thread membrane comprising the aromatic polyether ketone of excellent heat resistance is used, it can filter and purify the condensates at not lower than 70degC. Accordingly, impurities such as colloidal iron can be removed from the condensates, and the precipitation of cruds in the condensates to a steam generator and a turbine can be suppressed. (I.N.)

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

    DEFF Research Database (Denmark)

    Egsgaard, Helge

    1986-01-01

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

  13. Solid-phase Synthesis of Combinatorial 2,4-Disubstituted-1,3,5-Triazine via Amine Nucleophilic Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Sung Won [KIST Gangneung Institute, Gangneung (Korea, Republic of); Ham, Jungyeob [Gangneung-Wonju National University, Gangneung (Korea, Republic of); Chang, Young-Tae [National University of Singapore, Singapore (Singapore); Lee, Jae Wook [University of Science and Technology, Daejon (Korea, Republic of)

    2015-01-15

    In combinatorial chemistry, solid-phase synthesis is a popular approach formass production of small molecules. Compared to solution-phase synthesis, it is easy to prepare and purify a large number of heterocyclic small molecules via solid-phase chemistry; the overall reaction time is decreased as well. 1,3,5-Triazine is a nitrogen-containing heterocyclic aromatic scaffold that was shown to be a druggable scaffold in recent studies. These structures have been reported as anticancer, antimicrobial, and antiretroviral compounds, as CDKs and p38 MAP kinase inhibitors, as estrogen receptor modulators, and as inosine monophosphate dehydrogenase inhibitors. we designed and synthesized disubstituted triazine compounds as an analog of disubstituted pyrimidine compounds. These disubstituted triazine compounds possess a linear structure which may have biological activity similar to that of disubstituted pyrimidine. Here we report the solid-phase synthesis of disubstituted triazine compounds.

  14. Solid-phase Synthesis of Combinatorial 2,4-Disubstituted-1,3,5-Triazine via Amine Nucleophilic Reaction

    International Nuclear Information System (INIS)

    Moon, Sung Won; Ham, Jungyeob; Chang, Young-Tae; Lee, Jae Wook

    2015-01-01

    In combinatorial chemistry, solid-phase synthesis is a popular approach formass production of small molecules. Compared to solution-phase synthesis, it is easy to prepare and purify a large number of heterocyclic small molecules via solid-phase chemistry; the overall reaction time is decreased as well. 1,3,5-Triazine is a nitrogen-containing heterocyclic aromatic scaffold that was shown to be a druggable scaffold in recent studies. These structures have been reported as anticancer, antimicrobial, and antiretroviral compounds, as CDKs and p38 MAP kinase inhibitors, as estrogen receptor modulators, and as inosine monophosphate dehydrogenase inhibitors. we designed and synthesized disubstituted triazine compounds as an analog of disubstituted pyrimidine compounds. These disubstituted triazine compounds possess a linear structure which may have biological activity similar to that of disubstituted pyrimidine. Here we report the solid-phase synthesis of disubstituted triazine compounds

  15. Theoretical investigation of the gas-phase reactions of CrO(+) with ethylene.

    Science.gov (United States)

    Scupp, Thomas M; Dudley, Timothy J

    2010-01-21

    The potential energy surfaces associated with the reactions of chromium oxide cation (CrO(+)) with ethylene have been characterized using density functional, coupled-cluster, and multireference methods. Our calculations show that the most probable reaction involves the formation of acetaldehyde and Cr(+) via a hydride transfer involving the metal center. Our calculations support previous experimental hypotheses that a four-membered ring intermediate plays an important role in the reactivity of the system. We have also characterized a number of viable reaction pathways that lead to other products, including ethylene oxide. Due to the experimental observation that CrO(+) can activate carbon-carbon bonds, a reaction pathway involving C-C bond cleavage has also been characterized. Since many of the reactions involve a change in the spin state in going from reactants to products, locations of these spin surface crossings are presented and discussed. The applicability of methods based on Hartree-Fock orbitals is also discussed.

