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Sample records for gas phase structure

  1. Gas phase structure of transition metal dihydrides

    Demuynck, J.; Schaefer, H.F. III

    1980-01-01

    ESR and infrared spectroscopic measurements on matrix isolated MnH 2 and CrH 2 have recently suggested that these simple molecules may be bent. This result would be the opposite of that found experimentally for the transition metal dihalides MX 2 , known to be linear. Here the geometrical structure of MnH 2 has been investigated by molecular electronic structure theory. A large contracted Gaussian basis set [Mn(14s11p6p/9s8p3d), H(5s1p/3s1p)] was used in conjunction with self-consistent field and configuration interaction methods. These suggest that the 6 A 1 ground state of MnH 2 is linear. Further studies of the 3 A 1 state (one of several low-lying states) of TiH 2 also favor linearity, although this potential energy surface is extremely flat with respect to bending. Thus it appears probable that most MH 2 molecules, like the related MX 2 family, are linear

  2. A direct comparison of protein structure in the gas and solution phase: the Trp-cage

    Patriksson, Alexandra; Adams, Christopher M; Kjeldsen, Frank

    2007-01-01

    Molecular dynamics simulations of zwitterions of the Trp-cage protein in the gas phase show that the most stable ion in vacuo has preserved the charge locations acquired in solution. A direct comparison of the gas and solution-phase structures reveals that, despite the similarity in charge location...

  3. The gas phase structure of α -pinene, a main biogenic volatile organic compound

    Neeman, Elias M.; Avilés Moreno, Juan Ramón; Huet, Thérèse R.

    2017-12-01

    The gas phase structure of the bicyclic atmospheric aerosol precursor α-pinene was investigated employing a combination of quantum chemical calculation and Fourier transform microwave spectroscopy coupled to a supersonic jet expansion. The very weak rotational spectra of the parent species and all singly substituted 13C in natural abundance have been identified, from 2 to 20 GHz, and fitted to Watson's Hamiltonian model. The rotational constants were used together with geometrical parameters from density functional theory and ab initio calculations to determine the rs, r0, and rm(1 ) structures of the skeleton, without any structural assumption in the fit concerning the heavy atoms. The double C=C bond was found to belong to a quasiplanar skeleton structure containing 6 carbon atoms. Comparison with solid phase structure is reported. The significant differences of α-pinene in gas phase and other gas phase bicyclic monoterpene structures (β-pinene, nopinone, myrtenal, and bicyclo[3.1.1]heptane) are discussed.

  4. Molecular structure determination of cyclootane by ab initio and electron diffraction methods in the gas phase

    De Almeida, Wagner B.

    2000-01-01

    The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can ma...

  5. Biofilm structure and mass transfer in a gas phase trickle-bed biofilter.

    Zhu, X; Suidan, M T; Alonso, C; Yu, T; Kim, B J; Kim, B R

    2001-01-01

    Mass transport phenomena occurring in the biofilms of gas phase trickle-bed biofilters are investigated in this study. The effect of biofilm structure on mass transfer mechanisms is examined using experimental observation from the operating of biofilters, microelectrode techniques and microscopic examination. Since the biofilms of biofilters used for waste gas treatment are not completely saturated with water, there is not a distinguishable liquid layer outside the biofilm. Results suggest that due to this characteristic, gas phase substrates (such as oxygen or volatile organic compounds) may not be limited by the aqueous phase because transport of the compound into the biofilm can occur directly through non-wetted areas. On the other hand, for substrates that are present only in the liquid phase, such as nitrate, the mass transfer limitation is more serious because of the limited liquid supply. Microscopic observations show that a layered structure with void spaces exists within the biofilm. Oxygen concentration distributions along the depth of the biofilms are examined using an oxygen microelectrode. Results indicate that there are some high dissolved oxygen zones inside the biofilm, which suggests the existence of passages for oxygen transfer into the deeper sections of the biofilm in a gas phase trickle-bed biofilter. Both the low gas-liquid mass transfer resistance and the resulting internal structure contribute to the high oxygen penetration within the biofilms in gas phase trickle-bed biofilters.

  6. Comprehensive Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 3. Relating Solution-Phase to Gas-Phase Structures.

    Kondalaji, Samaneh Ghassabi; Khakinejad, Mahdiar; Valentine, Stephen J

    2018-06-01

    Molecular dynamics (MD) simulations have been utilized to study peptide ion conformer establishment during the electrospray process. An explicit water model is used for nanodroplets containing a model peptide and hydronium ions. Simulations are conducted at 300 K for two different peptide ion charge configurations and for droplets containing varying numbers of hydronium ions. For all conditions, modeling has been performed until production of the gas-phase ions and the resultant conformers have been compared to proposed gas-phase structures. The latter species were obtained from previous studies in which in silico candidate structures were filtered according to ion mobility and hydrogen-deuterium exchange (HDX) reactivity matches. Results from the present study present three key findings namely (1) the evidence from ion production modeling supports previous structure refinement studies based on mobility and HDX reactivity matching, (2) the modeling of the electrospray process is significantly improved by utilizing initial droplets existing below but close to the calculated Rayleigh limit, and (3) peptide ions in the nanodroplets sample significantly different conformers than those in the bulk solution due to altered physicochemical properties of the solvent. Graphical Abstract ᅟ.

  7. Molecular structure determination of cyclooctane by Ab Initio and electron diffraction methods in the gas phase

    Almeida, Wagner B. de

    2000-01-01

    The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can make a significant contribution for an unambiguous determination of the geometrical parameters. In this article the determination for an unambiguous determination of the geometrical parameters. In this article the determination of the molecular structure of the cyclooctane molecule by electron diffraction in the gas phase an initio calculations will be addressed, providing an example of a comparative analysis of theoretical and experimental predictions. (author)

  8. Probing the glycosidic linkage: secondary structures in the gas phase

    Simons, John P; Cristina Stanca-Kaposta, E; Cocinero, Emilio J; Liu, B [Chemistry Department, Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford OX1 3QZ (United Kingdom); Davis, Benjamin G; Gamblin, David P [Chemistry Department, Chemical Research Laboratory, 12 Mansfield Road, Oxford OX1 4TA (United Kingdom); Kroemer, Romano T [Sanofi-Aventis, CRVA, 13 quai Jules Guesde, BP14, 94403 Vitry-sur-Seine (France)], E-mail: John.Simons@chem.ox.ac.uk

    2008-10-15

    The functional importance of carbohydrates in biological processes, particularly those involving specific molecular recognition, is immense. Characterizing the three-dimensional (3D) structures of carbohydrates and glycoproteins, and their interactions with other molecules, not least the ubiquitous solvent, water, is a key starting point for understanding these processes. The combination of laser-based electronic and vibrational spectroscopy of mass-selected carbohydrate molecules and their hydrated complexes, conducted under molecular beam conditions, with ab initio computation is providing a uniquely powerful means of characterizing 3D carbohydrate conformations; the structures of their hydrated complexes, the hydrogen-bonded networks they support (or which support them); and the factors that determine their conformational and structural preferences.

  9. Probing the glycosidic linkage: secondary structures in the gas phase

    Simons, John P; Cristina Stanca-Kaposta, E; Cocinero, Emilio J; Liu, B; Davis, Benjamin G; Gamblin, David P; Kroemer, Romano T

    2008-01-01

    The functional importance of carbohydrates in biological processes, particularly those involving specific molecular recognition, is immense. Characterizing the three-dimensional (3D) structures of carbohydrates and glycoproteins, and their interactions with other molecules, not least the ubiquitous solvent, water, is a key starting point for understanding these processes. The combination of laser-based electronic and vibrational spectroscopy of mass-selected carbohydrate molecules and their hydrated complexes, conducted under molecular beam conditions, with ab initio computation is providing a uniquely powerful means of characterizing 3D carbohydrate conformations; the structures of their hydrated complexes, the hydrogen-bonded networks they support (or which support them); and the factors that determine their conformational and structural preferences.

  10. Probing Protein Structure and Folding in the Gas Phase by Electron Capture Dissociation

    Schennach, Moritz; Breuker, Kathrin

    2015-07-01

    The established methods for the study of atom-detailed protein structure in the condensed phases, X-ray crystallography and nuclear magnetic resonance spectroscopy, have recently been complemented by new techniques by which nearly or fully desolvated protein structures are probed in gas-phase experiments. Electron capture dissociation (ECD) is unique among these as it provides residue-specific, although indirect, structural information. In this Critical Insight article, we discuss the development of ECD for the structural probing of gaseous protein ions, its potential, and limitations.

  11. Gas Phase Structure of Amino Acids: La-Mb Studies

    Mata, I. Pena S.; Sanz, M. E.; Vaquero, V.; Cabezas, C.; Perez, C.; Blanco, S.; López, J. C.; Alonso, J. L.

    2009-06-01

    Recent improvements in our laser ablation molecular beam Fourier transform microwave (LA-MB-FTMW) spectrometer such as using Laval-type nozzles and picoseconds Nd:YAG lasers (30 to 150 ps) have allowed a major step forward in the capabilities of this experimental technique as demonstrated by the last results in serine cysteine and threonine^a for which seven, six and seven conformers have been respectively identified. Taking advantage of these improvements we have investigated the natural amino acids metionine, aspartic and glutamic acids and the γ-aminobutyric acid (GABA) with the aim of identify and characterize their lower energy conformers. Searches in the rotational spectra have lead to the identification of seven conformers of metionine, six and five of aspartic and glutamic acids, respectively, and seven for the γ-aminobutyric. These conformers have been unambiguously identified by their spectroscopic constants. In particular the ^{14}N nuclear quadrupole coupling constants, that depend heavily on the orientation of the amino group with respect to the principal inertial axes of the molecule, prove to be a unique tool to distinguish unambigously between conformations with similar rotational constants. For the γ-aminobutyric acid two of the seven observed structures are stablized by an intramolecular interaction n-π*. Two new conformers of proline have been identified together with the two previously observed. J. L. Alonso, C. Pérez, M. E. Sanz, J. C. López, S. Blanco, Phys.Chem.Chem.Phys., 2009, 11, 617. D. B. Atkinson, M. A. Smith, Rev. Sci. Instrum. 1995, 66, 4434 S. Blanco, M. E. Sanz, J. C. López, J. L. Alonso, Proc. Natl. Acad. Sci. USA2007, 104, 20183. M. E. Sanz, S. Blanco, J. C. López, J. L. Alonso, Angew. Chem. Int. Ed.,2008, 120, 6312. A. Lesarri, S. Mata, E. J. Cocinero, S. Blanco, J.C. López, J. L. Alonso, Angew. Chem. Int. Ed. , 2002, 41, 4673

  12. Structure of the gas-liquid annular two-phase flow in a nozzle section

    Yoshida, Kenji; Kataoka, Isao; Ohmori, Syuichi; Mori, Michitsugu

    2006-01-01

    Experimental studies on the flow behavior of gas-liquid annular two-phase flow passing through a nozzle section were carried out. This study is concerned with the central steam jet injector for a next generation nuclear reactor. In the central steam jet injector, steam/water annular two-phase flow is formed at the mixing nozzle. To make an appropriate design and to establish the high-performance steam injector system, it is very important to accumulate the fundamental data of the thermo-hydro dynamic characteristics of annular flow passing through a nozzle section. On the other hand, the transient behavior of multiphase flow, in which the interactions between two-phases occur, is one of the most interesting scientific issues and has attracted research attention. In this study, the transient gas-phase turbulence modification in annular flow due to the gas-liquid phase interaction is experimentally investigated. The annular flow passing through a throat section is under the transient state due to the changing cross sectional area of the channel and resultantly the superficial velocities of both phases are changed compared with a fully developed flow in a straight pipe. The measurements for the gas-phase turbulence were precisely performed by using a constant temperature hot-wire anemometer, and made clear the turbulence structure such as velocity profiles, fluctuation velocity profiles. The behavior of the interfacial waves in the liquid film flow such as the ripple or disturbance waves was also observed. The measurements for the liquid film thickness by the electrode needle method were also performed to measure the base film thickness, mean film thickness, maximum film thickness and wave height of the ripple or the disturbance waves. (author)

  13. Gas phase ion chemistry

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 2 covers the advances in gas phase ion chemistry. The book discusses the stabilities of positive ions from equilibrium gas-phase basicity measurements; the experimental methods used to determine molecular electron affinities, specifically photoelectron spectroscopy, photodetachment spectroscopy, charge transfer, and collisional ionization; and the gas-phase acidity scale. The text also describes the basis of the technique of chemical ionization mass spectrometry; the energetics and mechanisms of unimolecular reactions of positive ions; and the photodissociation

  14. Two-Phase Gas-Liquid Flow Structure Characteristics under Periodic Cross Forces Action

    V. V. Perevezentsev

    2015-01-01

    Full Text Available The article presents a study of two-phase gas-liquid flow under the action of periodic cross forces. The work objective is to obtain experimental data for further analysis and have structure characteristics of the two-phase flow movement. For research, to obtain data without disturbing effect on the flow were used optic PIV (Particle Image Visualization methods because of their noninvasiveness. The cross forces influence was provided by an experimental stand design to change the angular amplitudes and the periods of channel movement cycle with two-phase flow. In the range of volume gas rates was shown a water flow rate versus the inclination angle of immovable riser section and the characteristic angular amplitudes and periods of riser section inclination cycle under periodic cross forces. Data on distribution of average water velocity in twophase flow in abovementioned cases were also obtained. These data allowed us to draw a conclusion that a velocity distribution depends on the angular amplitude and on the period of the riser section roll cycle. This article belongs to publications, which study two-phase flows with no disturbing effect on them. Obtained data give an insight into understanding a pattern of twophase gas-liquid flow under the action of periodic cross forces and can be used to verify the mathematical models of the CFD thermo-hydraulic codes. In the future, the work development expects taking measurements with more frequent interval in the ranges of angular amplitudes and periods of the channel movement cycle and create a mathematical model to show the action of periodic cross forces on two-phase gas-liquid flow.

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

    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...

  16. Structure and dynamics of gas phase ions: Interplay between experiments and computations in IRMPD spectroscopy

    Coletti, Cecilia; Corinti, Davide; Paciotti, Roberto; Re, Nazzareno; Crestoni, Maria Elisa; Fornarini, Simonetta

    2017-11-01

    The investigation of the molecular structure and dynamics of ions in gas phase is an item of increasing interest, due the role such species play in many areas of chemistry and physics, not to mention that they often represent elusive intermediates in more complex reaction mechanisms. Infrared Multiple Photon Dissociation spectroscopy is today one of the most advanced technique to this purpose, because of its high sensitivity to even small structure changes. The interpretation of IRMPD spectra strongly relies on high level quantum mechanical computations, so that a close interplay is needed for a detailed understanding of structure and kinetics properties which can be gathered from the many applications of this powerful technique. Recent advances in experiment and theory in this field are here illustrated, with emphasis on recent progresses for the elucidation of the mechanism of action of cisplatin, one of the most widely used anticancer drugs.

  17. UPS and DFT investigation of the electronic structure of gas-phase trimesic acid

    Reisberg, L., E-mail: rebban@ut.ee [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia); Pärna, R. [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia); MAX IV Laboratory, Lund University, Fotongatan 2, 225 94 Lund (Sweden); Kikas, A.; Kuusik, I.; Kisand, V. [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia); Hirsimäki, M.; Valden, M. [Surface Science Laboratory, Optoelectronics Research Centre, Tampere University of Technology, FIN-33101 Tampere (Finland); Nõmmiste, E. [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia)

    2016-11-15

    Highlights: • In the current study outer valence band electronic structure of benzene-1,3,5-tricarboxylic acid was interpreted. • Experimental and calculated trimesic acid (TMA) spectrum were compared to ones of benzene and benzoic acid. • It is shown that similarities between MO energies and shapes for benzene and TMA exists. • Addition of carboxyl groups to the benzene ring clearly correlates with increasing binding energy of HOMO. - Abstract: Benzene-1,3,5-tricarboxylic acid (trimesic acid, TMA) molecules in gas-phase have been investigated by using valence band photoemission. The photoelectron spectrum in the binding energy region from 9 to 22 eV is interpreted by using density functional theory calculations. The electronic structure of TMA is compared with benzene and benzoic acid in order to demonstrate changes in molecular orbital energies induced by addition of carboxyl groups to benzene ring.

  18. Gas-phase structure and fragmentation pathways of singly protonated peptides with N-terminal arginine.

    Bythell, Benjamin J; Csonka, István P; Suhai, Sándor; Barofsky, Douglas F; Paizs, Béla

    2010-11-25

    The gas-phase structures and fragmentation pathways of the singly protonated peptide arginylglycylaspartic acid (RGD) are investigated by means of collision-induced-dissociation (CID) and detailed molecular mechanics and density functional theory (DFT) calculations. It is demonstrated that despite the ionizing proton being strongly sequestered at the guanidine group, protonated RGD can easily be fragmented on charge directed fragmentation pathways. This is due to facile mobilization of the C-terminal or aspartic acid COOH protons thereby generating salt-bridge (SB) stabilized structures. These SB intermediates can directly fragment to generate b(2) ions or facilely rearrange to form anhydrides from which both b(2) and b(2)+H(2)O fragments can be formed. The salt-bridge stabilized and anhydride transition structures (TSs) necessary to form b(2) and b(2)+H(2)O are much lower in energy than their traditional charge solvated counterparts. These mechanisms provide compelling evidence of the role of SB and anhydride structures in protonated peptide fragmentation which complements and supports our recent findings for tryptic systems (Bythell, B. J.; Suhai, S.; Somogyi, A.; Paizs, B. J. Am. Chem. Soc. 2009, 131, 14057-14065.). In addition to these findings we also report on the mechanisms for the formation of the b(1) ion, neutral loss (H(2)O, NH(3), guanidine) fragment ions, and the d(3) ion.

  19. Gas Phase Nanoparticle Synthesis

    Granqvist, Claes; Kish, Laszlo; Marlow, William

    This book deals with gas-phase nanoparticle synthesis and is intended for researchers and research students in nanomaterials science and engineering, condensed matter physics and chemistry, and aerosol science. Gas-phase nanoparticle synthesis is instrumental to nanotechnology - a field in current focus that raises hopes for environmentally benign, resource-lean manufacturing. Nanoparticles can be produced by many physical, chemical, and even biological routes. Gas-phase synthesis is particularly interesting since one can achieve accurate manufacturing control and hence industrial viability.

  20. Electron Scattering Studies of Gas Phase Molecular Structure at High Temperature

    Mawhorter, Richard J., Jr.

    A high precision counting electron diffraction study of the structure of gaseous sulfur dioxide as a function of temperature from 300(DEGREES) to 1000(DEGREES)K is presented. The results agree well with current theory, and yield insight into the effects of anharmonicity on molecular structure. Another aspect of molecular structure is the molecular charge density distribution. The difference (DELTA)(sigma) is between the electron scattering cross sections for the actual molecule and independent atom model (IAM) are a sensitive measure of the change in this distribution due to bond formation. These difference cross sections have been calculated using ab initio methods, and the results for a wide range of simple polyatomic molecules are presented. Such calculations are routinely done for a single, fixed molecular geometry, an approach which neglects the effects of the vibrational motion of real molecules. The effect of vibrational averaging is studied in detail for the three normal vibrational modes of H(,2)O in the ground state. The effects are small, lending credence to the practice of comparing cross sections calculated at a fixed geometry with inherently averaged experimental data. The efficacy of the standard formula used to account for vibrational averaging in the IAM is also examined. Finally, the nature of the ionic bond is probed with an experimental study of the structure of alkali chlorides, NaCl, KCl, RbCl, and CsCl, in the gas phase. Temperatures from 840-960(DEGREES)K were required to achieve the necessary vapor pressures of approximately 0.01 torr. A planar rhombic structure for the dimer molecule is confirmed, with a fairly uniform decrease of the chlorine-alkali-chlorine angle as the alkalis increase in size. The experiment also yields information on the amount of dimer present in the vapor, and these results are compared with thermodynamic values.

  1. The structure optimization of gas-phase surface discharge and its application for dye degradation

    Ying, CAO; Jie, LI; Nan, JIANG; Yan, WU; Kefeng, SHANG; Na, LU

    2018-05-01

    A gas-phase surface discharge (GSD) was employed to optimize the discharge reactor structure and investigate the dye degradation. A dye mixture of methylene blue, acid orange and methyl orange was used as a model pollutant. The results indicated that the reactor structure of the GSD system with the ratio of tube inner surface area and volume of 2.48, screw pitch between a high-voltage electrode of 9.7 mm, high-voltage electrode wire diameter of 0.8 mm, dielectric tube thickness of 2.0 mm and tube inner diameter of 16.13 mm presented a better ozone (O3) generation efficiency. Furthermore, a larger screw pitch and smaller wire diameter enhanced the O3 generation. After the dye mixture degradation by the optimized GSD system, 73.21% and 50.74% of the chemical oxygen demand (COD) and total organic carbon removal rate were achieved within 20 min, respectively, and the biochemical oxygen demand (BOD) and biodegradability (BOD/COD) improved.