  16. Condensed matter analogues of cosmology

    Science.gov (United States)

    Kibble, Tom; Srivastava, Ajit

    2013-10-01

    It is always exciting when developments in one branch of physics turn out to have relevance in a quite different branch. It would be hard to find two branches farther apart in terms of energy scales than early-universe cosmology and low-temperature condensed matter physics. Nevertheless ideas about the formation of topological defects during rapid phase transitions that originated in the context of the very early universe have proved remarkably fruitful when applied to a variety of condensed matter systems. The mathematical frameworks for describing these systems can be very similar. This interconnection has led to a deeper understanding of the phenomena in condensed matter systems utilizing ideas from cosmology. At the same time, one can view these condensed matter analogues as providing, at least in a limited sense, experimental access to the phenomena of the early universe for which no direct probe is possible. As this special issue well illustrates, this remains a dynamic and exciting field. The basic idea is that when a system goes through a rapid symmetry-breaking phase transition from a symmetric phase into one with spontaneously broken symmetry, the order parameter may make different choices in different regions, creating domains that when they meet can trap defects. The scale of those domains, and hence the density of defects, is constrained by the rate at which the system goes through the transition and the speed with which order parameter information propagates. This is what has come to be known as the Kibble-Zurek mechanism. The resultant scaling laws have now been tested in a considerable variety of different systems. The earliest experiments illustrating the analogy between cosmology and condensed matter were in liquid crystals, in particular on the isotropic-to-nematic transition, primarily because it is very easy to induce the phase transition (typically at room temperature) and to image precisely what is going on. This field remains one of the

  17. Fabrication of a Schottky junction diode with direct growth graphene on silicon by a solid phase reaction

    International Nuclear Information System (INIS)

    Kalita, Golap; Hirano, Ryo; Ayhan, Muhammed E; Tanemura, Masaki

    2013-01-01

    We demonstrate fabrication of a Schottky junction diode with direct growth graphene on n-Si by the solid phase reaction approach. Metal-assisted crystallization of a-C thin film was performed to synthesize transfer-free graphene directly on a SiO 2 patterned n-Si substrate. Graphene formation at the substrate and catalyst layer interface is achieved in presence of a Co catalytic and CoO carbon diffusion barrier layer. The as-synthesized material shows a linear current–voltage characteristic confirming the metallic behaviour of the graphene structure. The direct grown graphene on n-Si substrate creates a Schottky junction with a potential barrier of 0.44 eV and rectification diode characteristic. Our finding shows that the directly synthesized graphene on Si substrate by a solid phase reaction process can be a promising technique to fabricate an efficient Schottky junction device. (paper)

  18. Condensation During Nuclear Reactor Loca

    International Nuclear Information System (INIS)

    Rihan, Y.; Teamah, M.; Sorour, M.; Soliman, S.

    2008-01-01

    Two-phase channel flow with condensation is a common phenomenon occurs in a number of nuclear reactor accident scenarios. It also plays an important role during the operation of the safety coolant injection systems in advanced nuclear reactors. Semiempirical correlations and simple models based on the analogy between heat and mass transfer processes have been previously applied. Rigorous models, compatible with the state-of-the-art numerical algorithms used in thermal-hydraulic computer codes, are scare, and are of great interest. The objective of this research is to develop a method for modeling condensation, with noncondensable gases, compatible with the state-of-the-art numerical methods for the solution of multi-phase field equations. A methodology for modeling condensation, based on the stagnant film theory, and compatible with the reviewed numerical algorithms, is developed. The model treats the coupling between the heat and mass transfer processes, and allows for an implicit treatment of the mass and momentum exchange terms as the gas-liquid interphase, without iterations. The developed model was used in the application of loss of coolant in pressurized water reactor accidents

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

    International Nuclear Information System (INIS)

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

    2002-01-01

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

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

    Science.gov (United States)

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

    2013-12-01

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

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

    Science.gov (United States)

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

    2015-06-01

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

  2. Aldimine Formation Reaction, the First Step of the Maillard Early-phase Reaction, Might be Enhanced in Variant Hemoglobin, Hb Himeji.

    Science.gov (United States)

    Koga, Masafumi; Inada, Shinya; Shimizu, Sayoko; Hatazaki, Masahiro; Umayahara, Yutaka; Nishihara, Eijun

    2015-01-01

    Hb Himeji (β140Ala→Asp) is known as a variant hemoglobin in which glycation is enhanced and HbA1c measured by immunoassay shows a high value. The phenomenon of enhanced glycation in Hb Himeji is based on the fact that the glycation product of variant hemoglobin (HbX1c) shows a higher value than HbA1c. In this study, we investigated whether aldimine formation reaction, the first step of the Maillard early-phase reaction, is enhanced in Hb Himeji in vitro. Three non-diabetic subjects with Hb Himeji and four non-diabetic subjects without variant hemoglobin were enrolled. In order to examine aldimine formation reaction, whole blood cells were incubated with 500 mg/dl of glucose at 37°C for 1 hour and were analyzed by high-performance liquid chromatography. Both HbA1c and HbX1c were not increased in this condition. After incubation with glucose, labile HbA1c (LA1c) fraction increased in the controls (1.1±0.3%). In subjects with Hb Himeji increases in the labile HbX1c (LX1c) fraction as well as the LA1c fraction were observed, and the degree of increase in the LX1c fraction was significantly higher than that of the LA1c fraction (1.8±0.1% vs. 0.5±0.2%, Preaction might be enhanced in Hb Himeji in vitro. The 140th amino acid in β chain of hemoglobin is suggested to be involved in aldimine formation reaction. © 2015 by the Association of Clinical Scientists, Inc.

  3. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    International Nuclear Information System (INIS)

    Yeh, G.T.; Iskra, G.A.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength

  4. A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking

    International Nuclear Information System (INIS)

    Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Hayashi, Jun-ichiro

    2014-01-01

    The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C 3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures. - Highlights: • Analytical pyrolysis experiments provided data for kinetic modeling. • Detailed chemical kinetic model was used and evaluated. • Alkyne and diene were important intermediates for aromatic hydrocarbon formation. • Reaction pathways leading to aromatic hydrocarbons were proposed

  5. The formation of urea in space. I. Ion-molecule, neutral-neutral, and radical gas-phase reactions

    Science.gov (United States)

    Brigiano, Flavio Siro; Jeanvoine, Yannick; Largo, Antonio; Spezia, Riccardo

    2018-02-01

    Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N-C-O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C-O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims: We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods: We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results: Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.

  6. Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

    2011-07-01

    Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

  7. The reaction of nitromethane with hydrogen and deuterium atoms in the gas phase. A mechanistic study

    DEFF Research Database (Denmark)

    Lund Thomsen, E.; Nielsen, O.J.; Egsgaard, H.

    1993-01-01

    The mechanism of the reaction between H and CH3NO2, has been studied in a discharge flow system using electron paramagnetic resonance and modulated molecular beam mass spectrometry for the detection of reactants and products. Deuterium atoms have, in addition to CD3NO2, been used to support...... the proposed reaction mechanism. The reaction was studied with the atomic reactant in slight excess at 298 K and a total pressure of 2 Torr. Two concurrent reaction channels: (1a) H+CH3NO2-->HONO+.CH3 and (1b) H+CH3NO2-->CH3NO+.OH were observed. The branching ratio, k1a/(k1a+k1b), is 0.7+/-0.2....

  8. Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Ponomarev, DA; Nielsen, OJ

    2001-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms with iodobenzene (C6H5I) in 20-700 Torr of N-2, air, or O-2 diluent at 296 K. The reaction proceeds with a rate constant k(Cl + QH(5)I) = (3.3 +/- 0.7) x 10(-11) cm(3) molecule(-1) s(-1) to give...

  9. Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Berman, A D; Krylov, O V

    1978-01-01

    This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

  10. Systematic text condensation

    DEFF Research Database (Denmark)

    Malterud, Kirsti

    2012-01-01

    To present background, principles, and procedures for a strategy for qualitative analysis called systematic text condensation and discuss this approach compared with related strategies.......To present background, principles, and procedures for a strategy for qualitative analysis called systematic text condensation and discuss this approach compared with related strategies....

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

    Science.gov (United States)

    Dateo, Christopher E.; Walch, Stephen P.