  2. Ground-State Gas-Phase Structures of Inorganic Molecules Predicted by Density Functional Theory Methods

    Minenkov, Yury

    2017-11-29

    We tested a battery of density functional theory (DFT) methods ranging from generalized gradient approximation (GGA) via meta-GGA to hybrid meta-GGA schemes as well as Møller–Plesset perturbation theory of the second order and a single and double excitation coupled-cluster (CCSD) theory for their ability to reproduce accurate gas-phase structures of di- and triatomic molecules derived from microwave spectroscopy. We obtained the most accurate molecular structures using the hybrid and hybrid meta-GGA approximations with B3PW91, APF, TPSSh, mPW1PW91, PBE0, mPW1PBE, B972, and B98 functionals, resulting in lowest errors. We recommend using these methods to predict accurate three-dimensional structures of inorganic molecules when intramolecular dispersion interactions play an insignificant role. The structures that the CCSD method predicts are of similar quality although at considerably larger computational cost. The structures that GGA and meta-GGA schemes predict are less accurate with the largest absolute errors detected with BLYP and M11-L, suggesting that these methods should not be used if accurate three-dimensional molecular structures are required. Because of numerical problems related to the integration of the exchange–correlation part of the functional and large scattering of errors, most of the Minnesota models tested, particularly MN12-L, M11, M06-L, SOGGA11, and VSXC, are also not recommended for geometry optimization. When maintaining a low computational budget is essential, the nonseparable gradient functional N12 might work within an acceptable range of error. As expected, the DFT-D3 dispersion correction had a negligible effect on the internuclear distances when combined with the functionals tested on nonweakly bonded di- and triatomic inorganic molecules. By contrast, the dispersion correction for the APF-D functional has been found to shorten the bonds significantly, up to 0.064 Å (AgI), in Ag halides, BaO, BaS, BaF, BaCl, Cu halides, and Li and

  3. Structure Elucidation of Dimethylformamide-Solvated Alkylzinc Cations in the Gas Phase

    Dreiocker, F.; Oomens, J.; Meijer, Ajhm; Pickup, B. T.; Jackson, R. F. W.; Schafer, M.

    2010-01-01

    Organozinc iodides, useful for the synthesis of nonproteinogenic amino acids, are investigated in the gas phase by a combination of electrospray (ESI)-MS/MS, accurate ion mass measurements, and infrared multiphoton dissociation (IRMPD) spectroscopy employing a free electron laser. ESI allowed the

  4. Structure elucidation of dimethylformamide-solvated alkylzinc cations in the gas phase

    Dreiocker, F.; Oomens, J.; Meijer, A.J.H.M.; Pickup, B.T.; Jackson, R.F.W.; Schäfer, M.

    2010-01-01

    Organozinc iodides, useful for the synthesis of nonproteinogenic amino acids, are investigated in the gas phase by a combination of electrospray (ESI)-MS/MS, accurate ion mass measurements, and infrared multiphoton dissociation (IRMPD) spectroscopy employing a free electron laser. ESI allowed the

  5. Imaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules

    Boll, Rebecca; Rouzee, Arnaud; Adolph, Marcus

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular...

  6. Gas phase ion chemistry

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 1 covers papers on the advances of gas phase ion chemistry. The book discusses the advances in flow tubes and the measurement of ion-molecule rate coefficients and product distributions; the ion chemistry of the earth's atmosphere; and the classical ion-molecule collision theory. The text also describes statistical methods in reaction dynamics; the state selection by photoion-photoelectron coincidence; and the effects of temperature and pressure in the kinetics of ion-molecule reactions. The energy distribution in the unimolecular decomposition of ions, as well

  7. Gas phase pulse radiolysis

    Jonah, C.D.; Andong Liu; Mulac, W.A.

    1987-01-01

    Gas phase pulse radiolysis, a technique which can be used to study many different phenomena in chemistry and physics, is discussed. As a source of small radicals, pulse radiolysis is important to the field of chemistry, particularly to combustion and atmospheric kinetics. The reactions of 1,3-butadiene, allene, ethylene and acetylene with OH are presented. 52 refs., 1 fig., 1 tab

  8. Gas-Phase Thermolyses

    Carlsen, Lars; Egsgaard, Helge

    1982-01-01

    The unimolecular gas-phase thermolyses of 1,2,3-oxadithiolan 2-oxide and thiiran 1-oxide have been studied by the flash vacuum thermolysis–field ionization mass spectrometry (f.v.t.–f.i.m.s.) technique in the temperature range from 1 043 to 1 404 K. The reactions are rationalized in terms of sulp...

  9. Gas-Phase Thermolyses

    Carlsen, Lars; Egsgaard, Helge

    1982-01-01

    The unimolecular gas-phase thermolyses of the four methyl and ethyl monothioacetates (5)–(8) have been studied by the flash vacuum thermolysis–field ionization mass spectrometry technique in the temperature range 883–1 404 K. The types of reactions verified were keten formation, thiono–thiolo rea...

  10. Protein and Peptide Gas-phase Structure Investigation Using Collision Cross Section Measurements and Hydrogen Deuterium Exchange

    Khakinejad, Mahdiar

    Protein and peptide gas-phase structure analysis provides the opportunity to study these species outside of their explicit environment where the interaction network with surrounding molecules makes the analysis difficult [1]. Although gas-phase structure analysis offers a unique opportunity to study the intrinsic behavior of these biomolecules [2-4], proteins and peptides exhibit very low vapor pressures [2]. Peptide and protein ions can be rendered in the gas-phase using electrospray ionization (ESI) [5]. There is a growing body of literature that shows proteins and peptides can maintain solution structures during the process of ESI and these structures can persist for a few hundred milliseconds [6-9]. Techniques for monitoring gas-phase protein and peptide ion structures are categorized as physical probes and chemical probes. Collision cross section (CCS) measurement, being a physical probe, is a powerful method to investigate gas-phase structure size [3, 7, 10-15]; however, CCS values alone do not establish a one to one relation with structure(i.e., the CCS value is an orientationally averaged value [15-18]. Here we propose the utility of gas-phase hydrogen deuterium exchange (HDX) as a second criterion of structure elucidation. The proposed approach incudes extensive MD simulations to sample biomolecular ion conformation space with the production of numerous, random in-silico structures. Subsequently a CCS can be calculated for these structures and theoretical CCS values are compared with experimental values to produce a pool of candidate structures. Utilizing a chemical reaction model based on the gas-phase HDX mechanism, the HDX kinetics behavior of these candidate structures are predicted and compared to experimental results to nominate the best in-silico structures which match (chemically and physically) with experimental observations. For the predictive approach to succeed, an extensive technique and method development is essential. To combine CCS

  11. Gas-Phase Thermolysis

    Carlsen, Lars; Egsgaard, Helge; Schaumann, Ernst

    1980-01-01

    The unimolecular gas-phase thermolytic decomposition of three silylated thionocarboxylic acid derivatives (2b), (3), and (8) have been studied by the flash vacuum thermolysis–field ionization mass spectrometry technique in the temperature range from 783 to 1 404 K in order to elucidate its possible...... applicability as a route to thioketens. Only very minor amounts of the expected thioketens were found, whereas the corresponding ketens were obtained as the major products. A possible mechanism for keten formation is discussed....

  12. Activation of methane by zinc: gas-phase synthesis, structure, and bonding of HZnCH3.

    Flory, Michael A; Apponi, Aldo J; Zack, Lindsay N; Ziurys, Lucy M

    2010-12-08

    The methylzinc hydride molecule, HZnCH3, has been observed in the gas phase for the first time in the monomeric form using high-resolution spectroscopic techniques. The molecule was synthesized by two methods: the reaction of dimethylzinc with hydrogen gas and methane in an AC discharge and the reaction of zinc vapor produced in a Broida-type oven with methane in a DC discharge. HZnCH3 was identified on the basis of its pure rotational spectrum, which was recorded using millimeter/submillimeter direct-absorption and Fourier transform microwave techniques over the frequency ranges 332-516 GHz and 18-41 GHz, respectively. Multiple rotational transitions were measured for this molecule in seven isotopic variants. K-ladder structure was clearly present in all of the spectra, indicating a molecule with C3v symmetry and a (1)A1 ground electronic state. Extensive quadrupole hyperfine structure arising from the (67)Zn nucleus was observed for the H(67)ZnCH3 species, suggesting covalent bonding to the zinc atom. From the multiple isotopic substitutions, a precise structure for HZnCH3 has been determined. The influence of the axial hydrogen atom slightly distorts the methyl group but stabilizes the Zn-C bond. This study suggests that HZnCH3 can be formed through the oxidative addition of zinc to methane in the gas phase under certain conditions. HZnCH3 is the first metal-methane insertion complex to be structurally characterized.

  13. Evolution of the structure of a gas-liquid two-phase flow in a large vertical pipe

    Horst-Michael Prasser; Matthias Beyer; Helmar Carl; Sabine Gregor; Dirk Lucas; Peter Schuetz; Frank-Peter Weiss

    2005-01-01

    Full text of publication follows: Experimental results on the evolution of the radial gas fraction profiles, gas velocity profiles and bubble size distributions in a gas-liquid two-phase flow along a large vertical pipe of 194 mm inner diameter are presented. The tests were performed at the TOPFLOW facility in Rossendorf, where two wire-mesh sensors were used to measure sequences of two-dimensional distributions of local instantaneous gas fraction within the complete pipe cross-section with a lateral resolution of 3 mm and a sampling frequency of 2500 Hz. This data is the basis for a fast flow visualization and for the calculation of the mentioned profiles. The gas fraction profiles were obtained by averaging the sequences over time, velocities were measured by cross-correlation of the signals of the two sensors, which were located on a short (63 mm) distance behind each other. The high resolution of the mesh sensors allows to identify regions of connected measuring points in the data array, which are filled with the gas phase. This method was used to obtain the bubble size distributions. In the experiments, the superficial velocities ranged from 0.04 to 8 m/s for the gas phase and from 0.04 to 1.6 m/s for the liquid. In this way, the experiments cover the range from bubbly to churn turbulent flow regimes. The evolution of the flow structure was studied by varying the distance between the gas injection and the sensor position. This distance was changed by the help of a so-called variable gas injection set-up. It consists of 6 gas injection units, each of them equipped with three rings of orifices in the pipe wall for the gas injection. These rings are fed with the gas phase from ring chambers, which can be individually controlled by valves. The middle ring has orifices of 4 mm diameter, while the upper and the lower rings have nozzles of 1 mm diameter. In this way, 18 different inlet lengths and two different gas injection geometries can be chosen. The latter

  14. Tuning structural motifs and alloying of bulk immiscible Mo-Cu bimetallic nanoparticles by gas-phase synthesis

    Krishnan, Gopi; Verheijen, Marcel A.; Ten Brink, Gert H.; Palasantzas, George; Kooi, Bart J.

    2013-05-01

    Nowadays bimetallic nanoparticles (NPs) have emerged as key materials for important modern applications in nanoplasmonics, catalysis, biodiagnostics, and nanomagnetics. Consequently the control of bimetallic structural motifs with specific shapes provides increasing functionality and selectivity for related applications. However, producing bimetallic NPs with well controlled structural motifs still remains a formidable challenge. Hence, we present here a general methodology for gas phase synthesis of bimetallic NPs with distinctively different structural motifs ranging at a single particle level from a fully mixed alloy to core-shell, to onion (multi-shell), and finally to a Janus/dumbbell, with the same overall particle composition. These concepts are illustrated for Mo-Cu NPs, where the precise control of the bimetallic NPs with various degrees of chemical ordering, including different shapes from spherical to cube, is achieved by tailoring the energy and thermal environment that the NPs experience during their production. The initial state of NP growth, either in the liquid or in the solid state phase, has important implications for the different structural motifs and shapes of synthesized NPs. Finally we demonstrate that we are able to tune the alloying regime, for the otherwise bulk immiscible Mo-Cu, by achieving an increase of the critical size, below which alloying occurs, closely up to an order of magnitude. It is discovered that the critical size of the NP alloy is not only affected by controlled tuning of the alloying temperature but also by the particle shape.Nowadays bimetallic nanoparticles (NPs) have emerged as key materials for important modern applications in nanoplasmonics, catalysis, biodiagnostics, and nanomagnetics. Consequently the control of bimetallic structural motifs with specific shapes provides increasing functionality and selectivity for related applications. However, producing bimetallic NPs with well controlled structural motifs still

  15. Multiphase forces on bend structures – critical gas fraction for transition single phase gas to multiphase flow behaviour

    Belfroid, S.P.C.; Nennie, E.D.; Lewis, M.

    2016-01-01

    Piping structures are generally subjected to high dynamic loading due to multiphase forces. In particular subsea structures are very vulnerable as large flexibility is required to cope for instance with thermal stresses. The forces due to multiphase flow are characterized by a broadband spectrum

  16. The structural phase diagram and oxygen equilibrium partial pressure of YBa2CU3O6+x studied by neutron powder diffraction and gas volumetry

    Andersen, N.H.; Lebech, B.; Poulsen, H.F.

    1990-01-01

    An experimental technique based on neutron powder diffraction and gas volumetry is presented and used to study the structural phase diagram of YBa2Cu3O6+x under equilibrium conditions in an extended part of (x, T)-phase (0.15

  17. PIV Measurement of Transient 3-D (Liquid and Gas Phases) Flow Structures Created by a Spreading Flame over 1-Propanol

    Hassan, M. I.; Kuwana, K.; Saito, K.

    2001-01-01

    In the past, we measured three-D flow structure in the liquid and gas phases that were created by a spreading flame over liquid fuels. In that effort, we employed several different techniques including our original laser sheet particle tracking (LSPT) technique, which is capable of measuring transient 2-D flow structures. Recently we obtained a state-of-the-art integrated particle image velocimetry (IPIV), whose function is similar to LSPT, but it has an integrated data recording and processing system. To evaluate the accuracy of our IPIV system, we conducted a series of flame spread tests using the same experimental apparatus that we used in our previous flame spread studies and obtained a series of 2-D flow profiles corresponding to our previous LSPT measurements. We confirmed that both LSPT and IPIV techniques produced similar data, but IPIV data contains more detailed flow structures than LSPT data. Here we present some of newly obtained IPIV flow structure data, and discuss the role of gravity in the flame-induced flow structures. Note that the application of IPIV to our flame spread problems is not straightforward, and it required several preliminary tests for its accuracy including this IPIV comparison to LSPT.

  18. Application of structured illumination to gas phase thermometry using thermographic phosphor particles: a study for averaged imaging

    Zentgraf, Florian; Stephan, Michael; Berrocal, Edouard; Albert, Barbara; Böhm, Benjamin; Dreizler, Andreas

    2017-07-01

    Structured laser illumination planar imaging (SLIPI) is combined with gas phase thermometry measurements using thermographic phosphor (TGP) particles. The technique is applied to a heated jet surrounded by a coflow which is operated at ambient temperature. The respective air flows are seeded with a powder of BaMgAl10O17:Eu2+ (BAM) which is used as temperature-sensitive gas phase tracer. Upon pulsed excitation in the ultraviolet spectral range, the temperature is extracted based on the two-color ratio method combined with SLIPI. The main advantage of applying the SLIPI approach to phosphor thermometry is the reduction of particle-to-particle multiple light scattering and diffuse wall reflections, yielding a more robust calibration procedure as well as improving the measurement accuracy, precision, and sensitivity. For demonstration, this paper focuses on sample-averaged measurements of temperature fields in a jet-in-coflow configuration. Using the conventional approach, which in contrast to SLIPI is based on imaging with an unmodulated laser light sheet, we show that for the present setup typically 40% of the recorded signal is affected by the contribution of multiply scattered photons. At locations close to walls even up to 75% of the apparent signal is due to diffuse reflection and wall luminescence of BAM sticking at the surface. Those contributions lead to erroneous temperature fields. Using SLIPI, an unbiased two-color ratio field is recovered allowing for two-dimensional mean temperature reconstructions which exhibit a more realistic physical behavior. This is in contrast to results deduced by the conventional approach. Furthermore, using the SLIPI approach it is shown that the temperature sensitivity is enhanced by a factor of up to 2 at 270 °C. Finally, an outlook towards instantaneous SLIPI phosphorescence thermometry is provided.

  19. Ground-State Gas-Phase Structures of Inorganic Molecules Predicted by Density Functional Theory Methods

    Minenkov, Yury; Cavallo, Luigi

    2017-01-01

    -GGA approximations with B3PW91, APF, TPSSh, mPW1PW91, PBE0, mPW1PBE, B972, and B98 functionals, resulting in lowest errors. We recommend using these methods to predict accurate three-dimensional structures of inorganic molecules when intramolecular dispersion

  20. Structure and reactivity of molybdenum oxide cluster ions in the gas phase

    Goncharov, V.B.; Fialko, E.F.

    2002-01-01

    A set of cluster ions of molybdenum oxides Mo x O y + (x = 1-5, y = 1-15) was prepared using a combination of the ionic cyclotron resonance method and Knudsen effusion source. Dependence of concentration of different molybdenum oxide ions on the time of retention and their interaction with carbon monoxide was studied. It is shown that Mo x O y + ions with x>3 contain cyclic fragment Mo 3 O 9 in their structure. Oxygen binding energies within ionic clusters Mo x O y + were estimated [ru

  1. Gas-phase synthesis and structure of monomeric ZnOH: a model species for metalloenzymes and catalytic surfaces.

    Zack, Lindsay N; Sun, Ming; Bucchino, Matthew P; Clouthier, Dennis J; Ziurys, Lucy M

    2012-02-16

    Monomeric ZnOH has been studied for the first time using millimeter and microwave gas-phase spectroscopy. ZnOH is important in surface processes and at the active site of the enzyme carbonic anhydrase. In the millimeter-wave direct-absorption experiments, ZnOH was synthesized by reacting zinc vapor, produced in a Broida-type oven, with water. In the Fourier-transform microwave measurements, ZnOH was produced in a supersonic jet expansion of CH(3)OH and zinc vapor, created by laser ablation. Multiple rotational transitions of six ZnOH isotopologues in their X(2)A' ground states were measured over the frequency range of 22-482 GHz, and splittings due to fine and hyperfine structure were resolved. An asymmetric top pattern was observed in the spectra, showing that ZnOH is bent, indicative of covalent bonding. From these data, spectroscopic constants and an accurate structure were determined. The Zn-O bond length was found to be similar to that in carbonic anhydrase and other model enzyme systems.

  2. Using Gas-Phase Guest-Host Chemistry to Probe the Structures of b Ions of Peptides

    Somogyi, Árpád; Harrison, Alex G.; Paizs, Béla

    2012-12-01

    Middle-sized b n ( n ≥ 5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen-deuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small b n ( n ≤ 4) fragments do not form stable ammonia adducts. We propose that complex formation of b n ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear b n ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b 4 , b 5 , and b 7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H…O H-bonds; this stabilization is much stronger for macrocyclic b n isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest-host chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b 9 , b 9 -A, and b 9 -2A of A8YA, and b 13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures.

  3. The molecular structure of 4-methylpyridine-N-oxide: Gas-phase electron diffraction and quantum chemical calculations

    Belova, Natalya V.; Girichev, Georgiy V.; Kotova, Vitaliya E.; Korolkova, Kseniya A.; Trang, Nguyen Hoang

    2018-03-01

    The molecular structure of 4-methylpiridine-N-oxide, 4-MePyO, has been studied by gas-phase electron diffraction monitored by mass spectrometry (GED/MS) and quantum chemical (DFT) calculations. Both, quantum chemistry and GED analyses resulted in CS molecular symmetry with the planar pyridine ring. Obtained molecular parameters confirm the hyperconjugation in the pyridine ring and the sp2 hybridization concept of the nitrogen and carbon atoms in the ring. The experimental geometric parameters are in a good agreement with the parameters for non-substituted N-oxide and reproduced very closely by DFT calculations. The presence of the electron-donating CH3 substituent in 4-MePyO leads to a decrease of the ipso-angle and to an increase of r(N→O) in comparison with the non-substituted PyO. Electron density distribution analysis has been performed in terms of natural bond orbitals (NBO) scheme. The nature of the semipolar N→O bond is discussed.

  4. Studies of matrix diffusion in gas phase

    Hartikainen, K.; Timonen, J.; Vaeaetaeinen, K.; Pietarila, H.

    1994-03-01

    The diffusion of solutes from fractures into rock matrix is an important factor in the safety analysis of disposal of radioactive waste. Laboratory measurements are needed to complement field investigations for a reliable determination of the necessary transport parameters. Measurements of diffusion coefficients in tight rock samples are usually time consuming because the diffusion processes are slow. On the other hand it is well known that diffusion coefficients in the gas phase are roughly four orders of magnitude larger than those in the liquid phase. Therefore, for samples whose structures do not change much upon drying, it is possible to estimate the diffusion properties of the liquid phase when the properties of the gas phase are known. Advantages of the gas method are quick and easy measurements. In the measurements nitrogen was used as the carrier gas and helium as the tracer gas, and standard techniques have been used for helium detection. Techniques have been developed for both channel flow and through-diffusion measurements. The breakthrough curves have been measured in every experiment and all measurements have been modelled by using appropriate analytical models. As a result matrix porosities and effective diffusion coefficients in the gas phase have been determined. (12 refs., 21 figs., 6 tabs.)

  5. The structure and conformations of piracetam (2-oxo-1-pyrrolidineacetamide): Gas-phase electron diffraction and quantum chemical calculations

    Ksenafontov, Denis N.; Moiseeva, Natalia F.; Khristenko, Lyudmila V.; Karasev, Nikolai M.; Shishkov, Igor F.; Vilkov, Lev V.

    2010-12-01

    The geometric structure of piracetam was studied by quantum chemical calculations (DFT and ab initio), gas electron diffraction (GED), and FTIR spectroscopy. Two stable mirror symmetric isomers of piracetam were found. The conformation of pyrrolidine ring is an envelope in which the C4 atom deviates from the ring plane, the angle between the planes (C3 sbnd C4 sbnd C5) and (C2 sbnd C3 sbnd C5) is 154.1°. The direction of the deviation is the same as that of the side acetamide group. The piracetam molecule is stabilized in the gas phase by an intramolecular hydrogen bond between the N9H 2 group and the oxygen O6, bonded to C2. The principal structural parameters ( re, Å and ∠e, degrees; uncertainties are 3 σLS values) were found to be: r(С3 sbnd С4) = 1.533(1), r(C4 sbnd C5) = 1.540(1), r(N1 sbnd C5) = 1.456(1), r(C2 sbnd C3) = 1.520(1), r(N1 sbnd C7) = 1.452(1), r(C7 sbnd C8) = 1.537(1), r(N1 sbnd C2) = 1.365(2), r(C8 sbnd N9) = 1.360(2), r(C2 dbnd O6) = 1.229(1), r(C8 dbnd O10) = 1.221(1), ∠C2 sbnd N1 sbnd C5 = 113.4(6), ∠N1 sbnd C2 sbnd C3 = 106.9(6), ∠N1 sbnd C7 sbnd C8 = 111.9(6), ∠C7 sbnd C8 sbnd N9 = 112.5(6), ∠N1 sbnd C2 sbnd O6 = 123.0(4), ∠C3 sbnd N1 sbnd C7 = 120.4(4), ∠C7 sbnd C8 sbnd O10 = 120.2(4), ∠C5 sbnd N1 sbnd C2 sbnd O6 = 170(6), ∠C3 sbnd C2 sbnd N1 sbnd C7 = 178(6), ∠C2 sbnd N1 sbnd C7 sbnd C8 = 84.2, ∠N1 sbnd C7 sbnd C8 sbnd O10 = 111.9.

  6. Gas Phase Molecular Dynamics

    Hall, G.E.; Prrese, J.M.; Sears, T.J.; Weston, R.E.

    1999-01-01

    The goal of this research is the understanding of elementary chemical and physical processes important in the combustion of fossil fuels. Interest centers on reactions involving short-lived chemical intermediates and their properties. High-resolution high-sensitivity laser absorption methods are augmented by high temperature flow-tube reaction kinetics studies with mass spectrometric sampling. These experiments provide information on the energy levels, structures and reactivity of molecular flee radical species and, in turn, provide new tools for the study of energy flow and chemical bond cleavage in the radicals in chemical systems. The experimental work is supported by theoretical and computational work using time-dependent quantum wave packet calculations that provide insights into energy flow between the vibrational modes of the molecule

  7. Gas phase structures and charge localization in small aluminum oxide anions: Infrared photodissociation spectroscopy and electronic structure calculations

    Song, Xiaowei; Fagiani, Matias R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany); Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig (Germany); Gewinner, Sandy; Schöllkopf, Wieland [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany); Asmis, Knut R., E-mail: knut.asmis@uni-leipzig.de, E-mail: js@chemie.hu-berlin.de [Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig (Germany); Bischoff, Florian A.; Berger, Fabian; Sauer, Joachim, E-mail: knut.asmis@uni-leipzig.de, E-mail: js@chemie.hu-berlin.de [Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, D-10099 Berlin (Germany)

    2016-06-28

    We use cryogenic ion trap vibrational spectroscopy in combination with quantum chemical calculations to study the structure of mono- and dialuminum oxide anions. The infrared photodissociation spectra of D{sub 2}-tagged AlO{sub 1-4}{sup −} and Al{sub 2}O{sub 3-6}{sup −} are measured in the region from 400 to 1200 cm{sup −1}. Structures are assigned based on a comparison to simulated harmonic and anharmonic IR spectra derived from electronic structure calculations. The monoaluminum anions contain an even number of electrons and exhibit an electronic closed-shell ground state. The Al{sub 2}O{sub 3-6}{sup −} anions are oxygen-centered radicals. As a result of a delicate balance between localization and delocalization of the unpaired electron, only the BHLYP functional is able to qualitatively describe the observed IR spectra of all species with the exception of AlO{sub 3}{sup −}. Terminal Al–O stretching modes are found between 1140 and 960 cm{sup −1}. Superoxo and peroxo stretching modes are found at higher (1120-1010 cm{sup −1}) and lower energies (850-570 cm{sup −1}), respectively. Four modes in-between 910 and 530 cm{sup −1} represent the IR fingerprint of the common structural motif of dialuminum oxide anions, an asymmetric four-member Al–(O){sub 2}–Al ring.

  8. GAS PHASE STRUCTURE AND STABILITY OF COMPLEX FORMED BY H2O, NH3, H2S AND THEIR METHYL DERIVATIVES WITH THE CATION CO2+

    Cahyorini Kusumawardani

    2010-06-01

    Full Text Available Ab initio molecular orbital calculations at the Hartree-Fock-Self Consistent Field (HF-SCF have been performed in order to determine the structure and gas phase energies of complex formed by the Lewis bases of H2O, NH3, H2S and their methyl derivatives with the cation Co2+. The relative basicities of the base studied depend on both the substituent. The gas-phase interaction energies computed by the SCF method including electron correlation Møller-Plesset 2 (MP2 dan Configuration Iteration (CI were comparable in accuracy. The binding energies computed by these two methods reach the targeted chemical accuracy.   Keywords: ab initio calculation, cobalt complex, structure stability

  9. Soil-gas phase transport and structure parameters for soils under different management regimes and at two moisture levels

    Eden, Marie; Møldrup, Per; Schjønning, Per

    2012-01-01

    Measurements of diffusive and convective gas transport parameters can be used to describe soil functional architecture and reveal key factors for soil structure development. Undisturbed 100-cm(3) soil samples were sampled at the Long-term Research on Agricultural Systems experiment located...... displayed markedly lower D-P/D-0 values at similar air-filled porosity, illustrating soil structure effects on D-P/D-0. The Currie tortuosity-connectivity parameter, X=Log(D-P/D-0)/Log(epsilon), decreased with increasing bulk density in the intact samples at both moisture conditions, suggesting less...

  10. Solid gas reaction phase diagram under high gas pressure

    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

  11. Gas-Phase Reactivity of Microsolvated Anions

    Thomsen, Ditte Linde

    the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared......Gas-phase studies of ion-molecule reactions shed light on the intrinsic factors that govern reactivity; and even solvent effects can be examined in the gasphase environment by employing microsolvated ions. An area that has received considerable attention with regard to the interplay between...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  12. Simulation of phase structures

    Lawson, J.

    1995-01-01

    This memo outlines a procedure developed by the author to extract information from phase measurements and produce a simulated phase structure for use in modeling optical systems, including characteristic optics for the Beamlet and NIF laser systems. The report includes an IDL program listing

  13. Structural and magnetic properties of FePt nanoparticles from the gas phase; Strukturelle und magnetische Eigenschaften von FePt-Nanopartikeln aus der Gasphase

    Dmitrieva, O.

    2007-09-21

    In this work, we present the structural and magnetic characterization of FePt nanoparticles. The nanoparticles with mean size of about 6 nm were prepared by sputtering in the gas and subsequent inert gas condensation. The particles are annealed in the furnace during their flight prior to deposition on a substrate. The aim of this work is to prepare magnetically hard FePt nanoparticles in the L1{sub 0}-ordered phase. The structure of the particles was investigated by high-resolution transmission electron microscopy, and the investigations were supported by contrast simulations. The morphology of the particles varies with the sputter-gas pressure and with the annealing temperature. At a pressure of 0.5 mbar, the FePt-nanoparticles are multiply-twinned with an icosahedral structure and exhibit no formation of the L1{sub 0}-ordered phase. At a higher pressure of 1 mbar and an annealing temperature of 1000 C, the particles are partially single-crystalline. About 36 % of the particles are found to be in the L1{sub 0}-ordered state as was estimated by statistical counting supported by simulations. In order to activate the volume diffusion in the particles and to stabilize the formation of the L1{sub 0}-ordered state, the addition of nitrogen was used during the sputtering phase. In this phase, atomic nitrogen is incorporated interstitially into the structure of the primary particles. After annealing nitrogen effuses out of the particles and, thereby, increases the volume diffusion of the Fe and Pt atoms. The incorporation of nitrogen atoms during nucleation and their effusion at an annealing temperature of 1000 C was verified by electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS). Structural investigations on particles prepared in the presence of nitrogen shows that most of the particles are single-crystalline and about 70 % of them are L1{sub 0}-ordered. Detailed structural analysis of the nanoparticles was done by the exit wave

  14. Iodine removal from a gas phase

    Vikis, A. Ch.

    1982-01-01

    Iodine, e.g. radioactive iodine, present as one or more organic iodides, optionally with elemental iodine, in a gas phase (e.g. air) are removed by photochemically decomposing the organic iodides to elemental iodine, reacting the iodine produced, and any initially present with excess ozone, preferably photochemically produced in situ in the gas phase to produce solid iodine oxides, and removing the solid oxides from the gas phase. (author)

  15. Iodine removal from a gas phase

    Vikis, A.C.

    1984-01-01

    Iodine, e.g. radioactive iodine, present as one or more organic iodides, optionally with elemental iodine, in a gas phase (e.g. air) are removed by photochemically decomposing the organic iodides to elemental iodine, reacting the iodine produced, and any initially present with excess ozone, preferably photochemically produced in situ in the gas phase to produce solid iodine oxides, and removing the solid oxides from the gas phase

  16. Phase interaction in the metal-oxide melts-gas system the modeling of structure, properties and processes

    Boronenkov, V; Leontiev, L

    2012-01-01

    This monograph describes mathematical models that enable prediction of phase compositions for various technological processes, as developed on the base of a complex physico-chemical analysis of reaction. It studies thermodynamics and kinetics of specific stages of complex pyrometallurgical processes involving boron, carbon, sulfur, tungsten, phosphorus, and many more, as well as their exposure to all sorts of factors. First and foremost, this enables to optimize processes and technologies at the stage of design, while traditional empirical means of development of new technologies are basically incapable of providing an optimal solution. Simulation results of metals and alloys production, welding and coating technologies allow obtaining materials with pre-given composition, structure and properties in a cost-saving and conscious manner. Moreover, a so-called "inverse problem", i.e., selecting source materials which would ensure the required results, cannot be solved by any other means.

  17. GAS PHASE ION CHEMISTRY OF COUMARINS: AB INITIO ...

    B. S. Chandravanshi

    The gas phase ion chemistry of coumarins using electron ionization (EI), positive chemical ionization (PCI) and ... Figure 1. Generic chemical structures of the coumarins in this study. ..... Part of this work was conducted using the resources of ...

  18. Dynamic simulation of gas-liquid two-phase flow : effect of column aspect ratio on the flow structure

    Delnoij, E.; Kuipers, J.A.M.; van Swaaij, W.P.M.

    1997-01-01

    In this paper an Eulerian/Lagrangian model, describing the hydrodynamics of a gas-liquid bubble column, is presented. The model resolves the time dependent, two-dimensional motion of small, spherical gas bubbles in a liquid using the equation of motion. The model incorporates all relevant forces

  19. Dynamic simulation of gas-liquid two-phase flow: effect of column aspect ratio on the flow structure.

    Delnoij, E.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

    1997-01-01

    In this paper an Eulerian/Lagrangian model, describing the hydrodynamics of a gas-liquid bubble column, is presented. The model resolves the time dependent, two-dimensional motion of small, spherical gas bubbles in a liquid using the equation of motion. The model incorporates all relevant forces

  20. Identification of isomers in the gas phase and as adsorbates by near-edge X-ray absorption fine structure spectroscopy: Cis- and trans-stilbene

    Püttner, Ralph; Schmidt-Weber, Philipp; Kampen, Thorsten; Kolczewski, Christine; Hermann, Klaus; Horn, Karsten

    2017-01-01

    Highlights: • NEXAFS spectra of the cis- and trans-isomer of stilbene reveal distinct differences by which the isomers can be distinguished. • DFT calculations using the transition potential approach assign specific transitions that are different in the two isomers. • On Si(100), these differences in NEXAFS are also observed, suggesting that their conformations survive in the bonding situation. • NEXAFS is thus shown to be a sensitive tool to distinguish isomers in adsorbed species. - Abstract: Near-edge x-ray absorption fine structure spectra of the cis- and trans-isomers of stilbene in the gas phase reveal clear differences, which are analyzed by results from density-functional theory calculations using the transition potential approach. The differences between the two species also occur in stilbene adsorbed on Si(100), opening the way towards studying structural changes in molecules in different surface environments, and configurational switching in organic molecules on surfaces in particular.

  1. Identification of isomers in the gas phase and as adsorbates by near-edge X-ray absorption fine structure spectroscopy: Cis- and trans-stilbene

    Püttner, Ralph [Department of Physics, Freie Universität Berlin, 14195 Berlin (Germany); Schmidt-Weber, Philipp [Fritz Haber Institute of the Max Planck Society, 14195 Berlin (Germany); Kampen, Thorsten [SPECS Surface Nano Analysis GmbH, 13355 Berlin (Germany); Kolczewski, Christine [Deutsches Museum München, 80538 Munich (Germany); Hermann, Klaus [Fritz Haber Institute of the Max Planck Society, 14195 Berlin (Germany); Horn, Karsten, E-mail: horn@fhi-berlin.mpg.de [Fritz Haber Institute of the Max Planck Society, 14195 Berlin (Germany)

    2017-02-15

    Highlights: • NEXAFS spectra of the cis- and trans-isomer of stilbene reveal distinct differences by which the isomers can be distinguished. • DFT calculations using the transition potential approach assign specific transitions that are different in the two isomers. • On Si(100), these differences in NEXAFS are also observed, suggesting that their conformations survive in the bonding situation. • NEXAFS is thus shown to be a sensitive tool to distinguish isomers in adsorbed species. - Abstract: Near-edge x-ray absorption fine structure spectra of the cis- and trans-isomers of stilbene in the gas phase reveal clear differences, which are analyzed by results from density-functional theory calculations using the transition potential approach. The differences between the two species also occur in stilbene adsorbed on Si(100), opening the way towards studying structural changes in molecules in different surface environments, and configurational switching in organic molecules on surfaces in particular.

  2. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine

    2017-01-01

    in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations....

  3. An Introduction to the Gas Phase

    Vallance, Claire

    2017-11-01

    'An Introduction to the Gas Phase' is adapted from a set of lecture notes for a core first year lecture course in physical chemistry taught at the University of Oxford. The book is intended to give a relatively concise introduction to the gas phase at a level suitable for any undergraduate scientist. After defining the gas phase, properties of gases such as temperature, pressure, and volume are discussed. The relationships between these properties are explained at a molecular level, and simple models are introduced that allow the various gas laws to be derived from first principles. Finally, the collisional behaviour of gases is used to explain a number of gas-phase phenomena, such as effusion, diffusion, and thermal conductivity.

  4. Simple setup for gas-phase H/D exchange mass spectrometry coupled to electron transfer dissociation and ion mobility for analysis of polypeptide structure on a liquid chromatographic time scale.

    Mistarz, Ulrik H; Brown, Jeffery M; Haselmann, Kim F; Rand, Kasper D

    2014-12-02

    Gas-phase hydrogen/deuterium exchange (HDX) is a fast and sensitive, yet unharnessed analytical approach for providing information on the structural properties of biomolecules, in a complementary manner to mass analysis. Here, we describe a simple setup for ND3-mediated millisecond gas-phase HDX inside a mass spectrometer immediately after ESI (gas-phase HDX-MS) and show utility for studying the primary and higher-order structure of peptides and proteins. HDX was achieved by passing N2-gas through a container filled with aqueous deuterated ammonia reagent (ND3/D2O) and admitting the saturated gas immediately upstream or downstream of the primary skimmer cone. The approach was implemented on three commercially available mass spectrometers and required no or minor fully reversible reconfiguration of gas-inlets of the ion source. Results from gas-phase HDX-MS of peptides using the aqueous ND3/D2O as HDX reagent indicate that labeling is facilitated exclusively through gaseous ND3, yielding similar results to the infusion of purified ND3-gas, while circumventing the complications associated with the use of hazardous purified gases. Comparison of the solution-phase- and gas-phase deuterium uptake of Leu-Enkephalin and Glu-Fibrinopeptide B, confirmed that this gas-phase HDX-MS approach allows for labeling of sites (heteroatom-bound non-amide hydrogens located on side-chains, N-terminus and C-terminus) not accessed by classical solution-phase HDX-MS. The simple setup is compatible with liquid chromatography and a chip-based automated nanoESI interface, allowing for online gas-phase HDX-MS analysis of peptides and proteins separated on a liquid chromatographic time scale at increased throughput. Furthermore, online gas-phase HDX-MS could be performed in tandem with ion mobility separation or electron transfer dissociation, thus enabling multiple orthogonal analyses of the structural properties of peptides and proteins in a single automated LC-MS workflow.

  5. The structural phase diagram and oxygen equilibrium partial pressure of YBa 2Cu 3O 6+ x studied by neutron powder diffraction and gas volumetry

    Andersen, N. H.; Lebech, B.; Poulsen, H. F.

    1990-12-01

    An experimental technique based on neutron powder diffraction and gas volumetry is presented and used to study the structural phase diagram of YBa 2Cu 3O 6+ x under equilibrium conditions in an extended part of ( x, T)-phase (0.15< x<0.92 and 25° C< T<725°C). Our experimental observations lend strong support to a recent two-dimensional anisotropic next-nearest-neighbour Ising model calculation (the ASYNNNI model) of the basal plane oxygen ordering based of first principle interaction parameters. Simultaneous measurements of the oxygen equilibrium partial pressure show anomalies, one of which proves the thermodynamic stability of the orthorhombic OII double cell structure. Striking similarity with predictions of recent model calculations support that another anomaly may be interpreted to result from local one-dimensional fluctuations in the distribution of oxygen atoms in the basal plane of tetragonal YBCO. Our pressure data also indicate that x=0.92 is a maximum obtainable oxygen concentration for oxygen pressures below 760 Torr.

  6. Molecular structure determination of cyclooctane by Ab Initio and electron diffraction methods in the gas phase; Determinacao da estrutura molecular do ciclooctano por metodos Ab Initio e difracao de eletrons na fase gasosa

    Almeida, Wagner B. de [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Dept. de Quimica

    2000-10-01

    The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can make a significant contribution for an unambiguous determination of the geometrical parameters. In this article the determination for an unambiguous determination of the geometrical parameters. In this article the determination of the molecular structure of the cyclooctane molecule by electron diffraction in the gas phase an initio calculations will be addressed, providing an example of a comparative analysis of theoretical and experimental predictions. (author)

  7. Phase transition in the hadron gas model

    Gorenstein, M.I.; Petrov, V.K.; Zinov'ev, G.M.

    1981-01-01

    A class of statistical models of hadron gas allowing an analytical solution is considered. A mechanism of a possible phase transition in such a system is found and conditions for its occurence are determined [ru

  8. Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: a density functional study

    Filimonov, V.D.; Krasnokutskaya, E.L.; Lesina, Yu.A.; Chajkovskij, V.K.; Poleshchuk, O.X.

    2006-01-01

    The electronic and spatial structures of a broad spectrum of neutral compounds with X-Hal (X = N, O, Cl; Hal = Cl, Br, I) bonds and their protonated forms and of different electronic states of triiodide cation, I 3 + , were determined from density functional B3LYP/6-311G* quantum-chemical calculations. The effects of the structure of these compounds on the parameters of electrophilic reactivity were revealed and the thermochemical characteristics of homolytic and heterolytic X-Hal bond dissociation and of iodine transfer in hydroxyl-containing solvents were calculated. Due to low homolytic bond dissociation energies of X-I, the formation of molecular iodine and triiodide cation I 3 + becomes thermodynamically favorable and the cation should act as iodinating agent alternative to acylhypoiodites and N-iodoimides. The solvation effects of MeOH and CH 2 Cl 2 on the X-Hal bond homolysis and heterolysis were determined using the PCM model [ru

  9. Structures and electrochemical properties of pyrolytic carbon films infiltrated from gas phase into electro-conductive substrates derived from wood

    Ohzawa, Yoshimi; Mitani, Masami; Li, Jianling; Nakajima, Tsuyoshi

    2004-01-01

    Using the pressure-pulsed chemical vapor infiltration technique, pyrolytic carbon (pyrocarbon) films were deposited into two sorts of conductive porous substrates, that is, the carbonized wood (A) and the TiN-coated wood (B). Structures and electrochemical properties were investigated as the negative electrodes of lithium-ion secondary battery. The electrodes had the three-dimensionally continuous current paths in the pyrocarbon-based anodes without the organic binders and the additional conductive fillers. The pyrocarbon films adhered tightly to the carbonized wood or TiN as current collector. These macro-structures of electrodes were effective in improving the high rate property. The sort of substrates affected the nano-structure of pyrocarbon. The pyrocarbon in sample (A) had the relatively high crystallinity, whereas the pyrocarbon in sample (B) was disordered. The capacity of pyrocarbon in sample (B) was higher than that of sample (A), reflecting the disordered microstructure of pyrocarbon film (B). However, sample (A) showed higher Coulombic efficiency at first cycle (i.e. 87%) than that of sample (B), which would result from the high crystallinity, laminar microstructure and low surface area of pyrocarbon in sample (A)

  10. Experiment and theory at the convergence limit: accurate equilibrium structure of picolinic acid by gas-phase electron diffraction and coupled-cluster computations.