    2002-01-01

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

  12. Chromosome condensation and segmentation

    International Nuclear Information System (INIS)

    Viegas-Pequignot, E.M.

    1981-01-01

    Some aspects of chromosome condensation in mammalians -humans especially- were studied by means of cytogenetic techniques of chromosome banding. Two further approaches were adopted: a study of normal condensation as early as prophase, and an analysis of chromosome segmentation induced by physical (temperature and γ-rays) or chemical agents (base analogues, antibiotics, ...) in order to show out the factors liable to affect condensation. Here 'segmentation' means an abnormal chromosome condensation appearing systematically and being reproducible. The study of normal condensation was made possible by the development of a technique based on cell synchronization by thymidine and giving prophasic and prometaphasic cells. Besides, the possibility of inducing R-banding segmentations on these cells by BrdU (5-bromodeoxyuridine) allowed a much finer analysis of karyotypes. Another technique was developed using 5-ACR (5-azacytidine), it allowed to induce a segmentation similar to the one obtained using BrdU and identify heterochromatic areas rich in G-C bases pairs [fr

  13. Condensation in complex geometries

    International Nuclear Information System (INIS)

    Lauro, F.

    1975-01-01

    A mathematical evaluation of the condensation exchange coefficient can only succeds for well specified cases: small upright or inclined plates, horizontal tubes, small height vertical tubes. Among the main hypotheses accounted for this mathematical development in the case of the condensate, a laminar flow and uniform surface temperature are always considered. In practice certain shapes of surfaces significantly increase the heat transfer during the vapor condensation on a surface wet by the condensate. Such surfaces are rough surfaces such as the condensate is submitted to surface tension effects, negligeable for plane or large curvature surfaces, and the nature of the material may play an important role (temperature gradients). Results from tests on tubes with special shapes, performed in France or out of France, are given [fr

  14. One-pot aldol condensation and hydrodeoxygenation of biomass-derived carbonyl compounds for biodiesel synthesis.

    Science.gov (United States)

    Faba, Laura; Díaz, Eva; Ordóñez, Salvador

    2014-10-01

    Integrating reaction steps is of key interest in the development of processes for transforming lignocellulosic materials into drop-in fuels. We propose a procedure for performing the aldol condensation (reaction between furfural and acetone is taken as model reaction) and the total hydrodeoxygenation of the resulting condensation adducts in one step, yielding n-alkanes. Different combinations of catalysts (bifunctional catalysts or mechanical mixtures), reaction conditions, and solvents (aqueous and organic) have been tested for performing these reactions in an isothermal batch reactor. The results suggest that the use of bifunctional catalysts and aqueous phase lead to an effective integration of both reactions. Therefore, selectivities to n-alkanes higher than 50% were obtained using this catalyst at typical hydrogenation conditions (T=493 K, P=4.5 MPa, 24 h reaction time). The use of organic solvent, carbonaceous supports, or mechanical mixtures of monofunctional catalysts leads to poorer results owing to side effects; mainly, hydrogenation of reactants and adsorption processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Miyazaki, Tetsuo

    1991-01-01

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

  16. Winding Up of the Wave-Function Phase by an Insulator-to-Superfluid Transition in a Ring of Coupled Bose-Einstein Condensates

    International Nuclear Information System (INIS)

    Dziarmaga, Jacek; Meisner, Jakub; Zurek, Wojciech H.

    2008-01-01

    We study phase transition from the Mott insulator to superfluid in a periodic optical lattice. Kibble-Zurek mechanism predicts buildup of winding number through random walk of BEC phases, with the step size scaling as a third root of transition rate. We confirm this and demonstrate that this scaling accounts for the net winding number after the transition

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

    Science.gov (United States)

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

    2016-05-01

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

  18. Effect of an organoclay on the reaction-induced phase-separation in a dynamically asymmetric epoxy/PCL system

    Directory of Open Access Journals (Sweden)