    Vogt, Natalja; Marochkin, Ilya I; Rykov, Anatolii N

    2018-04-18

    The accurate molecular structure of picolinic acid has been determined from experimental data and computed at the coupled cluster level of theory. Only one conformer with the O[double bond, length as m-dash]C-C-N and H-O-C[double bond, length as m-dash]O fragments in antiperiplanar (ap) positions, ap-ap, has been detected under conditions of the gas-phase electron diffraction (GED) experiment (Tnozzle = 375(3) K). The semiexperimental equilibrium structure, rsee, of this conformer has been derived from the GED data taking into account the anharmonic vibrational effects estimated from the ab initio force field. The equilibrium structures of the two lowest-energy conformers, ap-ap and ap-sp (with the synperiplanar H-O-C[double bond, length as m-dash]O fragment), have been fully optimized at the CCSD(T)_ae level of theory in conjunction with the triple-ζ basis set (cc-pwCVTZ). The quality of the optimized structures has been improved due to extrapolation to the quadruple-ζ basis set. The high accuracy of both GED determination and CCSD(T) computations has been disclosed by a correct comparison of structures having the same physical meaning. The ap-ap conformer has been found to be stabilized by the relatively strong NH-O hydrogen bond of 1.973(27) Å (GED) and predicted to be lower in energy by 16 kJ mol-1 with respect to the ap-sp conformer without a hydrogen bond. The influence of this bond on the structure of picolinic acid has been analyzed within the Natural Bond Orbital model. The possibility of the decarboxylation of picolinic acid has been considered in the GED analysis, but no significant amounts of pyridine and carbon dioxide could be detected. To reveal the structural changes reflecting the mesomeric and inductive effects due to the carboxylic substituent, the accurate structure of pyridine has been also computed at the CCSD(T)_ae level with basis sets from triple- to 5-ζ quality. The comprehensive structure computations for pyridine as well as for

  11. The nuclear liquid gas phase transition and phase coexistence

    Chomaz, Ph.

    2001-01-01

    In this talk we will review the different signals of liquid gas phase transition in nuclei. From the theoretical side we will first discuss the foundations of the concept of equilibrium, phase transition and critical behaviors in infinite and finite systems. From the experimental point of view we will first recall the evidences for some strong modification of the behavior of hot nuclei. Then we will review quantitative detailed analysis aiming to evidence phase transition, to define its order and phase diagram. Finally, we will present a critical discussion of the present status of phase transitions in nuclei and we will draw some lines for future development of this field. (author)

  12. The nuclear liquid gas phase transition and phase coexistence

    Chomaz, Ph

    2001-07-01

    In this talk we will review the different signals of liquid gas phase transition in nuclei. From the theoretical side we will first discuss the foundations of the concept of equilibrium, phase transition and critical behaviors in infinite and finite systems. From the experimental point of view we will first recall the evidences for some strong modification of the behavior of hot nuclei. Then we will review quantitative detailed analysis aiming to evidence phase transition, to define its order and phase diagram. Finally, we will present a critical discussion of the present status of phase transitions in nuclei and we will draw some lines for future development of this field. (author)

  13. Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition.

    Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V

    2017-05-02

    Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO 2 oxide material are reported. Heterometallic compounds LiFeL 3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac) 3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac) 3 (1) and LiFe(ptac) 3 (2) that consist of discrete heterocyclic tetranuclear molecules Li 2 Fe 2 L 6 . The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L] + peaks (M = Li 2 Fe 2 L 6 ). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac) 3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1 H and 7 Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure

  14. Techniques in Gas Phase Thermolyses

    Egsgaard, Helge; Larsen, Elfinn; Carlsen, Lars

    1982-01-01

    Basic principles, capabilities and limitations of collision activation mass spectrometry are reported, with special reference to real-time analysis of flash vacuum thermolytically generated products. The analytical utility is demonstrated in terms of structure elucidation and isomerization studies...

  15. Determination of molecular structure of succinic acid in a very complex conformational landscape: Gas-phase electron diffraction (GED) and ab initio studies

    Vogt, Natalja; Abaev, Maxim A.; Rykov, Anatolii N.; Shishkov, Igor F.

    2011-06-01

    The molecular structure of succinic acid has been investigated by the gas-phase electron diffraction (GED) method for the first time. According to predictions of MP2/cc-pVTZ calculations, the molecule has 18 stable conformers with the C sbnd C sbnd C sbnd C chain in the gauche ( G) or anti ( A) configuration, and four of them, I ( G), II ( A), III ( G) and IV ( A) belonging to the C 2, C 2h, C 1 and C 1 point groups, respectively, with relative energies ΔE ZPE within 2.2 kcal/mol can be present at the experimental temperature of 445 K in noticeable amounts. The ratio of the conformers I:II:III:IV = 45(15):20(15):10(assumed):25(15) (in %) has been determined in the GED analysis guided by theoretical predictions. To take into account vibrational effects, the corrections Δ( r e - r a) to the experimental r a bond lengths were calculated from the MP2/cc-pVTZ quadratic and cubic force constants. The obtained equilibrium structural parameters of the dominant conformer I are the following (bond lengths in Å, angles in degrees): r e(C sp3sbnd C sp3) = 1.508(3), r e(C sp3sbnd C sp2) = 1.499(2), r e(C sbnd O) = 1.343(2), r e(C dbnd O) = 1.202(1), e(C sbnd C sbnd C) = 111.8(4), e(C sbnd C sbnd O) = 112.0(4), e(O sbnd C dbnd O) = 123.0(1), τ(C sbnd C sbnd C sbnd C) = 69.9(11). Yielding the best agreement with the GED structure, the MP2/cc-pVQZ approximation overestimates the C sbnd O and C dbnd O bond lengths by ca. 0.005(2) Å.

  16. The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

    Groenewold, Gary S.; van Stipdonk, Michael J.; Oomens, Jos; de Jong, Wibe; McIlwain, Michael E.

    2011-01-01

    The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (nu3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the ν 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The structure was calculated using density functional theory (B3LYP functional), which produced a structure in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  17. Experimental station for gas phase fluorescence spectroscopy

    Stankiewicz, M.; Garcia, E. Melero; Ruiz, J. Alvarez; Erman, P.; Hatherly, P.A.; Kivimaeki, A.; Rachlew, E.; Rius i Riu, J.

    2004-01-01

    The details of an experimental setup for gas phase atomic and molecular fluorescence measurements using synchrotron radiation are described in this article. The most significant part of the apparatus is an optical arrangement, which allows for simultaneous measurements of dispersed as well as total fluorescence intensity using an effusive gas jet and an inbuilt gas cell assembled in a convenient plug and measure configuration. The first measurements concerning fluorescence of the N 2 molecule around the N 1s edge obtained with this setup are presented

  18. The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

    Groenewold, G.S.; van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; McIlwain, Michael E.

    2011-01-01

    The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate v 3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (v 3 ) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the v 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  19. Gas flow headspace liquid phase microextraction.

    Yang, Cui; Qiu, Jinxue; Ren, Chunyan; Piao, Xiangfan; Li, Xifeng; Wu, Xue; Li, Donghao

    2009-11-06

    There is a trend towards the use of enrichment techniques such as microextraction in the analysis of trace chemicals. Based on the theory of ideal gases, theory of gas chromatography and the original headspace liquid phase microextraction (HS-LPME) technique, a simple gas flow headspace liquid phase microextraction (GF-HS-LPME) technique has been developed, where the extracting gas phase volume is increased using a gas flow. The system is an open system, where an inert gas containing the target compounds flows continuously through a special gas outlet channel (D=1.8mm), and the target compounds are trapped on a solvent microdrop (2.4 microL) hanging on the microsyringe tip, as a result, a high enrichment factor is obtained. The parameters affecting the enrichment factor, such as the gas flow rate, the position of the microdrop, the diameter of the gas outlet channel, the temperatures of the extracting solvent and of the sample, and the extraction time, were systematically optimized for four types of polycyclic aromatic hydrocarbons. The results were compared with results obtained from HS-LPME. Under the optimized conditions (where the extraction time and the volume of the extracting sample vial were fixed at 20min and 10mL, respectively), detection limits (S/N=3) were approximately a factor of 4 lower than those for the original HS-LPME technique. The method was validated by comparison of the GF-HS-LPME and HS-LPME techniques using data for PAHs from environmental sediment samples.

  20. Molecular structure and conformational composition of 1,3-dihydroxyacetone studied by combined analysis of gas-phase electron diffraction data, rotational constants, and results of theoretical calculations. Ideal gas thermodynamic properties of 1,3-dihydroxyacetone.

    Dorofeeva, Olga V; Vogt, Natalja; Vogt, Jürgen; Popik, Mikhail V; Rykov, Anatolii N; Vilkov, Lev V

    2007-07-19

    The molecular structure of 1,3-dihydroxyacetone (DHA) has been studied by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) data, ab initio, and density functional theory calculations. The equilibrium re structure of DHA was determined by a joint analysis of the GED data and rotational constants taken from the literature. The anharmonic vibrational corrections to the internuclear distances (re-ra) and to the rotational constants (B(i)e-B(i)0) needed for the estimation of the re structure were calculated from the B3LYP/cc-pVTZ cubic force field. It was found that the experimental data are well reproduced by assuming that DHA consists of a mixture of three conformers. The most stable conformer of C2v symmetry has two hydrogen bonds, whereas the next two lowest energy conformers (Cs and C1 symmetry) have one hydrogen bond and their abundance is about 30% in total. A combined analysis of GED and MW data led to the following equilibrium structural parameters (re) of the most abundant conformer of DHA (the uncertainties in parentheses are 3 times the standard deviations): r(C=O)=1.215(2) A, r(C-C)=1.516(2) A, r(C-O)=1.393(2) A, r(C-H)=1.096(4) A, r(O-H)=0.967(4) A, angleC-C=O=119.9(2) degrees, angleC-C-O=111.0(2) degrees, angleC-C-H=108.2(7) degrees, angleC-O-H=106.5(7) degrees. These structural parameters reproduce the experimental B(i)0 values within 0.05 MHz. The experimental structural parameters are in good agreement with those obtained from theoretical calculations. Ideal gas thermodynamic functions (S degrees (T), C degrees p(T), and H degrees (T)-H degrees (0)) of DHA were calculated on the basis of experimental and theoretical molecular parameters obtained in this work. The enthalpy of formation of DHA, -523+/-4 kJ/mol, was calculated by the atomization procedure using the G3X method.

  1. Gas Phase Sulfur, Chlorine and Potassium Chemistry in Biomass Combustion

    Løj, Lusi Hindiyarti

    2007-01-01

    Gas Phase Sulfur, Chlorine and Alkali Metal Chemistry in Biomass Combustion Concern about aerosols formation, deposits, corrosion, and gaseous emissions during biomass combustion, especially straw, continues to be a driving force for investigation on S, Cl, K-containing species under combustions...... conditions. These trace species contained in the biomass structure will be released to the gas phase during combustion and contribute to the problems generated during the process. The investigation during this PhD project is done to stepwise improve the understanding in the chemistry and reduce...... the uncertainties. In the present work, the detailed kinetic model for gas phase sulfur, chlorine, alkali metal, and their interaction has been updated. The K/O/H/Cl chemistry, S chemistry, and their interaction can reasonably predict a range of experimental data. In general, understanding of the interaction...

  2. Comparison of electrical and optical characteristics in gas-phase and gas-liquid phase discharges

    Qazi, H. I. A.; Li, He-Ping, E-mail: liheping@tsinghua.edu.cn; Zhang, Xiao-Fei; Bao, Cheng-Yu [Department of Engineering Physics, Tsinghua University, Beijing 100084 (China); Nie, Qiu-Yue [School of Electrical Engineering and Automation, Harbin Institute of Technology, Harbin, Heilongjiang Province 150001 (China)

    2015-12-15

    This paper presents an AC-excited argon discharge generated using a gas-liquid (two-phase) hybrid plasma reactor, which mainly consists of a powered needle electrode enclosed in a conical quartz tube and grounded deionized water electrode. The discharges in the gas-phase, as well as in the two-phase, exhibit two discharge modes, i.e., the low current glow-like diffuse mode and the high current streamer-like constrict mode, with a mode transition, which exhibits a negative resistance of the discharges. The optical emission spectral analysis shows that the stronger diffusion of the water vapor into the discharge region in the two-phase discharges boosts up the generation of OH (A–X) radicals, and consequently, leads to a higher rotational temperature in the water-phase plasma plume than that of the gas-phase discharges. Both the increase of the power input and the decrease of the argon flow rate result in the increase of the rotational temperature in the plasma plume of the water-phase discharge. The stable two-phase discharges with a long plasma plume in the water-phase under a low power input and gas flow rate may show a promising prospect for the degradation of organic pollutants, e.g., printing and dyeing wastewater, in the field of environmental protection.

  3. Ionic liquid stationary phases for gas chromatography.

    Poole, Colin F; Poole, Salwa K

    2011-04-01

    This article provides a summary of the development of ionic liquids as stationary phases for gas chromatography beginning with early work on packed columns that established details of the retention mechanism and established working methods to characterize selectivity differences compared with molecular stationary phases through the modern development of multi-centered cation and cross-linked ionic liquids for high-temperature applications in capillary gas chromatography. Since there are many reviews on ionic liquids dealing with all aspects of their chemical and physical properties, the emphasis in this article is placed on the role of gas chromatography played in the design of ionic liquids of low melting point, high thermal stability, high viscosity, and variable selectivity for separations. Ionic liquids provide unprecedented opportunities for extending the selectivity range and temperature-operating range of columns for gas chromatography, an area of separation science that has otherwise been almost stagnant for over a decade. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Probing peptide fragment ion structures by combining sustained off-resonance collision-induced dissociation and gas-phase H/D exchange (SORI-HDX) in Fourier transform ion-cyclotron resonance (FT-ICR) instruments.

    Somogyi, Arpád

    2008-12-01

    The usefulness of gas-phase H/D exchange is demonstrated to probe heterogeneous fragment and parent ion populations. Singly and multiply protonated peptides/proteins were fragmented by using sustained off-resonance irradiation collision-induced dissociation (SORI-CID). The fragments and the surviving precursor ions then all undergo H/D exchange in the gas-phase with either D(2)O or CD(3)OD under the same experimental conditions. Usually, 10 to 60 s of reaction time is adequate to monitor characteristic differences in the H/D exchange kinetic rates. These differences are then correlated to isomeric ion structures. The SORI-HDX method can be used to rapidly test fragment ion structures and provides useful insights into peptide fragmentation mechanisms.

  5. Preconcentration in gas or liquid phases using adsorbent thin films

    Antonio Pereira Nascimento Filho

    2006-03-01

    Full Text Available The possibility of preconcentration on microchannels for organic compounds in gas or liquid phases was evaluated. Microstructures with different geometries were mechanically machined using poly(methyl methacrylate - PMMA as substrates and some cavities were covered with cellulose. The surfaces of the microchannels were modified by plasma deposition of hydrophilic or hydrophobic films using 2-propanol and hexamethyldisilazane (HMDS, respectively. Double layers of HMDS + 2-propanol were also used. Adsorption characterization was made by Quartz Crystal Measurements (QCM technique using reactants in a large polarity range that showed the adsorption ability of the structures depends more on the films used than on the capillary phenomena. Cellulose modified by double layer film showed a high retention capacity for all gaseous compounds tested. However, structures without plasma deposition showed low retention capacity. Microchannels modified with double layers or 2-propanol plasma films showed higher retention than non-modified ones on gas or liquid phase.

  6. Gas phase reactive collisions, experimental approach

    Canosa A.

    2012-01-01

    Full Text Available Since 1937 when the first molecule in space has been identified, more than 150 molecules have been detected. Understanding the fate of these molecules requires having a perfect view of their photochemistry and reactivity with other partners. It is then crucial to identify the main processes that will produce and destroy them. In this chapter, a general view of experimental techniques able to deliver gas phase chemical kinetics data at low and very low temperatures will be presented. These techniques apply to the study of reactions between neutral reactants on the one hand and reactions involving charge species on the other hand.

  7. Phase transitions in a vortex gas

    Shah, P.A.

    1995-01-01

    It has been shown recently that the motion of solitons at couplings around a critical coupling can be reduced to the dynamics of particles (the zeros of the Higgs field) on a curved manifold with potential. The curvature gives a velocity-dependent force, and the magnitude of the potential is proportional to the distance from a critical coupling. In this paper we apply this approximation to determining the equation of state of a gas of vortices in the abelian Higgs model. We derive a virial expansion using certain known integrals of the metric, and the second virial coefficient is calculated, determining the behaviour of the gas at low densities. A formula for determining higher-order coefficients is given. At low densities and temperatures T >>λ the equation of state is of the Van der Waals form (P+b N 2 /A 2 )(A-aN) = NT with a=4π and b=-4.89πλ where λ is a measure of the distance from critical coupling. It is found that there is no phase transition in a low-density type-II gas, but there is a transition in the type-I case between a condensed and gaseous state. We conclude with a discussion of the relation of our results to vortex behaviour in superconductors. ((orig.))

  8. Simple setup for gas-phase h/d exchange mass spectrometry coupled to electron transfer dissociation and ion mobility for analysis of polypeptide structure on a liquid chromatographic time scale

    Mistarz, Ulrik Hvid; Brown, Jeffery M; Haselmann, Kim F

    2014-01-01

    gas immediately upstream or downstream of the primary skimmer cone. The approach was implemented on three commercially available mass spectrometers and required no or minor fully reversible reconfiguration of gas-inlets of the ion source. Results from gas-phase HDX-MS of peptides using the aqueous ND3....../D2O as HDX reagent indicate that labeling is facilitated exclusively through gaseous ND3, yielding similar results to the infusion of purified ND3-gas, while circumventing the complications associated with the use of hazardous purified gases. Comparison of the solution-phase- and gas-phase deuterium...

  9. Berry's Phase and Fine Structure

    Binder, B

    2002-01-01

    Irrational numbers can be assigned to physical entities based on iterative processes of geometric objects. It is likely that iterative round trips of vector signals include a geometric phase component. If so, this component will couple back to the round trip frequency or path length generating an non-linear feedback loop (i.e. induced by precession). In this paper such a quantum feedback mechanism is defined including generalized fine structure constants in accordance with the fundamental gravitomagnetic relation of spin-orbit coupling. Supported by measurements, the general relativistic and topological background allows to propose, that the deviation of the fine structure constant from 1/137 could be assigned to Berry's phase. The interpretation is straightforward: spacetime curvature effects can be greatly amplified by non-linear phase-locked feedback-loops adjusted to single-valued phase relationships in the quantum regime.

  10. Probing the Binding Interfaces of Protein Complexes Using Gas-Phase H/D Exchange Mass Spectrometry

    Mistarz, Ulrik H; Brown, Jeffery M; Haselmann, Kim F

    2016-01-01

    Fast gas-phase hydrogen/deuterium exchange mediated by ND3 gas and measured by mass spectrometry (gas-phase HDX-MS) is a largely unharnessed, fast, and sensitive method for probing primary- and higher-order polypeptide structure. Labeling of heteroatom-bound non-amide hydrogens in a sub-milliseco......Fast gas-phase hydrogen/deuterium exchange mediated by ND3 gas and measured by mass spectrometry (gas-phase HDX-MS) is a largely unharnessed, fast, and sensitive method for probing primary- and higher-order polypeptide structure. Labeling of heteroatom-bound non-amide hydrogens in a sub......-millisecond time span after electrospray ionization by ND3 gas can provide structural insights into protein conformers present in solution. Here, we have explored the use of gas-phase HDX-MS for probing the higher-order structure and binding interfaces of protein complexes originating from native solution...

  11. Phase transitions in a gas of anyons

    MacKenzie, R.; Nebia-Rahal, F.; Paranjape, M. B.; Richer, J.

    2010-01-01

    We continue our numerical Monte Carlo simulation of a gas of closed loops on a 3 dimensional lattice, however, now in the presence of a topological term added to the action which corresponds to the total linking number between the loops. We compute the linking number using a novel approach employing certain notions from knot theory. Adding the topological term converts the particles into anyons. Interpreting the model as an effective theory that describes the 2+1-dimensional Abelian Higgs model in the asymptotic strong-coupling regime, the topological linking number simply corresponds to the addition to the action of the Chern-Simons term. The system continues to exhibit a phase transition as a function of the vortex mass as it becomes small. We find the following new results. The Chern-Simons term has no effect on the Wilson loop. On the other hand, it does effect the 't Hooft loop of a given configuration, adding the linking number of the 't Hooft loop with all of the dynamical vortex loops. We find the unexpected result that both the Wilson loop and the 't Hooft loop exhibit a perimeter law even though there are no massless particles in the theory, in both phases of the theory. It should be noted that our method suffers from numerical instabilities if the coefficient of the Chern-Simons term is too large; thus, we have restricted our results to small values of this parameter. Furthermore, interpreting the lattice loop gas as an effective theory describing the Abelian Higgs model is only known to be true in the infinite coupling limit; for strong but finite coupling this correspondence is only a conjecture, the validity of which is beyond the scope of this article.