    J. Rotrekl

    2013-12-01

    Full Text Available The addition of layered silicates can significantly affect the phase behaviour of both immiscible thermoplastic blends and partially miscible thermoset systems that undergo reaction-induced phase separation (RIPS during curing. This study focuses on the phase behaviour of polycaprolactone (PCL/epoxy in the presence of organically modified montmorillonite (oMMT. Due to the high dynamic asymmetry caused by the differences in the molecular weights and viscosities of the PCL and the uncured epoxy, the critical point is localised at low PCL concentrations, as indicated by the pseudophase diagram. The addition of oMMT to the system led to the marked shift of the critical point towards higher concentrations of PCL, with an increase in the oMMT content occurring as a consequence of the preferential localisation of the clay in the epoxy phase, making this phase more dynamically slow. Significant changes in morphology, including phase inversion of the PCL/epoxy systems caused by the presence of oMMT, were recorded for PCL concentrations ranging from 10 to 30%.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-06-01

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

  20. Spectroscopy of dark soliton states in Bose-Einstein condensates

    International Nuclear Information System (INIS)

    Bongs, K; Burger, S; Hellweg, D; Kottke, M; Dettmer, S; Rinkleff, T; Cacciapuoti, L; Arlt, J; Sengstock, K; Ertmer, W

    2003-01-01

    Experimental and numerical studies of the velocity field of dark solitons in Bose-Einstein condensates are presented. The formation process after phase imprinting as well as the propagation of the emerging soliton are investigated using spatially resolved Bragg spectroscopy of soliton states in Bose-Einstein condensates of 87 Rb. A comparison of experimental data to results from numerical simulations of the Gross-Pitaevskii equation clearly identifies the flux underlying a dark soliton propagating in a Bose-Einstein condensate. The results allow further optimization of the phase imprinting method for creating collective excitations of Bose-Einstein condensates

  1. L1{sub 0} phase transition in FePt thin films via direct interface reaction

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaohong; Sun Hongyu; Wang Fengqing; Li Wei; Zhang Xiangyi [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, 066004 Qinhuangdao (China); Liu Baoting; Guo Jianxin [College of Physics Science and Technology, Hebei University, 071002 Baoding (China)], E-mail: xyzh66@ysu.edu.cn

    2008-12-07

    Lowering the L1{sub 0} ordering temperature of FePt films is of great significance for their application as an ultrahigh density magnetic recording medium. In this study, the L1{sub 0} ordering process of FePt thin films deposited directly on Si substrates has been significantly accelerated by the interface reaction between the thin film and the Si substrate, and thus the thin films show a low L1{sub 0} ordering temperature of T = 310 deg. C as compared with those deposited on Si/SiO{sub 2} substrates. The accelerated L1{sub 0} ordering transition is predominantly dependent on the rapid growth of the ordered domains during the interface reaction. The film thickness has an important effect on the interface reaction and thus can be used to tune the L1{sub 0} ordering process of the FePt films.

  2. L10 phase transition in FePt thin films via direct interface reaction

    International Nuclear Information System (INIS)

    Li Xiaohong; Sun Hongyu; Wang Fengqing; Li Wei; Zhang Xiangyi; Liu Baoting; Guo Jianxin

    2008-01-01

    Lowering the L1 0 ordering temperature of FePt films is of great significance for their application as an ultrahigh density magnetic recording medium. In this study, the L1 0 ordering process of FePt thin films deposited directly on Si substrates has been significantly accelerated by the interface reaction between the thin film and the Si substrate, and thus the thin films show a low L1 0 ordering temperature of T = 310 deg. C as compared with those deposited on Si/SiO 2 substrates. The accelerated L1 0 ordering transition is predominantly dependent on the rapid growth of the ordered domains during the interface reaction. The film thickness has an important effect on the interface reaction and thus can be used to tune the L1 0 ordering process of the FePt films.