  12. Transferring pharmaceuticals into the gas phase

    Christen, Wolfgang; Krause, Tim; Rademann, Klaus

    2008-11-01

    The dissolution of molecules of biological interest in supercritical carbon dioxide is investigated using pulsed molecular beam mass spectrometry. Due to the mild processing temperatures of most supercritical fluids, their adiabatic expansion into vacuum permits to transfer even thermally very sensitive substances into the gas phase, which is particularly attractive for pharmaceutical and biomedical applications. In addition, supercritical CO2constitutes a chemically inert solvent that is compatible with hydrocarbon-free ultrahigh vacuum conditions. Here, we report on the dissolution and pulsed supersonic jet expansion of caffeine (C8H10N4O2), the provitamin menadione (C11H8O2), and the amino acid derivative l-phenylalanine tert-butyl ester hydrochloride (C6H5CH2CH(NH2)COOC(CH3)3[dot operator]HCl), into vacuum. An on-axis residual gas analyzer is used to monitor the relative amounts of solute and solvent in the molecular beam as a function of solvent densityE The excellent selectivity and sensitivity provided by mass spectrometry permits to probe even trace amounts of solutes. The strong density variation of CO2 close to the critical point results in a pronounced pressure dependence of the relative ion currents of solute and solvent molecules, reflecting a substantial change in solubility.

  13. Computational phase diagrams of noble gas hydrates under pressure

    Teeratchanan, Pattanasak, E-mail: s1270872@sms.ed.ac.uk; Hermann, Andreas, E-mail: a.hermann@ed.ac.uk [Centre for Science at Extreme Conditions and SUPA, School of Physics and Astronomy, The University of Edinburgh, Edinburgh EH9 3FD (United Kingdom)

    2015-10-21

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

  14. Resolving Gas-Phase Metallicity In Galaxies

    Carton, David

    2017-06-01

    Chapter 2: As part of the Bluedisk survey we analyse the radial gas-phase metallicity profiles of 50 late-type galaxies. We compare the metallicity profiles of a sample of HI-rich galaxies against a control sample of HI-'normal' galaxies. We find the metallicity gradient of a galaxy to be strongly correlated with its HI mass fraction {M}{HI}) / {M}_{\\ast}). We note that some galaxies exhibit a steeper metallicity profile in the outer disc than in the inner disc. These galaxies are found in both the HI-rich and control samples. This contradicts a previous indication that these outer drops are exclusive to HI-rich galaxies. These effects are not driven by bars, although we do find some indication that barred galaxies have flatter metallicity profiles. By applying a simple analytical model we are able to account for the variety of metallicity profiles that the two samples present. The success of this model implies that the metallicity in these isolated galaxies may be in a local equilibrium, regulated by star formation. This insight could provide an explanation of the observed local mass-metallicity relation. Chapter 3 We present a method to recover the gas-phase metallicity gradients from integral field spectroscopic (IFS) observations of barely resolved galaxies. We take a forward modelling approach and compare our models to the observed spatial distribution of emission line fluxes, accounting for the degrading effects of seeing and spatial binning. The method is flexible and is not limited to particular emission lines or instruments. We test the model through comparison to synthetic observations and use downgraded observations of nearby galaxies to validate this work. As a proof of concept we also apply the model to real IFS observations of high-redshift galaxies. From our testing we show that the inferred metallicity gradients and central metallicities are fairly insensitive to the assumptions made in the model and that they are reliably recovered for galaxies

  15. Experiments and theory on pentacene in the thin film phase: structural, electronic, transport properties, and gas response to oxygen, nitrogen, and ambient air

    Parisse, P.; Picozzi, S.; Passacantando, M.; Ottaviano, L.

    2007-01-01

    We investigated the morphological, structural, electronic, and transport properties of pentacene thin films grown by vacuum thermal evaporation on different inert substrates at room temperature. The results of our atomic force microscopy (AFM), X-ray diffraction and scanning tunnelling microscopy (STM) analysis show a structure in the so called 'thin film phase' with 1-2 μm sized grains. Atomic terraces are clearly evidenced with AFM and give an inter-planar spacing of 1.54 nm corresponding to the (001) distance. The Scanning Tunneling Spectroscopy measurements show an HOMO-LUMO gap of 2.2 eV. After vacuum thermal evaporation on patterned substrates with different inter-electrodes distances, we have performed in situ measurements of the electrical response of such thin films. We found for these films a resistivity of ρ = 4.7 ± 0.2 . 10 4 Ω m, that is an order of magnitude lower than the value reported to date in literature for single crystals of pentacene. This value is not affected by the presence of grain boundaries. The resistivity is further reduced by a factor 8.9 ± 0.7, 14 ± 1, 2.3 ± 0.3 upon exposure to oxygen, nitrogen and ambient air, respectively. In addition density functional theory calculations have been performed to investigate the electronic structure of pentacene in this specific phase, focusing on the effects on the relevant electronic properties of the relative orientation of the molecules within the crystalline unit cell, so far experimentally unknown. Our results show that the energy bandwidth and band-gap are crucially affected by the molecular stacking. Furthermore, by comparing our theoretical spectra with the scanning tunneling spectroscopy (STS) measurements, we propose a molecular arrangement that gives a good agreement with experiments as far as the relevant orbitals are concerned. For this polymorph, we find a HOMO and LUMO bandwidth of ∼ 0.7 eV and ∼ 0.8 eV, respectively, which are significantly larger than those obtained for

  16. Statistical parameter characteristics of gas-phase fluctuations for gas-liquid intermittent flow

    Matsui, G.; Monji, H.; Takaguchi, M. [Univ. of Tsukuba (Japan)

    1995-09-01

    This study deals with theoretical analysis on the general behaviour of statistical parameters of gas-phase fluctuations and comparison of statistical parameter characteristics for the real void fraction fluctuations measured with those for the wave form modified the real fluctuations. In order to investigate the details of the relation between the behavior of the statistical parameters in real intermittent flow and analytical results obtained from information on the real flow, the distributions of statistical parameters for general fundamental wave form of gas-phase fluctuations are discussed in detail. By modifying the real gas-phase fluctuations to a trapezoidaly wave, the experimental results can be directly compared with the analytical results. The analytical results for intermittent flow show that the wave form parameter, and the total amplitude of void fraction fluctuations, affects strongly on the statistical parameter characteristics. The comparison with experiment using nitrogen gas-water intermittent flow suggests that the parameters of skewness and excess may be better as indicators of flow pattern. That is, the macroscopic nature of intermittent flow can be grasped by the skewness and the excess, and the detailed flow structure may be described by the mean and the standard deviation.

  17. Statistical parameter characteristics of gas-phase fluctuations for gas-liquid intermittent flow

    Matsui, G.; Monji, H.; Takaguchi, M.

    1995-01-01

    This study deals with theoretical analysis on the general behaviour of statistical parameters of gas-phase fluctuations and comparison of statistical parameter characteristics for the real void fraction fluctuations measured with those for the wave form modified the real fluctuations. In order to investigate the details of the relation between the behavior of the statistical parameters in real intermittent flow and analytical results obtained from information on the real flow, the distributions of statistical parameters for general fundamental wave form of gas-phase fluctuations are discussed in detail. By modifying the real gas-phase fluctuations to a trapezoidaly wave, the experimental results can be directly compared with the analytical results. The analytical results for intermittent flow show that the wave form parameter, and the total amplitude of void fraction fluctuations, affects strongly on the statistical parameter characteristics. The comparison with experiment using nitrogen gas-water intermittent flow suggests that the parameters of skewness and excess may be better as indicators of flow pattern. That is, the macroscopic nature of intermittent flow can be grasped by the skewness and the excess, and the detailed flow structure may be described by the mean and the standard deviation

  18. Charge Mediated Compaction and Rearrangement of Gas-Phase Proteins: A Case Study Considering Two Proteins at Opposing Ends of the Structure-Disorder Continuum

    Jhingree, Jacquelyn R.; Bellina, Bruno; Pacholarz, Kamila J.; Barran, Perdita E.

    2017-07-01

    Charge reduction in the gas phase provides a direct means of manipulating protein charge state, and when coupled to ion mobility mass spectrometry (IM-MS), it is possible to monitor the effect of charge on protein conformation in the absence of solution. Use of the electron transfer reagent 1,3-dicyanobenzene, coupled with IM-MS, allows us to monitor the effect of charge reduction on the conformation of two proteins deliberately chosen from opposite sides of the order to disorder continuum: bovine pancreatic trypsin inhibitor (BPTI) and beta casein. The ordered BPTI presents compact conformers for each of three charge states accompanied by narrow collision cross-section distributions (TWCCSDN2→He). Upon reduction of BPTI, irrespective of precursor charge state, the TWCCSN2→He decreases to a similar distribution as found for the nESI generated ion of identical charge. The behavior of beta casein upon charge reduction is more complex. It presents over a wide charge state range (9-28), and intermediate charge states (13-18) have broad TWCCSDN2→He with multiple conformations, where both compaction and rearrangement are seen. Further, we see that the TWCCSDN2→He of the latter charge states are even affected by the presence of radical anions. Overall, we conclude that the flexible nature of some proteins result in broad conformational distributions comprised of many families, even for single charge states, and the barrier between different states can be easily overcome by an alteration of the net charge.

  19. Phase gradients in acceleration structures

    Decker, F.J.; Jobe, R.K.

    1990-05-01

    In linear accelerators with two or more bunches the beam loading of one bunch will influence the energy and energy spread the following bunches. This can be corrected by quickly changing the phase of a travelling wave structure, so that each bunch recieves a slightly different net phase. At the SLAC Linear Collider (SLC) three bunches, two (e + ,e - ) for the high energy collisions and one (e - -scavenger) for producing positrons should sit at different phases, due to their different tasks. The two e - -bunches are extracted from the damping ring at the same cycle time about 60 ns apart. Fast phase switching of the RF to the bunch length compressor in the Ring-To-Linac (RTL) section can produce the necessary advance of the scavenger bunch (about 6 degree in phase). This allows a low energy spread of this third bunch at the e + -production region at 2/3 of the linac length, while the other bunches are not influenced. The principles and possible other applications of this fast phase switching as using it for multi-bunches, as well as the experimental layout for the actual RTL compressor are presented

  20. Fundamental thermochemical properties of amino acids: gas-phase and aqueous acidities and gas-phase heats of formation.

    Stover, Michele L; Jackson, Virgil E; Matus, Myrna H; Adams, Margaret A; Cassady, Carolyn J; Dixon, David A

    2012-03-08

    The gas-phase acidities of the 20 L-amino acids have been predicted at the composite G3(MP2) level. A broad range of structures of the neutral and anion were studied to determine the lowest energy conformer. Excellent agreement is found with the available experimental gas-phase deprotonation enthalpies, and the calculated values are within experimental error. We predict that tyrosine is deprotonated at the CO(2)H site. Cysteine is predicted to be deprotonated at the SH but the proton on the CO(2)H is shared with the S(-) site. Self-consistent reaction field (SCRF) calculations with the COSMO parametrization were used to predict the pK(a)'s of the non-zwitterion form in aqueous solution. The differences in the non-zwitterion pK(a) values were used to estimate the free energy difference between the zwitterion and nonzwitterion forms in solution. The heats of formation of the neutral compounds were calculated from atomization energies and isodesmic reactions to provide the first reliable set of these values in the gas phase. Further calculations were performed on five rare amino acids to predict their heats of formation, acidities, and pK(a) values.

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

    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.

  2. Gas-phase spectroscopy of ferric heme-NO complexes

    Wyer, J.A.; Jørgensen, Anders; Pedersen, Bjarke

    2013-01-01

    and significantly blue-shifted compared to ferric heme nitrosyl proteins (maxima between 408 and 422 nm). This is in stark contrast to the Q-band absorption where the protein microenvironment is nearly innocent in perturbing the electronic structure of the porphyrin macrocycle. Photodissociation is primarily...... maxima of heme and its complexes with amino acids and NO. Not so innocent: Weakly bound complexes between ferric heme and NO were synthesised in the gas phase, and their absorption measured from photodissociation yields. Opposite absorption trends in the Soret-band are seen upon NO addition to heme ions...

  3. Comparison of catalytic ethylene polymerization in slurry and gas phase

    Daftaribesheli, Majid

    2009-01-01

    Polyethylene (PE) with the annual consumption of 70 million tones in 2007 is mostly produced in slurry, gas-phase or combination of both processes. This work focuses on a comparison between the slurry and gas phase processes. Why does PE produced in theses two processes can show extremely different

  4. Modeling the Phase Composition of Gas Condensate in Pipelines

    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.

  5. Raman study of vibrational dynamics of aminopropylsilanetriol in gas phase

    Volovšek, V.; Dananić, V.; Bistričić, L.; Movre Šapić, I.; Furić, K.

    2014-01-01

    Raman spectrum of aminopropylsilanetriol (APST) in gas phase has been recorded at room temperature in macro chamber utilizing two-mirror technique over the sample tube. Unlike predominantly trans molecular conformation in condensed phase, the spectra of vapor show that the molecules are solely in gauche conformation with intramolecular hydrogen bond N⋯Hsbnd O which reduces the molecular energy in respect to trans conformation by 0.152 eV. The assignment of the molecular spectra based on the DFT calculation is presented. The strong vibrational bands at 354 cm-1, 588 cm-1 and 3022 cm-1 are proposed for verifying the existence of the ring like, hydrogen bonded structure. Special attention was devoted to the high frequency region, where hydrogen bond vibrations are coupled to stretchings of amino and silanol groups.

  6. Closed-cage tungsten oxide clusters in the gas phase.

    Singh, D M David Jeba; Pradeep, T; Thirumoorthy, Krishnan; Balasubramanian, Krishnan

    2010-05-06

    During the course of a study on the clustering of W-Se and W-S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W-O clusters. Three distinct species, W(6)O(19)(-), W(13)O(29)(-), and W(14)O(32)(-), stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W(13) and W(14) clusters were observed for the first time in the gas phase.

  7. STRUCTURED MOLECULAR GAS REVEALS GALACTIC SPIRAL ARMS

    Sawada, Tsuyoshi [Joint ALMA Office, Alonso de Cordova 3107, Vitacura, Santiago 763-0355 (Chile); Hasegawa, Tetsuo [NAOJ Chile Observatory, Joaquin Montero 3000 Oficina 702, Vitacura, Santiago 763-0409 (Chile); Koda, Jin, E-mail: sawada.tsuyoshi@nao.ac.jp [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794-3800 (United States)

    2012-11-01

    We explore the development of structures in molecular gas in the Milky Way by applying the analysis of the brightness distribution function and the brightness distribution index (BDI) in the archival data from the Boston University-Five College Radio Astronomy Observatory {sup 13}CO J = 1-0 Galactic Ring Survey. The BDI measures the fractional contribution of spatially confined bright molecular emission over faint emission extended over large areas. This relative quantity is largely independent of the amount of molecular gas and of any conventional, pre-conceived structures, such as cores, clumps, or giant molecular clouds. The structured molecular gas traced by higher BDI is located continuously along the spiral arms in the Milky Way in the longitude-velocity diagram. This clearly indicates that molecular gas changes its structure as it flows through the spiral arms. Although the high-BDI gas generally coincides with H II regions, there is also some high-BDI gas with no/little signature of ongoing star formation. These results support a possible evolutionary sequence in which unstructured, diffuse gas transforms itself into a structured state on encountering the spiral arms, followed by star formation and an eventual return to the unstructured state after the spiral arm passage.

  8. The gas industry in Britain: future structures

    McKinnon, J.

    1993-01-01

    This paper is intended to provide a summary of the kind of structural changes to British Gas that can be considered in order to enable effective competition to develop in the gas market. It draws on an extensive analysis undertaken by the Office of Gas Supply (OFGAS) of recent developments in the gas market, the need to ensure the safety, efficiency and security of gas supplies under different structures and how regulation may change with different structures. Many of these issues covered are complex, and can each be discussed at length, but the intention of this paper is to provide an overview of the key options for a restructured gas market. OFGAS has also examined the regulatory environment within which competitors to British Gas who have emerged or who are likely to emerge in the future may be expected to operate. This paper describes the range of structural options we see. At one end of the spectrum there is the option of continuing with a vertically integrated but more heavily regulated monopoly; at the other end is a fully competitive structure with no or much reduced regulation. In between, there are various combinations between the degree of regulation and the extent of competition that can be considered. In analysing future structural options, we believe it necessary to consider the complete gas supply chain. The analysis therefore considers the offshore production or importation of gas, its purchase at the beach, its reception and processing at terminals, its transportation from terminal meters to customers' meters, its storage and sale to final customers. (author)

  9. Wigner Distribution Functions as a Tool for Studying Gas Phase Alkali Metal Plus Noble Gas Collisions

    2014-03-27

    WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS NOBLE GAS COLLISIONS THESIS Keith A. Wyman, Second Lieutenant, USAF...the U.S. Government and is not subject to copyright protection in the United States. AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR...APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS

  10. Atomic and molecular physics in the gas phase

    Toburen, L.H.

    1990-09-01

    The spatial and temporal distributions of energy deposition by high-linear-energy-transfer radiation play an important role in the subsequent chemical and biological processes leading to radiation damage. Because the spatial structures of energy deposition events are of the same dimensions as molecular structures in the mammalian cell, direct measurements of energy deposition distributions appropriate to radiation biology are infeasible. This has led to the development of models of energy transport based on a knowledge of atomic and molecular interactions process that enable one to simulate energy transfer on an atomic scale. Such models require a detailed understanding of the interactions of ions and electrons with biologically relevant material. During the past 20 years there has been a great deal of progress in our understanding of these interactions; much of it coming from studies in the gas phase. These studies provide information on the systematics of interaction cross sections leading to a knowledge of the regions of energy deposition where molecular and phase effects are important and that guide developments in appropriate theory. In this report studies of the doubly differential cross sections, crucial to the development of stochastic energy deposition calculations and track structure simulation, will be reviewed. Areas of understanding are discussed and directions for future work addressed. Particular attention is given to experimental and theoretical findings that have changed the traditional view of secondary electron production for charged particle interactions with atomic and molecular targets

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

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

    1980-01-01

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

  12. The Ultrafast Wolff Rearrangement in the Gas Phase

    Steinbacher, Andreas; Roeding, Sebastian; Brixner, Tobias; Nuernberger, Patrick

    The Wolff rearrangement of gas-phase 5-diazo Meldrum's acid is disclosed with femtosecond ion spectroscopy. Distinct differences are found for 267 nm and 200 nm excitation, the latter leading to even two ultrafast rearrangement reactions.

  13. Reticulated Vitreous Carbon Electrodes for Gas Phase Pulsed Corona Reactors

    Locke, B

    1998-01-01

    A new design for gas phase pulsed corona reactors incorporating reticulated vitreous carbon electrodes is demonstrated to be effective for the removal of nitrogen oxides from synthetic air mixtures...

  14. Reticulated Vitreous Carbon Electrodes for Gas Phase Pulsed Corona Reactors

    LOCKE, B

    1999-01-01

    A new design for gas phase pulsed corona reactors incorporating reticulated vitreous carbon electrodes is demonstrated to be effective for the removal of nitrogen oxides from synthetic air mixtures...

  15. Diode Laser Raman Scattering Prototype Gas-Phase Environmental Monitoring

    Benner, Robert

    1999-01-01

    We proposed developing a diode-laser-based, full spectrum Raman scattering instrument incorporating a multipass, external cavity enhancement cell for full spectrum, gas phase analysis of environmental pollutants...

  16. Laser spectroscopy and gas-phase chemistry in CVD

    Ho, P.; Breiland, W.G.; Coltrin, M.E.

    1986-01-01

    The experimental work involves the use of laser spectroscopic techniques for in situ measurements on the gas phase in a chemical vapor deposition reactor. The theoretical part of the program consists of a computer model of the coupled fluid mechanics and gas-phase chemical kinetics of silane decomposition and subsequent reactions of intermediate species. The laser measurements provide extensive data for thoroughly testing the predictive capabilities of the model

  17. Comparison of catalytic ethylene polymerization in slurry and gas phase

    Daftaribesheli, Majid

    2009-01-01

    Polyethylene (PE) with the annual consumption of 70 million tones in 2007 is mostly produced in slurry, gas-phase or combination of both processes. This work focuses on a comparison between the slurry and gas phase processes. Why does PE produced in theses two processes can show extremely different properties and extremely different reaction behaviour even if the same Ziegler-Natta (ZN) catalyst is used? Generally, it is known that the reason can be found in the differences of local condition...

  18. Void fraction fluctuations in two-phase gas-liquid flow

    Ulbrich, R.

    1987-01-01

    Designs of the apparatus in which two-phase gas-liquid flow occurs are usually based on the mean value of parameters such as pressure drop and void fraction. The flow of two-phase mixtures generally presents a very complicated flow structure, both in terms of the unsteady formation on the interfacial area and in terms of the fluctuations of the velocity, pressure and other variables within the flow. When the gas void fraction is near 0 or 1 / bubble or dispersed flow regimes / then oscillations of void fraction are very small. The intermittent flow such as plug and slug/ froth is characterized by alternately flow portions of liquid and gas. It influences the change of void fractions in time. The results of experimental research of gas void fraction fluctuations in two-phase adiabatic gas-liquid flow in a vertical pipe are presented

  19. Porous Silicon Structures as Optical Gas Sensors.

    Levitsky, Igor A

    2015-08-14

    We present a short review of recent progress in the field of optical gas sensors based on porous silicon (PSi) and PSi composites, which are separate from PSi optochemical and biological sensors for a liquid medium. Different periodical and nonperiodical PSi photonic structures (bares, modified by functional groups or infiltrated with sensory polymers) are described for gas sensing with an emphasis on the device specificity, sensitivity and stability to the environment. Special attention is paid to multiparametric sensing and sensor array platforms as effective trends for the improvement of analyte classification and quantification. Mechanisms of gas physical and chemical sorption inside PSi mesopores and pores of PSi functional composites are discussed.

  20. Electron spectrometer for gas-phase spectroscopy

    Bozek, J.D.; Schlachter, A.S. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    An electron spectrometer for high-resolution spectroscopy of gaseous samples using synchrotron radiation has been designed and constructed. The spectrometer consists of a gas cell, cylindrical electrostatic lens, spherical-sector electron energy analyzer, position-sensitive detector and associated power supplies, electronics and vacuum pumps. Details of the spectrometer design are presented together with some representative spectra.

  1. Gas hydrate phase equilibria measurement techniques and phase rule considerations

    Beltran, Juan G.; Bruusgaard, Hallvard; Servio, Phillip

    2012-01-01

    Highlights: → Inconsistencies found in hydrate literature. → Clarification to the number of variables needed to satisfy and justify equilibrium data. → Application of phase rule to mixed hydrate systems. → Thermodynamically consistent format to present data. - Abstract: A brief review of the Gibbs phase rule for non-reacting systems and its correct application to clathrate hydrates is presented. Clarification is provided for a common mistake found in hydrate phase-equilibria literature, whereby initial compositions are used as intensive variables to satisfy the Gibbs phase rule instead of the equilibrium values. The system of (methane + carbon dioxide + water) under (hydrate + liquid + vapor) equilibrium is used as a case study to illustrate key points and suggestions to improve experimental techniques are proposed.

  2. Device to remove hydrogen isotopes from a gas phase

    Morlock, G.; Wiesemes, J.; Bachner, D.

    1977-01-01

    The device described here guarantees the selective removal of hydrogen isotopes from gas phases in order to prevent the occurence of explosive H 2 gas mixtures, or to separate off radioactive tritium in nuclear plants from the gas phase. It consists of a closed container whose walls are selectively penetrable by hydrogen isotopes. It is simultaneously filled compactly and presssure-resistant with a metal bulk (e.g. powder, sponges or the like of titanium or other hydrogen isotope binding metal). Walling and bulk are maintained at suitable working temperatures by means of a system according to the Peltier effect. The whole thing is safeguarded by protective walling. (RB) [de

  3. FORTRAN program for calculating liquid-phase and gas-phase thermal diffusion column coefficients

    Rutherford, W.M.

    1980-01-01

    A computer program (COLCO) was developed for calculating thermal diffusion column coefficients from theory. The program, which is written in FORTRAN IV, can be used for both liquid-phase and gas-phase thermal diffusion columns. Column coefficients for the gas phase can be based on gas properties calculated from kinetic theory using tables of omega integrals or on tables of compiled physical properties as functions of temperature. Column coefficients for the liquid phase can be based on compiled physical property tables. Program listings, test data, sample output, and users manual are supplied for appendices

  4. Molecular Structure of 3,3-Diethylpenthane (Tetraethylmethane) in the Gas Phase As Determined by Electron Diffraction and ab Initio Calculations

    Adler, R. W.; Allen, P. R.; Hnyk, Drahomír; Rankin, D. W. H.; Robertson, H. E.; Smart, B. A.; Gillespie, R. J.; Bytheway, I.

    1999-01-01

    Roč. 64, č. 12 (1999), s. 4226-4232 ISSN 0022-3263 Institutional research plan: CEZ:AV0Z4032918 Keywords : structure * initio calculations * 3,3-Diethylpentane Subject RIV: CC - Organic Chemistry Impact factor: 3.440, year: 1999

  5. Toward a Rational Design of Highly Folded Peptide Cation Conformations. 3D Gas-Phase Ion Structures and Ion Mobility Characterization

    Pepin, R.; Laszlo, K. J.; Marek, Aleš; Peng, B.; Bush, M. F.; Lavanant, H.; Afonso, C.; Tureček, F.

    2016-01-01

    Roč. 27, č. 10 (2016), s. 1647-1660 ISSN 1044-0305 Institutional support: RVO:61388963 Keywords : peptide ions * ion mobility * collisional cross sections * density functional theory calculations * ion structures * polar effects Subject RIV: CC - Organic Chemistry Impact factor: 2.786, year: 2016

  6. Catalytic combustion in gas stoves - Phase II

    Hjelm, Anna-Karin [CATATOR AB, Lund (Sweden)

    2003-06-01

    Several independent studies show that gas stoves to some degree contribute to the indoor emissions of NO{sub x} especially in situations were the ventilation flow is poor. The peak-NO{sub x} concentrations can reach several hundred ppb but the integral concentration seldom exceeds about 20 - 50 ppb, which corresponds to an indoor-outdoor ratio of about 1 - 2.5. Epidemiological studies indicate increasing problems with respiratory symptoms in sensitive people at concentrations as low as 15 ppb of NO{sub 2}. Consequently, the NO{sub x}-concentration in homes where gas stoves are used is high enough to cause health effects. However, in situations where the ventilation flow is high (utilisation of ventilation hoods) the NO{sub x}-emissions are not likely to cause any health problems. This study has been aimed at investigating the possibilities to reduce the NO{sub x} emissions from gas stoves by replacing the conventional flame combustion with catalytic combustion. The investigation is requested by Swedish Gas Center, and is a following-up work of an earlier conducted feasibility study presented in April-2002. The present investigation reports on the possibility to use cheap and simple retro-fit catalytic design suggestions for traditional gas stoves. Experiments have been conducted with both natural and town gas, and parameters such as emissions of NO{sub x}, CO and unburned fuel gas and thermal efficiency, etc, have been examined and are discussed. The results show that it is possible to reduce the NO{sub x} emissions up to 80% by a simple retro-fit installation, without decreasing the thermal efficiency of the cooking plate. The measured source strengths correspond to indoor NO{sub x} concentrations that are below or equal to the average outdoor concentration, implying that no additional detrimental health effects are probable. The drawback of the suggested installations is that the concentration of CO and in some cases also CH{sub 4} are increased in the flue gases

  7. Phase equilibria and phase structures of polymer blends

    Chalykh, Anatolii E; Gerasimov, Vladimir K

    2004-01-01

    Experimental, methodical and theoretical studies dealing with phase equilibria and phase structures of polymer blends are generalised. The general and specific features of the change in solubility of polymers with changes in the molecular mass and copolymer composition and upon the formation of three-dimensional cross-linked networks are described. The results of the effect of the prehistory on the phase structure and the non-equilibrium state of polymer blends are considered in detail.

  8. STRUCTURE, PHASE COMPOSITION AND PROPERTIES OF GAS-THERMAL COVERINGS OF MECHANICALLY ALLOYED THERMOREACTING COMPOSITE POWDERS OF NICKEL-ALUMINIUM SYSTEM

    F. G. Lovshenko

    2015-01-01

    Full Text Available The presented results show that coverings from mechanically alloyed thermoreacting powders of system «nickel–aluminum» are nonequilibrium multiphase systems which basis represents solid solution of aluminum in nickel. It has the microcrystalline type of structure which is characterized by an advanced surface of borders of the grains and subgrains stabilized by nanodimensional inclusions of oxides and alyuminid. These coverings surpass by 1,2–1,6 times analogs in durability, hardness and wear resistance.

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

    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.

  10. Analysis of volatile phase transport in soils using natural radon gas as a tracer

    Chen, C.; Thomas, D.M.

    1992-01-01

    We have conducted a field study of soil gas transport processes using radon gas as a naturally occurring tracer. The experiment monitored soil gas radon activity, soil moisture, and soil temperature at three depths in the shallow soil column; barometric pressure, rainfall and wind speed were monitored at the soil surface. Linear and multiple regression analysis of the data sets has shown that the gas phase radon activities under natural environmental conditions are influenced by soil moisture content, barometric pressure variations, soil temperature and soil structure. The effect of wind speed on subsurface radon activities under our field conditions has not been demonstrated

  11. Fragmentation pathways of O-alkyl methylphosphonothionocyanidates in the gas phase: toward unambiguous structural characterization of chemicals in the Chemical Weapons Convention framework.

    Saeidian, Hamid; Babri, Mehran; Ashrafi, Davood; Sarabadani, Mansour; Naseri, Mohammad Taghi

    2013-08-01

    The electron-impact (EI) mass spectra of a series of O-alkyl methylphosphonothionocyanidates were studied for Chemical Weapons Convention (CWC) purposes. General EI fragmentation pathways were constructed and discussed, and collision-induced dissociation studies of the major EI ions were performed to confirm proposed fragment structures by analyzing fragment ions of deuterated analogs and by use of density functional theory (DFT) calculations. Thiono-thiolo rearrangement, McLafferty-type rearrangement, and a previously unknown intramolecular electrophilic aromatic substitution reaction were observed and confirmed. The study also focused on differentiation of isomeric compounds. Retention indices for all compounds, and an electrophilicity index for several compounds, are reported and interpreted.

  12. Characterizing the correlations between local phase fractions of gas-liquid two-phase flow with wire-mesh sensor.

    Tan, C; Liu, W L; Dong, F

    2016-06-28

    Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas-liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas-liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue 'Supersensing through industrial process tomography'. © 2016 The Author(s).

  13. Liquid-gas phase transition in asymmetric nuclear matter at finite temperature

    Maruyama, Toshiki; Tatsumi, Toshitaka; Chiba, Satoshi

    2010-01-01

    Liquid-gas phase transition is discussed in warm asymmetric nuclear matter. Some peculiar features are figured out from the viewpoint of the basic thermodynamics about the phase equilibrium. We treat the mixed phase of the binary system based on the Gibbs conditions. When the Coulomb interaction is included, the mixed phase is no more uniform and the sequence of the pasta structures appears. Comparing the results with those given by the simple bulk calculation without the Coulomb interaction, we extract specific features of the pasta structures at finite temperature.

  14. Liquid-gas phase transition in asymmetric nuclear matter at finite temperature

    Maruyama, Toshiki; Tatsumi, Toshitaka; Chiba, Satoshi

    2010-03-01

    Liquid-gas phase transition is discussed in warm asymmetric nuclear matter. Some peculiar features are figured out from the viewpoint of the basic thermodynamics about the phase equilibrium. We treat the mixed phase of the binary system based on the Gibbs conditions. When the Coulomb interaction is included, the mixed phase is no more uniform and the sequence of the pasta structures appears. Comparing the results with those given by the simple bulk calculation without the Coulomb interaction, we extract specific features of the pasta structures at finite temperature.

  15. Microfabricated Gas Phase Chemical Analysis Systems

    FRYE-MASON, GREGORY CHARLES; HELLER, EDWIN J.; HIETALA, VINCENT M.; KOTTENSTETTE, RICHARD; LEWIS, PATRICK R.; MANGINELL, RONALD P.; MATZKE, CAROLYN M.; WONG, CHUNGNIN C.

    1999-01-01

    A portable, autonomous, hand-held chemical laboratory ((micro)ChemLab(trademark)) is being developed for trace detection (ppb) of chemical warfare (CW) agents and explosives in real-world environments containing high concentrations of interfering compounds. Microfabrication is utilized to provide miniature, low-power components that are characterized by rapid, sensitive and selective response. Sensitivity and selectivity are enhanced using two parallel analysis channels, each containing the sequential connection of a front-end sample collector/concentrator, a gas chromatographic (GC) separator, and a surface acoustic wave (SAW) detector. Component design and fabrication and system performance are described

  16. Ab initio structural and spectroscopic study of HPS{sup x} and HSP{sup x} (x = 0,+1,−1) in the gas phase

    Yaghlane, Saida Ben [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications – LSAMA, Université de Tunis, Tunis (Tunisia); Cotton, C. Eric; Francisco, Joseph S., E-mail: francisc@purdue.edu, E-mail: hochlaf@univ-mlv.fr [Department of Chemistry and Department of Earth and Atmospheric Science, Purdue University, West Lafayette, Indiana 49707 (United States); Linguerri, Roberto; Hochlaf, Majdi, E-mail: francisc@purdue.edu, E-mail: hochlaf@univ-mlv.fr [Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, Université Paris-Est, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2013-11-07

    Accurate ab initio computations of structural and spectroscopic parameters for the HPS/HSP molecules and corresponding cations and anions have been performed. For the electronic structure computations, standard and explicitly correlated coupled cluster techniques in conjunction with large basis sets have been adopted. In particular, we present equilibrium geometries, rotational constants, harmonic vibrational frequencies, adiabatic ionization energies, electron affinities, and, for the neutral species, singlet-triplet relative energies. Besides, the full-dimensional potential energy surfaces (PESs) for HPS{sup x} and HSP{sup x} (x = −1,0,1) systems have been generated at the standard coupled cluster level with a basis set of augmented quintuple-zeta quality. By applying perturbation theory to the calculated PESs, an extended set of spectroscopic constants, including τ, first-order centrifugal distortion and anharmonic vibrational constants has been obtained. In addition, the potentials have been used in a variational approach to deduce the whole pattern of vibrational levels up to 4000 cm{sup −1} above the minima of the corresponding PESs.

  17. CASCADER: An m-chain gas-phase radionuclide transport and fate model

    Cawlfield, D.E.; Been, K.B.; Emer, D.F.; Lindstrom, F.T.; Shott, G.J.

    1993-06-01

    Chemicals and radionuclides move either in the gas-phase, liquid-phase, or both phases in soils. They may be acted upon by either biological or abiotic processes through advection and/or diffusion. Furthermore, parent and daughter radionuclides may decay as they are transported in the soil. This is volume two to the CASCADER series, titled CASCADR8. It embodies the concepts presented in volume one of this series. To properly understand how the CASCADR8 model works, the reader should read volume one first. This volume presents the input and output file structure for CASCADR8, and a set of realistic scenarios for buried sources of radon gas

  18. CASCADER: An M-chain gas-phase radionuclide transport and fate model

    Cawlfield, D.E.; Emer, D.F.; Lindstrom, F.T.; Shott, G.J.

    1993-09-01

    Chemicals and radionuclides move either in the gas-phase, liquid-phase, or both phases in soils. They may be acted upon by either biological or abiotic processes through advection and/or dispersion. Additionally during the transport of parent and daughter radionuclides in soil, radionuclide decay may occur. This version of CASCADER called CASCADR9 starts with the concepts presented in volumes one and three of this series. For a proper understanding of how the model works, the reader should read volume one first. Also presented in this volume is a set of realistic scenarios for buried sources of radon gas, and the input and output file structure for CASCADER9

  19. Influence of the pipe diameter on the structure of the gas-liquid interface in a vertical two-phase pipe flow

    Prasser, H. M.; Beyer, M.; Boettger, A.; Carl, H.; Lucas, D.; Schaffrath, A.; Schutz, P.; Weiss, F. P.; Zschau, J.

    2003-01-01

    Two-phase flow tests in a 194.1 mm diameter vertical pipe (DN200) with an air-water mixture are reported. Close to the upper end of a 9 m tall test section a wire-mesh sensor is installed that delivers instantaneous void fraction distributions over the entire cross section with time resolution of 2500 frames per second. The sensor disposes of 64 x 64 measuring points, which corresponds to a spatial resolution of 3 mm. Beside an fast flow visualisations, void-fraction profiles and bubble size distributions were obtained. Earlier, similar experiments were carried out in a pipe of 51.2 mm inner diameter (DN50). A comparison of the data from the two different facilities allows to study the scaling effects on void fraction profiles, bubbles size distributions and the flow patterns. In the small pipe, the increase of the air flow rate leads to a transition from bubbly via slug to churn turbulent flow. The transition to slug flow is accompanied by the appearance of a second peak in the bubble size distribution that corresponds to the class of large Taylor bubbles. A similar qualitative behaviour was found in the large pipe, though the large bubble fraction has a significantly bigger mean diameter at identical superficial velocities, the peak is less tall but wider. Bubbles move more freely than in the small pipe, since the confining action of the pipe walls to the flow is less pronounced, while the large Taylor bubbles occupy almost the entire cross section in case of the small pipe. Furthermore, the bubbles show much more deformations in the large pipe. Shapes of such large bubbles were characterised in three dimensions for the first time. They can rather be complicated and far from the shape of ideal Taylor bubbles. Also the small bubble fraction tends to bigger sizes in the large pipe

  20. SVOC partitioning between the gas phase and settled dust indoors

    Weschler, Charles J.; Nazaroff, William W.

    2010-09-01

    Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps in crafting measurement programs for epidemiological studies designed to probe potential associations between exposure to these compounds and adverse health effects. In this paper, we analyze published data from nineteen studies that cumulatively report measurements of dustborne and airborne SVOCs in more than a thousand buildings, mostly residences, in seven countries. In aggregate, measured median data are reported in these studies for 66 different SVOCs whose octanol-air partition coefficients ( Koa) span more than five orders of magnitude. We use these data to test a simple equilibrium model for estimating the partitioning of an SVOC between the gas phase and settled dust indoors. The results demonstrate, in central tendency, that a compound's octanol-air partition coefficient is a strong predictor of its abundance in settled dust relative to its gas phase concentration. Using median measured results for each SVOC in each study, dustborne mass fractions predicted using Koa and gas-phase concentrations correlate reasonably well with measured dustborne mass fractions ( R2 = 0.76). Combined with theoretical understanding of SVOC partitioning kinetics, the empirical evidence also suggests that for SVOCs with high Koa values, the mass fraction in settled dust may not have sufficient time to equilibrate with the gas phase concentration.

  1. Synthesizing lattice structures in phase space

    Guo, Lingzhen; Marthaler, Michael

    2016-01-01

    In one dimensional systems, it is possible to create periodic structures in phase space through driving, which is called phase space crystals (Guo et al 2013 Phys. Rev. Lett. 111 205303). This is possible even if for particles trapped in a potential without periodicity. In this paper we discuss ultracold atoms in a driven optical lattice, which is a realization of such a phase space crystals. The corresponding lattice structure in phase space is complex and contains rich physics. A phase space lattice differs fundamentally from a lattice in real space, because its coordinate system, i.e., phase space, has a noncommutative geometry, which naturally provides an artificial gauge (magnetic) field. We study the behavior of the quasienergy band structure and investigate the dissipative dynamics. Synthesizing lattice structures in phase space provides a new platform to simulate the condensed matter phenomena and study the intriguing phenomena of driven systems far away from equilibrium. (paper)

  2. Local gas- and liquid-phase measurements for air-water two-phase flows in a rectangular channel

    Zhou, X.; Sun, X.; Williams, M.; Fu, Y.; Liu, Y.

    2014-01-01

    Local gas- and liquid-phase measurements of various gas-liquid two-phase flows, including bubbly, cap-bubbly, slug, and churn-turbulent flows, were performed in an acrylic vertical channel with a rectangular cross section of 30 mm x 10 mm and height of 3.0 m. All the measurements were carried out at three measurement elevations along the flow channel, with z/D h = 9, 72, and 136, respectively, to study the flow development. The gas-phase velocity, void fraction, and bubble number frequency were measured using a double-sensor conductivity probe. A high-speed imaging system was utilized to perform the flow regime visualization and to provide additional quantitative information of the two-phase flow structure. An image processing scheme was developed to obtain the gas-phase velocity, void fraction, Sauter mean diameter, bubble number density, and interfacial area concentration. The liquid-phase velocity and turbulence measurements were conducted using a particle image velocimetry-planar laser-induced fluorescence (PIV-PLIF) system, which enables whole-field and high-resolution data acquisition. An optical phase separation method, which uses fluorescent particles and optical filtration technique, is adopted to extract the velocity information of the liquid phase. An image pre-processing scheme is imposed on the raw PIV images acquired to remove noises due to the presence of bubble residuals and optically distorted particles in the images captured by the PIV-PLIF system. Due to the better light access and less bubble distortion in the narrow rectangular channel, the PIV-PLIF system were able to perform reasonably well in flows of even higher void fractions as compared to the situations with circular pipe test sections. The flow conditions being studied covered various flow regime transitions, void fractions, and liquid-phase flow Reynolds numbers. The obtained experimental data can also be used to validate two-phase CFD results. (author)

  3. Phase space analysis of some interacting Chaplygin gas models

    Khurshudyan, M. [Academy of Sciences of Armenia, Institute for Physical Research, Ashtarak (Armenia); Tomsk State University of Control Systems and Radioelectronics, Laboratory for Theoretical Cosmology, Tomsk (Russian Federation); Tomsk State Pedagogical University, Department of Theoretical Physics, Tomsk (Russian Federation); Myrzakulov, R. [Eurasian National University, Eurasian International Center for Theoretical Physics, Astana (Kazakhstan)

    2017-02-15

    In this paper we discuss a phase space analysis of various interacting Chaplygin gas models in general relativity. Linear and nonlinear sign changeable interactions are considered. For each case appropriate late time attractors of field equations are found. The Chaplygin gas is one of the dark fluids actively considered in modern cosmology due to the fact that it is a joint model of dark energy and dark matter. (orig.)