  3. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gray, S.K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  4. Vortex sorter for Bose-Einstein condensates

    International Nuclear Information System (INIS)

    Whyte, Graeme; Veitch, John; Courtial, Johannes; Oehberg, Patrik

    2004-01-01

    We have designed interferometers that sort Bose-Einstein condensates into their vortex components. The Bose-Einstein condensates in the two arms of the interferometer are rotated with respect to each other through fixed angles; different vortex components then exit the interferometer in different directions. The method we use to rotate the Bose-Einstein condensates involves asymmetric phase imprinting and is itself new. We have modeled rotation through fixed angles and sorting into vortex components with even and odd values of the topological charge of two-dimensional Bose-Einstein condensates in a number of states (pure or superposition vortex states for different values of the scattering length). Our scheme may have applications for quantum information processing

  5. Isotope effects in gas-phase chemical reactions and photodissociation processes: Overview

    International Nuclear Information System (INIS)

    Kaye, J.A.

    1992-01-01

    The origins of isotope effects in equilibrium and non-equilibrium chemical processes are reviewed. In non-equilibrium processes, attention is given to isotope effects in simple bimolecular reactions, symmetry-related reactions, and photodissociation processes. Recent examples of isotope effects in these areas are reviewed. Some indication of other scientific areas for which measurements and/or calculations of isotope effects are used is also given. Examples presented focus on neutral molecule chemistry and in many cases complement examples considered in greater detail in the other chapters of this volume

  6. Kinetics and mechanism of solid-phase reactions of formation of yttrium ferrite with garnet structure

    Energy Technology Data Exchange (ETDEWEB)

    Pashchenko, V P; Yakushevskaya, F T; Chalyi, V P

    1977-04-01

    The perovskite phase is formed in the process of ferrogarnet formation both from the mixture of Y and Fe oxides and from mutually precipitated carbonates. The amount of the perovskite phase decreases with increasing duration of annealing. The process of the ferritoformation in the investigated systems can be presented as isovalent cationic substitution on the basis of the crystalline structure of Y/sub 2/O/sub 3/ with the formation of the perovskite structure. When the Fe concentration in orthoferrite increases, the phase with a garnet structure is formed.

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

    International Nuclear Information System (INIS)

    Xiong Guohong; Wang Minquan; Fan Xianping; Tang Xiaoming

    1993-01-01

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

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

    Science.gov (United States)

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

    1993-02-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-02-01

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

  10. ANALYTIC APPROXIMATION OF CARBON CONDENSATION ISSUES IN TYPE II SUPERNOVAE

    Energy Technology Data Exchange (ETDEWEB)

    Clayton, Donald D., E-mail: claydonald@gmail.com [Department of Physics and Astronomy, Clemson University, Clemson, SC (United States)

    2013-01-01

    I present analytic approximations for some issues related to condensation of graphite, TiC, and silicon carbide in oxygen-rich cores of supernovae of Type II. Increased understanding, which mathematical analysis can support, renders researchers more receptive to condensation in O-rich supernova gases. Taking SN 1987A as typical, my first analysis shows why the abundance of CO molecules reaches an early maximum in which free carbon remains more abundant than CO. This analysis clarifies why O-rich gas cannot oxidize C if {sup 56}Co radioactivity is as strong as in SN 1987A. My next analysis shows that the CO abundance could be regarded as being in chemical equilibrium if the CO molecule is given an effective binding energy rather than its laboratory dissociation energy. The effective binding energy makes the thermal dissociation rate of CO equal to its radioactive dissociation rate. This preserves possible relevance for the concept of chemical equilibrium. My next analysis shows that the observed abundances of CO and SiO molecules in SN 1987A rule out frequent suggestions that equilibrium condensation of SUNOCONs has occurred following atomic mixing of the He-burning shell with more central zones in such a way as to reproduce roughly the observed spectrum of isotopes in SUNOCONs while preserving C/O > 1. He atoms admixed along with the excess carbon would destroy CO and SiO molecules, leaving their observed abundances unexplained. The final analysis argues that a chemical quasiequilibrium among grains (but not gas) may exist approximately during condensation, so that its computational use is partially justified as a guide to which mineral phases would be stable against reactions with gas. I illustrate this point with quasiequilibrium calculations by Ebel and Grossman that have shown that graphite is stable even when O/C >1 if prominent molecules are justifiably excluded from the calculation of chemical equilibrium.