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

    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)

  5. Gas-phase transport of fission products

    Tang, I.N.; Munkelwitz, H.R.

    1982-01-01

    The paper presents the results of an experimental investigation to show the importance of nuclear aerosol formation as a mechanism for semi-volatile fission product transport under certain postulated HTGR accident conditions. Simulated fission product Sr and Ba as oxides are impregnated in H451 graphite and released at elevated temperatures into a dry helium flow. In the presence of graphite, the oxides are quantitatively reduced to metals, which subsequently vaporize at temperatures much lower than required for the oxides alone to vaporize in the absence of graphite. A substantial fraction of the released material is associated with particulate matter, which is collected on filters located downstream at ambient temperatures. Increasing carrier-gas flow rate greatly enhances the extent of particulate transport. The release and transport of simulated fission product Ag as metal are also investigated. Electron microscopic examinations of the collected Sr and Ag aerosols show large agglomerates composed of primary particles roughly 0.06 to 0.08 μm in diameter

  6. Understanding Gas-Phase Ammonia Chemistry in Protoplanetary Disks

    Chambers, Lauren; Oberg, Karin I.; Cleeves, Lauren Ilsedore

    2017-01-01

    Protoplanetary disks are dynamic regions of gas and dust around young stars, the remnants of star formation, that evolve and coagulate over millions of years in order to ultimately form planets. The chemical composition of protoplanetary disks is affected by both the chemical and physical conditions in which they develop, including the initial molecular abundances in the birth cloud, the spectrum and intensity of radiation from the host star and nearby systems, and mixing and turbulence within the disk. A more complete understanding of the chemical evolution of disks enables a more complete understanding of the chemical composition of planets that may form within them, and of their capability to support life. One element known to be essential for life on Earth is nitrogen, which often is present in the form of ammonia (NH3). Recent observations by Salinas et al. (2016) reveal a theoretical discrepancy in the gas-phase and ice-phase ammonia abundances in protoplanetary disks; while observations of comets and protostars estimate the ice-phase NH3/H2O ratio in disks to be 5%, Salinas reports a gas-phase NH3/H2O ratio of ~7-84% in the disk surrounding TW Hydra, a young nearby star. Through computational chemical modeling of the TW Hydra disk using a reaction network of over 5000 chemical reactions, I am investigating the possible sources of excess gas-phase NH3 by determining the primary reaction pathways of NH3 production; the downstream chemical effects of ionization by ultraviolet photons, X-rays, and cosmic rays; and the effects of altering the initial abundances of key molecules such as N and N2. Beyond providing a theoretical explanation for the NH3 ice/gas discrepancy, this new model may lead to fuller understanding of the gas-phase formation processes of all nitrogen hydrides (NHx), and thus fuller understanding of the nitrogen-bearing molecules that are fundamental for life as we know it.

  7. Computing optimal interfacial structure of modulated phases

    Xu, Jie; Wang, Chu; Shi, An-Chang; Zhang, Pingwen

    2016-01-01

    We propose a general framework of computing interfacial structures between two modulated phases. Specifically we propose to use a computational box consisting of two half spaces, each occupied by a modulated phase with given position and orientation. The boundary conditions and basis functions are chosen to be commensurate with the bulk structures. It is observed that the ordered nature of modulated structures stabilizes the interface, which enables us to obtain optimal interfacial structures...

  8. Gas-phase photocatalysis in μ-reactors

    Vesborg, Peter Christian Kjærgaard; Olsen, Jakob Lind; Henriksen, Toke Riishøj

    2010-01-01

    Gas-phase photocatalysis experiments may benefit from the high sensitivity and good time response in product detection offered by μ-reactors. We demonstrate this by carrying out CO oxidation and methanol oxidation over commercial TiO2 photocatalysts in our recently developed high-sensitivity reac......Gas-phase photocatalysis experiments may benefit from the high sensitivity and good time response in product detection offered by μ-reactors. We demonstrate this by carrying out CO oxidation and methanol oxidation over commercial TiO2 photocatalysts in our recently developed high...

  9. Post-flame gas-phase sulfation of potassium chloride

    Li, Bo; Sun, Zhiwei; Li, Zhongshan

    2013-01-01

    The sulfation of KCl during biomass combustion has implications for operation and emissions: it reduces the rates of deposition and corrosion, it increases the formation of aerosols, and it leads to higher concentrations of HCl and lower concentrations of SO2 in the gas phase. Rigorously homogene......The sulfation of KCl during biomass combustion has implications for operation and emissions: it reduces the rates of deposition and corrosion, it increases the formation of aerosols, and it leads to higher concentrations of HCl and lower concentrations of SO2 in the gas phase. Rigorously...

  10. Reactive intermediates in the gas phase generation and monitoring

    Setser, D W

    2013-01-01

    Reactive Intermediates in the Gas Phase: Generation and Monitoring covers methods for reactive intermediates in the gas phase. The book discusses the generation and measurement of atom and radical concentrations in flow systems; the high temperature flow tubes, generation and measurement of refractory species; and the electronically excited long-lived states of atoms and diatomic molecules in flow systems. The text also describes the production and detection of reactive species with lasers in static systems; the production of small positive ions in a mass spectrometer; and the discharge-excite

  11. Porous Silicon Structures as Optical Gas Sensors

    Igor A. Levitsky

    2015-08-01

    Full Text Available We present a short review of recent progress in the field of optical gas sensors based on porous silicon (PSi and PSi composites, which are separate from PSi optochemical and biological sensors for a liquid medium. Different periodical and nonperiodical PSi photonic structures (bares, modified by functional groups or infiltrated with sensory polymers are described for gas sensing with an emphasis on the device specificity, sensitivity and stability to the environment. Special attention is paid to multiparametric sensing and sensor array platforms as effective trends for the improvement of analyte classification and quantification. Mechanisms of gas physical and chemical sorption inside PSi mesopores and pores of PSi functional composites are discussed.

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

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

    2017-07-01

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

  13. Visualization of velocity field and phase distribution in gas-liquid two-phase flow by NMR imaging

    Matsui, G.; Monji, H.; Obata, J.

    2004-01-01

    NMR imaging has been applied in the field of fluid mechanics, mainly single phase flow, to visualize the instantaneous flow velocity field. In the present study, NMR imaging was used to visualize simultaneously both the instantaneous phase structure and velocity field of gas-liquid two-phase flow. Two methods of NMR imaging were applied. One is useful to visualize both the one component of liquid velocity and the phase distribution. This method was applied to horizontal two-phase flow and a bubble rising in stagnant oil. It was successful in obtaining some pictures of velocity field and phase distribution on the cross section of the pipe. The other is used to visualize a two-dimensional velocity field. This method was applied to a bubble rising in a stagnant water. The velocity field was visualized after and before the passage of a bubble at the measuring cross section. Furthermore, the distribution of liquid velocity was obtained. (author)

  14. Structural Nervous System, Phase I

    National Aeronautics and Space Administration — GTL's SNS technology aids in the operation of new or existing structural health monitoring (SHM) systems by integrating data and power pathways into the structure....

  15. Structural phase transitions and Huang scattering

    Yamada, Yasusada

    1980-01-01

    The usefulness of the application of the concept of Huang scattering to the understandings of the origin of diffuse scatterings near structural phase transitions are discussed. It is pointed out that in several phase transitions, the observed diffuse scatterings can not be interpreted in terms of critical fluctuations of the order parameters associated with the structural phase transitions, and that they are rather interpreted as Huang scattering due to random distribution of individual order parameter which is 'dressed' by strain fields. Examples to show effective applications of this concept to analyze the experimental X-ray data and whence to understand microscopic mechanisms of structural phase transitions are presented. (author)

  16. Analytical study of solids-gas two phase flow

    Hosaka, Minoru

    1977-01-01

    Fundamental studies were made on the hydrodynamics of solids-gas two-phase suspension flow, in which very small solid particles are mixed in a gas flow to enhance the heat transfer characteristics of gas cooled high temperature reactors. Especially, the pressure drop due to friction and the density distribution of solid particles are theoretically analyzed. The friction pressure drop of two-phase flow was analyzed based on the analytical result of the single-phase friction pressure drop. The calculated values of solid/gas friction factor as a function of solid/gas mass loading are compared with experimental results. Comparisons are made for Various combinations of Reynolds number and particle size. As for the particle density distribution, some factors affecting the non-uniformity of distribution were considered. The minimum of energy dispersion was obtained with the variational principle. The suspension density of particles was obtained as a function of relative distance from wall and was compared with experimental results. It is concluded that the distribution is much affected by the particle size and that the smaller particles are apt to gather near the wall. (Aoki, K.)

  17. SVOC partitioning between the gas phase and settled dust indoors

    Weschler, Charles J.; Nazaroff, W. W.

    2010-01-01

    Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps...

  18. Gas-Phase IR Spectroscopy of Deprotonated Amino Acids

    Oomens, J.; Steill, J. D.; Redlich, B.

    2009-01-01

    Gas-phase infrared multiple photon dissociation (IRMPD) spectra have been recorded for the conjugate bases of a series of amino acids (Asp, Cys, Glu, Phe, Set, Trp, Tyr). The spectra are dominated by strong symmetric and antisymmetric carboxylate stretching modes around 1300 and 1600 cm(-1),

  19. Gas phase toluene isopropylation over high silica mordenite

    Mordenite (HM) catalysts with three different Si/Al ratios were compared for their activity and selectivities in gas phase toluene isopropylation with isopropanol. Catalyst with Si/Al ratio 44.9 offered better cumene selectivity, hence, it was chosen for detailed kinetic investigations. The influence of various process parameters ...

  20. Isothermal phase equilibria for the (HFC-32 + HFC-134a) mixed-gas hydrate system

    Miyauchi, Hiroshi; Yasuda, Kenjiro; Matsumoto, Yuuki; Hashimoto, Shunsuke; Sugahara, Takeshi; Ohgaki, Kazunari

    2012-01-01

    Highlights: ► Structural phase transition results in the heterogeneous azeotropic-like behaviour. ► HFC-134a molecules, in spite of an s-II former, occupy the large cages of s-I. ► Negative azeotropic-like behaviour becomes more remarkable at higher temperatures. - Abstract: Isothermal phase equilibria (pressure-composition relations in hydrate, gas, and aqueous phases) in the {difluoromethane (HFC-32) + 1,1,1,2-tetrafluoroethane (HFC-134a)} mixed-gas hydrate system were measured at the temperatures 274.15 K, 279.15 K, and 283.15 K. The heterogeneous azeotropic-like behaviour derived from the structural phase transition of (HFC-32 + HFC-134a) mixed-gas hydrates appears over the whole temperature range of the present study. In addition to the heterogeneous azeotropic-like behaviour, the isothermal phase equilibrium curves of the (HFC-32 + HFC-134a) mixed-gas hydrate system exhibit the negative homogeneous azeotropic-like behaviour at temperatures 279.15 K and 283.15 K. The negative azeotropic-like behaviour, which becomes more remarkable at higher temperatures, results in the lower equilibrium pressure of (HFC-32 + HFC-134a) mixed-gas hydrates than those of both simple HFC-32 and HFC-134a hydrates. Although the HFC-134a molecule forms the simple structure-II hydrate at the temperatures, the present findings reveal that HFC-134a molecules occupy a part of the large cages of the structure-I mixed-gas hydrate.

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

    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

  2. Highly Selective Continuous Gas-Phase Methoxycarbonylation of Ethylene with Supported Ionic Liquid Phase (SILP) Catalysts

    Khokarale, Santosh Govind; Garcia Suárez, Eduardo José; Fehrmann, Rasmus

    2017-01-01

    Supported ionic liquid phase (SILP) technology was applied for the first time to the Pd-catalyzed continuous, gas-phase methoxycarbonylation of ethylene to selectively produce methyl propanoate (MP) in high yields. The influence of catalyst and reaction parameters such as, for example, ionic liquid...

  3. Continuous gas-phase hydroformylation of 1-butene using supported ionic liquid phase (SILP) catalysts

    Haumann, Marco; Dentler, Katharina; Joni, Joni

    2007-01-01

    The concept of supported ionic liquid phase (SILP) catalysis has been extended to 1-butene hydroformylation. A rhodium-sulfoxantphos complex was dissolved in [BMIM][n-C8H17OSO3] and this solution was highly dispersed on silica. Continuous gas-phase experiments in a fixed-bed reactor revealed...

  4. Gas Price Formation, Structure and Dynamics

    Davoust, R.

    2008-07-01

    Our study, focused on gas prices in importing economies, describes wholesale prices and retail prices, their evolution for the last one or two decades, the economic mechanisms of price formation. While an international market for oil has developed thanks to moderate storage and transportation charges, these costs are much higher in the case of natural gas, which involves that this energy is still traded inside continental markets. There are three regional gas markets around the world: North America (the United States, importing mainly from Canada and Mexico), Europe (importing mainly from Russia, Algeria and Norway) and Asia (Japan, Korea, Taiwan, China and India, importing mainly from Indonesia, Malaysia and Australia). A market for gas has also developed in South America, but it will not be covered by our paper. In Europe and the US, due to large domestic resources and strong grids, natural gas is purchased mostly through pipelines. In Northeast Asia, there is a lack of such infrastructures, so imported gas takes mainly the form of Liquefied Natural Gas (LNG), shipped on maritime tankers. Currently, the LNG market is divided into two zones: the Atlantic Basin (Europe and US) and the Pacific Basin (Asia and the Western Coast of America). For the past few years, the Middle East and Africa have tended to be crucial suppliers for both LNG zones. Gas price formation varies deeply between regional markets, depending on several structural factors (regulation, contracting practises, existence of a spot market, liquidity, share of imports). Empirically, the degree of market opening (which corresponds to the seniority in the liberalization process) seems to be the primary determinant of pricing patterns. North America has the most liberalized and well-performing natural gas industry in the world. Gas pricing is highly competitive and is based on supply/demand balances. Spot and futures markets are developed. The British gas sector is also deregulated and thus follows a

  5. Gas Price Formation, Structure and Dynamics

    Davoust, R.

    2008-01-01

    Our study, focused on gas prices in importing economies, describes wholesale prices and retail prices, their evolution for the last one or two decades, the economic mechanisms of price formation. While an international market for oil has developed thanks to moderate storage and transportation charges, these costs are much higher in the case of natural gas, which involves that this energy is still traded inside continental markets. There are three regional gas markets around the world: North America (the United States, importing mainly from Canada and Mexico), Europe (importing mainly from Russia, Algeria and Norway) and Asia (Japan, Korea, Taiwan, China and India, importing mainly from Indonesia, Malaysia and Australia). A market for gas has also developed in South America, but it will not be covered by our paper. In Europe and the US, due to large domestic resources and strong grids, natural gas is purchased mostly through pipelines. In Northeast Asia, there is a lack of such infrastructures, so imported gas takes mainly the form of Liquefied Natural Gas (LNG), shipped on maritime tankers. Currently, the LNG market is divided into two zones: the Atlantic Basin (Europe and US) and the Pacific Basin (Asia and the Western Coast of America). For the past few years, the Middle East and Africa have tended to be crucial suppliers for both LNG zones. Gas price formation varies deeply between regional markets, depending on several structural factors (regulation, contracting practises, existence of a spot market, liquidity, share of imports). Empirically, the degree of market opening (which corresponds to the seniority in the liberalization process) seems to be the primary determinant of pricing patterns. North America has the most liberalized and well-performing natural gas industry in the world. Gas pricing is highly competitive and is based on supply/demand balances. Spot and futures markets are developed. The British gas sector is also deregulated and thus follows a

  6. Laser spectroscopy of a halocarbocation in the gas phase: CH2I+.

    Tao, Chong; Mukarakate, Calvin; Reid, Scott A

    2006-07-26

    We report the first gas-phase observation of the electronic spectrum of a simple halocarbocation, CH2I+. The ion was generated rotationally cold (Trot approximately 20 K) using pulsed discharge methods and was detected via laser spectroscopy. The identity of the spectral carrier was confirmed by modeling the rotational contour observed in the excitation spectra and by comparison of ground state vibrational frequencies determined by single vibronic level emission spectroscopy with Density Functional Theory (DFT) predictions. The transition was assigned as 3A1 gas phase should open new avenues for study of the structure and reactivity of these important ions.

  7. SILP catalysis in gas-phase hydroformylation and carbonylation

    Riisager, A.; Fehrmann, R. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Haumann, M.; Wasserscheid, P. [Univ. Erlangen-Nuernberg (Germany). Lehrstuhl fuer Chemische Reaktionstechnik

    2006-07-01

    Supported ionic liquid phase (SILP) catalysts are new materials consisting of an ionic liquid-metal catalyst solution highly dispersed on a porous support. The use of a non-volatile, ionic liquid catalyst phase in SILP catalysts results in a stable heterogeneous-type material with selectivity and efficiency like homogeneous catalysts. The silica-supported SILP Rh-bisphosphine hydroformylation catalyst exhibited good activities and excellent selectivities in gas phase hydroformylation with stability exceeding 700 hours time-on-stream. Spectroscopic and kinetic data confirmed the homogeneous nature of the catalyst. In the Rh- SILP catalysed carbonylation of methanol the formation of undesired by-products could be suppressed by variation of residence time and gas pressure. (orig.)

  8. Zpif's law in the liquid gas phase transition of nuclei

    Ma, Y.G.

    1999-01-01

    Zpif's law in the field of linguistics is tested in the nuclear disassembly within the framework of isospin dependent lattice gas model. It is found that the average cluster charge (or mass) of rank n in the charge (or mass) list shows exactly inversely to its rank, i.e., there exists Zpif's law, at the phase transition temperature. This novel criterion shall be helpful to search the nuclear liquid gas phase transition experimentally and theoretically. In addition, the finite size scaling of the effective phase transition temperature at which the Zpif's law appears is studied for several systems with different mass and the critical exponents of ν and β are tentatively extracted. (orig.)

  9. Capacitive Structures for Gas and Biological Sensing

    Sapsanis, Christos

    2015-04-01

    The semiconductor industry was benefited by the advances in technology in the last decades. This fact has an impact on the sensors field, where the simple transducer was evolved into smart miniaturized multi-functional microsystems. However, commercially available gas and biological sensors are mostly bulky, expensive, and power-hungry, which act as obstacles to mass use. The aim of this work is gas and biological sensing using capacitive structures. Capacitive sensors were selected due to its design simplicity, low fabrication cost, and no DC power consumption. In the first part, the dominant structure among interdigitated electrodes (IDEs), fractal curves (Peano and Hilbert) and Archimedean spiral was investigated from capacitance density perspective. The investigation consists of geometrical formula calculations, COMSOL Multiphysics simulations and cleanroom fabrication of the capacitors on a silicon substrate. Moreover, low-cost fabrication on flexible plastic PET substrate was conducted outside cleanroom with rapid prototyping using a maskless laser etching. The second part contains the humidity, Volatile Organic compounds (VOCs) and Ammonia sensing of polymers, Polyimide and Nafion, and metal-organic framework (MOF), Cu(bdc)2.xH2O using IDEs and tested in an automated gas setup for experiment control and data extraction. The last part includes the biological sensing of C - reactive protein (CRP) quantification, which is considered as a biomarker of being prone to cardiac diseases and Bovine serum albumin (BSA) protein quantification, which is used as a reference for quantifying unknown proteins.

  10. An absorbing phase transition from a structured active particle phase

    Lopez, Cristobal [Instituto Mediterraneo de Estudios Avanzados IMEDEA (CSIC-UIB), Campus de la Universidad de las Islas Baleares, E-07122 Palma de Mallorca (Spain); Ramos, Francisco [Departamento de Electromagnetismo y Fisica de la Materia and Instituto de Fisica Teorica y Computacional Carlos I, Facultad de Ciencias, Universidad de Granada, 18071 Granada (Spain); Hernandez-GarcIa, Emilio [Instituto Mediterraneo de Estudios Avanzados IMEDEA (CSIC-UIB), Campus de la Universidad de las Islas Baleares, E-07122 Palma de Mallorca (Spain)

    2007-02-14

    In this work we study the absorbing state phase transition of a recently introduced model for interacting particles with neighbourhood-dependent reproduction rates. The novelty of the transition is that as soon as the active phase is reached by increasing a control parameter a periodically arranged structure of particle clusters appears. A numerical study in one and two dimensions shows that the system falls into the directed percolation universality class.