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

    Science.gov (United States)

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

    2016-01-01

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

  12. A macrothermodynamic approach to the limit of reversible capillary condensation.

    Science.gov (United States)

    Trens, Philippe; Tanchoux, Nathalie; Galarneau, Anne; Brunel, Daniel; Fubini, Bice; Garrone, Edoardo; Fajula, François; Di Renzo, Francesco

    2005-08-30

    The threshold of reversible capillary condensation is a well-defined thermodynamic property, as evidenced by corresponding states treatment of literature and experimental data on the lowest closure point of the hysteresis loop in capillary condensation-evaporation cycles for several adsorbates. The nonhysteretical filling of small mesopores presents the properties of a first-order phase transition, confirming that the limit of condensation reversibility does not coincide with the pore critical point. The enthalpy of reversible capillary condensation can be calculated by a Clausius-Clapeyron approach and is consistently larger than the condensation heat in unconfined conditions. Calorimetric data on the capillary condensation of tert-butyl alcohol in MCM-41 silica confirm a 20% increase of condensation heat in small mesopores. This enthalpic advantage makes easier the overcoming of the adhesion forces by the capillary forces and justifies the disappearing of the hysteresis loop.

  13. CONDENSED MATTER: STRUCTURE, THERMAL AND MECHANICAL PROPERTIES: Phase-field simulation of the effect of interaction among ordered domains on interdiffusion in Ni-Al-Cr alloys

    Science.gov (United States)

    Zhang, Yu-Xiang; Wang, Jin-Cheng; Yang, Yu-Juan; Yang, Gen-Cang; Zhou, Yao-He

    2009-10-01

    The effect of interaction among γ' ordered domains on the interdiffusion process in γ + γ'/γ and γ + γ'/γ + γ' diffusion couples is investigated by using the phase-field method, in which bulk free energy and mobility are linked with thermodynamic and kinetic databases. Simulated results show that the interaction among γ' ordered domains has great influence on the microstructure, the interdiffusion velocity and the volume fraction of γ' phase on both sides of the diffusion couples.

  14. Sedimentary condensation and authigenesis

    Science.gov (United States)

    Föllmi, Karl

    2016-04-01

    Most marine authigenic minerals form in sediments, which are subjected to condensation. Condensation processes lead to the formation of well individualized, extremely thin ( 100ky), and which experienced authigenesis and the precipitation of glaucony, verdine, phosphate, iron and manganese oxyhydroxides, iron sulfide, carbonate and/or silica. They usually show complex internal stratigraphies, which result from an interplay of sediment accumulation, halts in sedimentation, sediment winnowing, erosion, reworking and bypass. They may include amalgamated faunas of different origin and age. Hardgrounds may be part of condensed beds and may embody strongly condensed beds by themselves. Sedimentary condensation is the result of a hydrodynamically active depositional regime, in which sediment accumulation, winnowing, erosion, reworking and bypass are processes, which alternate as a function of changes in the location and intensity of currents, and/or as the result of episodic high-energy events engendered by storms and gravity flow. Sedimentary condensation has been and still is a widespread phenomenon in past and present-day oceans. The present-day distribution of glaucony and verdine-rich sediments on shelves and upper slopes, phosphate-rich sediments and phosphorite on outer shelves and upper slopes, ferromanganese crusts on slopes, seamounts and submarine plateaus, and ferromanganese nodules on abyssal seafloors is a good indication of the importance of condensation processes today. In the past, we may add the occurrence of oolitic ironstone, carbonate hardgrounds, and eventually also silica layers in banded iron formations as indicators of the importance of condensation processes. Besides their economic value, condensed sediments are useful both as a carrier of geochemical proxies of paleoceanographic and paleoenvironmental change, as well as the product of episodes of paleoceanographic and paleoenvironmental change themselves.

  15. Effect of local allergen priming on early, late, delayed-phase, and epicutaneous skin reactions

    NARCIS (Netherlands)

    Weller, F. R.; Weller, M. S.; Jansen, H. M.; de Monchy, J. G.

    1996-01-01

    Allergic disease is reflected in a chronic inflammatory response to an allergen. It is thought that local allergen priming underlies this chronicity. To assess the effect of allergen priming on the amplitude and histologic effect of the allergic reaction, four sequential, intracutaneous skin tests

  16. Effect of local allergen priming on early, late, delayed-phase, and epicutaneous skin reactions

    NARCIS (Netherlands)

    Weller, FR; Weller, MS; Jansen, HM; deMonchy, JGR

    1996-01-01

    Allergic disease is renected in a chronic inflammatory response to an allergen. It is thought that local allergen priming underlies this chronicity. To assess the effect of allergen priming on the amplitude and histologic effect of the allergic reaction, four sequential, intracutaneous skin tests

  17. Aqueous-phase Suzuki-Miyaura cross-coupling reactions of free halopurine bases

    Czech Academy of Sciences Publication Activity Database

    Čapek, Petr; Vrábel, Milan; Hasník, Zbyněk; Pohl, Radek; Hocek, Michal

    -, č. 20 (2006), s. 3515-3526 ISSN 0039-7881 R&D Projects: GA ČR(CZ) GA203/05/0043 Institutional research plan: CEZ:AV0Z40550506 Keywords : purines * cross-coupling * reactions Subject RIV: CC - Organic Chemistry Impact factor: 2.333, year: 2006

  18. Thermochemistry of the reactions between CN+ and H2O in the gas phase

    Science.gov (United States)

    Ijjaali, Fatima; Alcami, Manuel; Mo, Otilia; Yanez, Manuel

    The [H2, C, N, O]+ potential energy surface (PES) has been explored by means of high-level ab initio calculations, carried out in the framework of the G2 theory. From this survey we concluded that the predominant products of the CN+ +H2O reaction are the result of the dissociation of HNCOH+ species and to a much lesser extent of the CNHOH+ cation to yield CNH+ +OH. According to our results HCN+ should not be a product of this reaction because all pathways leading to its formation are unfavourable with regards to other competitive processes. Other reactive channels lead to the formation of the H2ONC+ structure which dissociates into CN + H2O+. The loss of NH(3Σ) and O(3P) seems to take place following spin-forbidden reaction paths through an intersystem crossing between the singlet and the triplet PESs. The global minimum of the PES, H2NCO+ is easily accessible and should lead to the loss of carbon monoxide which has not been experimentally observed in CN+ + H2O reactions. We cannot oOEer a clear explanation for this disagreement between theory and experiment.

  19. Isotope effects for base-promoted, gas-phase proton transfer reactions

    International Nuclear Information System (INIS)

    Grabowski, J.J.; Cheng, Xueheng

    1991-01-01

    Proton transfer reactions are among the most basic, the most common and the most important of chemical transformations; despite their apparent simplicity, much is unknown about this most fundamental of all chemical processes. Active interest in understanding the underlying principles of organic proton transfer reactions continues because of efforts being made to develop the theory of elementary chemical processes, because of the resurgence of interest in mechanistic organic chemistry and because of the resurgence of interest in mechanistic organic chemistry processes, because of the resurgence of interest in mechanistic organic chemistry and because of the dynamic role played by proton transfers in biochemical transformations. As organic chemists, the authors have used the flowing afterglow technique to gain an appreciation of the fundamental issues involved in reaction mechanisms by examining such processes in a solvent-free environment under thermally-equilibrated (300 K) conditions. Recent characterization of the facile production of both acetate and the monoenolate anion from the interaction of hydroxide or fluoride with acetic acid reinforces the idea that much yet must be learned about proton transfers/proton abstractions in general. Earlier work by Riveros and co-workers on competitive H vs D abstraction from α-d 1 -toluenes and by Noest and Nibbering on competitive H vs D abstraction from α,α,α-d 3 -acetone, in combination with the acetic acid results, challenged the author's to assemble a comprehensive picture of the competitive nature of proton transfer reactions for anionic base-promoted processes

  20. DFT study of the reactions of Mo and Mo with CO2 in gas phase

    Indian Academy of Sciences (India)

    understanding the mechanism of second-row metal reacting with CO2. The minimum energy ... et al.18 performed an IR study on the reaction of laser- ablated Mo atom .... indicate that the weak electrostatic interaction between. Mo. + and CO2 ...