  11. Gas-phase synthesis of semiconductor nanocrystals and its applications

    Mandal, Rajib

    Luminescent nanomaterials is a newly emerging field that provides challenges not only to fundamental research but also to innovative technology in several areas such as electronics, photonics, nanotechnology, display, lighting, biomedical engineering and environmental control. These nanomaterials come in various forms, shapes and comprises of semiconductors, metals, oxides, and inorganic and organic polymers. Most importantly, these luminescent nanomaterials can have different properties owing to their size as compared to their bulk counterparts. Here we describe the use of plasmas in synthesis, modification, and deposition of semiconductor nanomaterials for luminescence applications. Nanocrystalline silicon is widely known as an efficient and tunable optical emitter and is attracting great interest for applications in several areas. To date, however, luminescent silicon nanocrystals (NCs) have been used exclusively in traditional rigid devices. For the field to advance towards new and versatile applications for nanocrystal-based devices, there is a need to investigate whether these NCs can be used in flexible and stretchable devices. We show how the optical and structural/morphological properties of plasma-synthesized silicon nanocrystals (Si NCs) change when they are deposited on stretchable substrates made of polydimethylsiloxane (PDMS). Synthesis of these NCs was performed in a nonthermal, low-pressure gas phase plasma reactor. To our knowledge, this is the first demonstration of direct deposition of NCs onto stretchable substrates. Additionally, in order to prevent oxidation and enhance the luminescence properties, a silicon nitride shell was grown around Si NCs. We have demonstrated surface nitridation of Si NCs in a single step process using non?thermal plasma in several schemes including a novel dual-plasma synthesis/shell growth process. These coated NCs exhibit SiNx shells with composition depending on process parameters. While measurements including

  12. Structural arrest in an ideal gas.

    van Ketel, Willem; Das, Chinmay; Frenkel, Daan

    2005-04-08

    We report a molecular dynamics study of a simple model system that has the static properties of an ideal gas, yet exhibits nontrivial "glassy" dynamics behavior at high densities. The constituent molecules of this system are constructs of three infinitely thin hard rods of length L, rigidly joined at their midpoints. The crosses have random but fixed orientation. The static properties of this system are those of an ideal gas, and its collision frequency can be computed analytically. For number densities NL(3)/V>1, the single-particle diffusivity goes to zero. As the system is completely structureless, standard mode-coupling theory cannot describe the observed structural arrest. Nevertheless, the system exhibits many dynamical features that appear to be mode-coupling-like. All high-density incoherent intermediate scattering functions collapse onto master curves that depend only on the wave vector.

  13. Gas phase decontamination of gaseous diffusion process equipment

    Bundy, R.D.; Munday, E.B.; Simmons, D.W.; Neiswander, D.W.

    1994-01-01

    D ampersand D of the process facilities at the gaseous diffusion plants (GDPs) will be an enormous task. The EBASCO estimate places the cost of D ampersand D of the GDP at the K-25 Site at approximately $7.5 billion. Of this sum, nearly $4 billion is associated with the construction and operation of decontamination facilities and the dismantlement and transport of contaminated process equipment to these facilities. In situ long-term low-temperature (LTLT) gas phase decontamination is being developed and demonstrated at the K-25 site as a technology that has the potential to substantially lower these costs while reducing criticality and safeguards concerns and worker exposure to hazardous and radioactive materials. The objective of gas phase decontamination is to employ a gaseous reagent to fluorinate nonvolatile uranium deposits to form volatile LJF6, which can be recovered by chemical trapping or freezing. The LTLT process permits the decontamination of the inside of gas-tight GDP process equipment at room temperature by substituting a long exposure to subatmospheric C1F for higher reaction rates at higher temperatures. This paper outlines the concept for applying LTLT gas phase decontamination, reports encouraging laboratory experiments, and presents the status of the design of a prototype mobile system. Plans for demonstrating the LTLT process on full-size gaseous diffusion equipment are also outlined briefly

  14. Preconceptual design of the gas-phase decontamination demonstration cart

    Munday, E.B.

    1993-12-01

    Removal of uranium deposits from the interior surfaces of gaseous diffusion equipment will be a major portion of the overall multibillion dollar effort to decontaminate and decommission the gaseous diffusion plants. Long-term low-temperature (LTLT) gas-phase decontamination is being developed at the K-25 Site as an in situ decontamination process that is expected to significantly lower the decontamination costs, reduce worker exposure to radioactive materials, and reduce safeguard concerns. This report documents the preconceptual design of the process equipment that is necessary to conduct a full-scale demonstration of the LTLT method in accordance with the process steps listed above. The process equipment and method proposed in this report are not intended to represent a full-scale production campaign design and operation, since the gas evacuation, gas charging, and off-gas handling systems that would be cost effective in a production campaign are not cost effective for a first-time demonstration. However, the design presented here is expected to be applicable to special decontamination projects beyond the demonstration, which could include the Deposit Recovery Program. The equipment will therefore be sized to a 200 ft size 1 converter (plus a substantial conservative design margin), which is the largest item of interest for gas phase decontamination in the Deposit Recovery Program. The decontamination equipment will allow recovery of the UF 6 , which is generated from the reaction of ClF 3 with the uranium deposits, by use of NaF traps

  15. Cold flame on Biofilm - Transport of Plasma Chemistry from Gas to Liquid Phase

    Kong, Michael

    2014-10-01

    One of the most active and fastest growing fields in low-temperature plasma science today is biological effects of gas plasmas and their translation in many challenges of societal importance such as healthcare, environment, agriculture, and nanoscale fabrication and synthesis. Using medicine as an example, there are already three FDA-approved plasma-based surgical procedures for tissue ablation and blood coagulation and at least five phase-II clinical trials on plasma-assisted wound healing therapies. A key driver for realizing the immense application potential of near room-temperature ambient pressure gas plasmas, commonly known as cold atmospheric plasmas or CAP, is to build a sizeable interdisciplinary knowledge base with which to unravel, optimize, and indeed design how reactive plasma species interact with cells and their key components such as protein and DNA. Whilst a logical objective, it is a formidable challenge not least since existing knowledge of gas discharges is largely in the gas-phase and therefore not directly applicable to cell-containing matters that are covered by or embedded in liquid (e.g. biofluid). Here, we study plasma inactivation of biofilms, a jelly-like structure that bacteria use to protect themselves and a major source of antimicrobial resistance. As 60--90% of biofilm is made of water, we develop a holistic model incorporating physics and chemistry in the upstream CAP-generating region, a plasma-exit region as a buffer for as-phase transport, and a downstream liquid region bordering the gas buffer region. A special model is developed to account for rapid chemical reactions accompanied the transport of gas-phase plasma species through the gas-liquid interface and for liquid-phase chemical reactions. Numerical simulation is used to illustrate how key reactive oxygen species (ROS) are transported into the liquid, and this is supported with experimental data of both biofilm inactivation using plasmas and electron spin spectroscopy (ESR

  16. Gas-liquid two-phase flows in double inlet cyclones for natural gas separation

    Yang, Yan; Wang, Shuli; Wen, Chuang

    2017-01-01

    The gas-liquid two-phase flow within a double inlet cyclone for natural gasseparation was numerically simulated using the discrete phase model. The numericalapproach was validated with the experimental data, and the comparison resultsagreed well with each other. The simulation results showed...... that the strong swirlingflow produced a high centrifugal force to remove the particles from the gas mixture.The larger particles moved downward on the internal surface and were removeddue to the outer vortex near the wall. Most of the tiny particles went into the innervortex zones and escaped from the up...

  17. Angular intensity of a gas-phase field ionization source

    Orloff, J.; Swanson, L.W.

    1979-01-01

    Angular intensities of 1 μA sr -1 have been measured for a gas-phase field ionization source in an optical column under practical operating conditions. The source, which was differentially pumped and cooled to 77 K, utilized a -oriented iridium emitter and precooled hydrogen gas at 10 -2 Torr. The ion beam was collimated with an electrostatic lens and detected below an aperture subtending 0.164 msr. A transmitted current of approx.10 -10 A was measured at voltages corresponding to a field of approx. =2.2 V/A at the emitter

  18. The Structural Phase Transition in Solid DCN

    Dietrich, O. W.; Mackenzie, Gordon A.; Pawley, G. S.

    1975-01-01

    Neutron scattering measurements on deuterated hydrogen cyanide have shown that the structural phase change from a tetragonal to an orthorhombic form at 160K is a first-order transition. A transverse acoustic phonon mode, which has the symmetry of the phase change, was observed at very low energies...

  19. Experimental on two sensors combination used in horizontal pipe gas-water two-phase flow

    Wu, Hao; Dong, Feng

    2014-01-01

    Gas-water two phase flow phenomenon widely exists in production and living and the measurement of it is meaningful. A new type of long-waist cone flow sensor has been designed to measure two-phase mass flow rate. Six rings structure of conductance probe is used to measure volume fraction and axial velocity. The calibration of them have been made. Two sensors have been combined in horizontal pipeline experiment to measure two-phase flow mass flow rate. Several model of gas-water two-phase flow has been discussed. The calculation errors of total mass flow rate measurement is less than 5% based on the revised homogeneous flow model

  20. Tax issues in structuring gas process arrangements

    Iverach, R.J.

    1999-01-01

    The current status of various tax issues regarding ownership, operation and financing of gas processing facilities in Canada was discussed. Frequently, energy companies are not taxed because of their large pools of un-depreciated capital cost and other resource related accounts. In addition, their time horizons for taxability are being extended in line with the expansion of their businesses. However, other investors are fully taxable, hence they wish to shelter their income through the use of tax efficient investment arrangements. This paper provides a detailed description of the tax treatment of gas processing facilities, tax implications of various structures between the producer and the investor such as lease, processing fee arrangements etc., and use of 'Canadian Renewable and Conservation Expense' (CRCE) for cogeneration projects within processing plants. All these need to be considered before completing a financing transaction involving a gas processing facility, since the manner in which the transaction is completed will determine the advantages and benefits from an income tax perspective. The accounting and legal aspects must be similarly scrutinized to ensure that the intended results for all parties are achieved. 8 figs

  1. Industrial aspects of gas-liquid two-phase flow

    Hewitt, G.F.

    1977-01-01

    The lecture begins by reviewing the various types of plant in which two phase flow occurs. Specifically, boiling plant, condensing plant and pipelines are reviewed, and the various two phase flow problems occurring in them are described. Of course, many other kinds of chemical engineering plant involve two phase flow, but are somewhat outside the scope of this lecture. This would include distillation columns, vapor-liquid separators, absorption towers etc. Other areas of industrial two phase flow which have been omitted for space reasons from this lecture are those concerned with gas/solids, liquid/solid and liquid/liquid flows. There then follows a description of some of the two phase flow processes which are relevant in industrial equipment and where special problems occur. The topics chosen are as follows: (1) pressure drop; (2) horizontal tubes - separation effects non-uniformites in heat transfer coefficient, effect of bends on dryout; (3) multicomponent mixtures - effects in pool boiling, mass transfer effects in condensation and Marangoni effects; (4) flow distribution - manifold problems in single phase flow, separation effects at a single T-junction in two phase flow and distribution in manifolds in two phase flow; (5) instability - oscillatory instability, special forms of instability in cryogenic systems; (6) nucleate boiling - effect of variability of surface, unresolved problems in forced convective nucleate boiling; and (7) shell side flows - flow patterns, cross flow boiling, condensation in cross flow

  2. The Structural Phase Transition in Octaflournaphtalene

    Mackenzie, Gordon A.; Arthur, J. W.; Pawley, G. S.

    1977-01-01

    The phase transition in octafluoronaphthalene has been investigated by Raman scattering and neutron powder diffraction. The weight of the experimental evidence points to a unit cell doubling in the a direction, but with no change in space group symmetry. Lattice dynamics calculations support...... this evidence and indicate that the mechanism of the phase transition may well be the instability of a zone boundary acoustic mode of librational character. The structure of the low-temperature phase has been refined and the Raman spectra of the upper and lower phases are reported....

  3. Long-lived gas-phase radicals from combustion

    Kaneko, Takashi; Furusawa, Koji; Amano, Toshiji; Okubo, Yoichi; Tsuchiya, Jun' ichi; Yoshizawa, Fujiroku; Akutsu, Yoshiaki; Tamura, Masamitsu; Yoshida, Tadao (Univ. of Tokyo (Japan))

    1989-04-20

    On indoor air pollution or fire, it is feared that the gas-phase radicals from the combustion of inflammables or fuel seriously exert an influence on the organisms as harmful matter. The gas-phase radicals were studied using the electron spin resonance (ESR) spin-trapping technique. For the spin trap solution, 0.1 mol solution of {alpha}-phenyl-N-t-butylnitron in benzene was used. As a result, apparently long-lived and highly reactive oxygen-centered radicals were detected in the smoke from polyethylene, polypropylene, polystyrene, polymethylmethacrylate, cellulose, kerosene, benzene, acetone, methanol and butylalcohol. It is suggested that the production mechanism for the radicals should be different from olefin-NOx-air system reaction, which is considered for the radicals from cigarette smoke. 11 refs., 6 figs., 2 tabs.

  4. Molecular structures of Se(SCH3)2 and Te(SCH3)2 using gas-phase electron diffraction and ab initio and DFT geometry optimisations.

    Fleischer, Holger; Wann, Derek A; Hinchley, Sarah L; Borisenko, Konstantin B; Lewis, James R; Mawhorter, Richard J; Robertson, Heather E; Rankin, David W H

    2005-10-07

    The molecular structures of Se(SCH(3))(2) and Te(SCH(3))(2) were investigated using gas-phase electron diffraction (GED) and ab initio and DFT geometry optimisations. While parameters involving H atoms were refined using flexible restraints according to the SARACEN method, parameters that depended only on heavy atoms could be refined without restraints. The GED-determined geometric parameters (r(h1)) are: rSe-S 219.1(1), rS-C 183.2(1), rC-H 109.6(4) pm; angleS-Se-S 102.9(3), angleSe-S-C 100.6(2), angleS-C-H (mean) 107.4(5), phiS-Se-S-C 87.9(20), phiSe-S-C-H 178.8(19) degrees for Se(SCH(3))(2), and rTe-S 238.1(2), rS-C 184.1(3), rC-H 110.0(6) pm; angleS-Te-S 98.9(6), angleTe-S-C 99.7(4), angleS-C-H (mean) 109.2(9), phiS-Te-S-C 73.0(48), phiTe-S-C-H 180.1(19) degrees for Te(SCH(3))(2). Ab initio and DFT calculations were performed at the HF, MP2 and B3LYP levels, employing either full-electron basis sets [3-21G(d) or 6-31G(d)] or an effective core potential with a valence basis set [LanL2DZ(d)]. The best fit to the GED structures was achieved at the MP2 level. Differences between GED and MP2 results for rS-C and angleS-Te-S were explained by the thermal population of excited vibrational states under the experimental conditions. All theoretical models agreed that each compound exists as two stable conformers, one in which the methyl groups are on the same side (g(+)g(-) conformer) and one in which they are on different sides (g(+)g(+) conformer) of the S-Y-S plane (Y = Se, Te). The conformational composition under the experimental conditions could not be resolved from the GED data. Despite GED R-factors and ab initio and DFT energies favouring the g(+)g(+) conformer, it is likely that both conformers are present, for Se(SCH(3))(2) as well as for Te(SCH(3))(2).

  5. Multiple Multidentate Halogen Bonding in Solution, in the Solid State, and in the (Calculated) Gas Phase.

    Jungbauer, Stefan H; Schindler, Severin; Herdtweck, Eberhardt; Keller, Sandro; Huber, Stefan M

    2015-09-21

    The binding properties of neutral halogen-bond donors (XB donors) bearing two multidentate Lewis acidic motifs toward halides were investigated. Employing polyfluorinated and polyiodinated terphenyl and quaterphenyl derivatives as anion receptors, we obtained X-ray crystallographic data of the adducts of three structurally related XB donors with tetraalkylammonium chloride, bromide, and iodide. The stability of these XB complexes in solution was determined by isothermal titration calorimetry (ITC), and the results were compared to X-ray analyses as well as to calculated binding patterns in the gas phase. Density functional theory (DFT) calculations on the gas-phase complexes indicated that the experimentally observed distortion of the XB donors during multiple multidentate binding can be reproduced in 1:1 complexes with halides, whereas adducts with two halides show a symmetric binding pattern in the gas phase that is markedly different from the solid state structures. Overall, this study demonstrates the limitations in the transferability of binding data between solid state, solution, and gas phase in the study of complex multidentate XB donors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Gas phase fractionation method using porous ceramic membrane

    Peterson, Reid A.; Hill, Jr., Charles G.; Anderson, Marc A.

    1996-01-01

    Flaw-free porous ceramic membranes fabricated from metal sols and coated onto a porous support are advantageously used in gas phase fractionation methods. Mean pore diameters of less than 40 .ANG., preferably 5-20 .ANG. and most preferably about 15 .ANG., are permeable at lower pressures than existing membranes. Condensation of gases in small pores and non-Knudsen membrane transport mechanisms are employed to facilitate and increase membrane permeability and permselectivity.

  7. Gas Phase Hydrogenation of Levulinic Acid to gamma-Valerolactone

    Bonrath, Werner; Castelijns, Anna Maria Cornelia Francisca; de Vries, Johannes Gerardus; Guit, Rudolf Philippus Maria; Schuetz, Jan; Sereinig, Natascha; Vaessen, Henricus Wilhelmus Leonardus Marie

    The gas phase hydrogenation of levulinic acid to gamma-valerolactone over copper and ruthenium based catalysts in a continuous fixed-bed reactor system was investigated. Among the catalysts a copper oxide based one [50-75 % CuO, 20-25 % SiO2, 1-5 % graphite, 0.1-1 % CuCO3/Cu(OH)(2)] gave

  8. The gas chimney formation during the steam explosion premixing phase

    Leskovar, M.

    2001-01-01

    The crucial part in isothermal premixing experiment simulation is the correct prediction of the gas chimney, which forms when the spheres penetrate into water. The first simulation results with the developed original combined multiphase model showed that the gas chimney starts to close at the wrong place at the top of the chimney and not in the middle, like it was observed in the experiments. To find the physical explanation for this identified weakness of our numerical model a comprehensive parametric analysis (mesh size, initial water-air surface thickness, water density, momentum coupling starting position) has been performed. It was established that the reason for the unphysical gas chimney closing at the top could be the gradual air-water density transition in the experiment model, since there is due to the finite differences description always a transition layer with intermediate phases density over the pure water phase. It was shown that this difference between our numerical model and the experiment can be somewhat compensated if the spheres interfacial drag coefficient at the upmost mesh plane of the unphysical air-water transition layer is artificially risen. On this way a more correct gas chimney formation can be obtained.(author)

  9. Structure and reactivity of C7H7+ ions from the decay of tritiated toluenes. Part 1. Reactions of free tolyl ions with methanol in the gas and liquid phases

    Cacace, F.; Ciranni, G.; Sparapani, C.; Speranza, M.

    1984-01-01

    Labeled tolyl cations from the decay of ring-multitritiated toluene have been allowed to react with methanol in the liquid and the gas phases, at pressures ranging from 6 to 100 torr, yielding methyl tolyl ethers as the major products, without appreciable formation of benzyl methyl ether. The isomeric composition of the products from the gaseous systems depends on the pressure, the percentage of o-tolyl ether increasing at the expense of the para isomer as the methanol pressure is reduced. The results show that the three tolyl ions exist as distinct species in the dilute gas state. When formed in a sufficiently excited state, as from the β decay of a 3 H atom in toluene, they undergo appreciable interconversion, without detectable isomerization to the benzyl cation, at least within the pressure range accessible to the decay technique. 50 references, 1 table

  10. Reconstructive structural phase transitions in dense Mg

    Yao Yansun; Klug, Dennis D

    2012-01-01

    The question raised recently about whether the high-pressure phase transitions of Mg follow a hexagonal close-packed (hcp) → body centered cubic (bcc) or hcp → double hexagonal close-packed (dhcp) → bcc sequence at room temperature is examined by the use of first principles density functional methods. Enthalpy calculations show that the bcc structure replaces the hcp structure to become the most stable structure near 48 GPa, whereas the dhcp structure is never the most stable structure in the pressure range of interest. The characterized phase-transition mechanisms indicate that the hcp → dhcp transition is also associated with a higher enthalpy barrier. At room temperature, the structural sequence hcp → bcc is therefore more energetically favorable for Mg. The same conclusion is also reached from the simulations of the phase transitions using metadynamics methods. At room temperature, the metadynamics simulations predict the onset of a hcp → bcc transition at 40 GPa and the transition becomes more prominent upon further compression. At high temperatures, the metadynamics simulations reveal a structural fluctuation among the hcp, dhcp, and bcc structures at 15 GPa. With increasing pressure, the structural evolution at high temperatures becomes more unambiguous and eventually settles to a bcc structure once sufficient pressure is applied. (paper)

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

    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...

  12. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

    Do, D D; Do, H D; Nicholson, D

    2009-01-29

    We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

  13. GAS PHASE SELECTIVE PHOTOXIDATION OF ALCOHOLS USING LIGHT-ACTIVATED TITANIUM DIOXIDE AND MOLECULAR OXYGEN

    Gas Phase Selective Oxidation of Alcohols Using Light-Activated Titanium Dioxide and Molecular Oxygen Gas phase selective oxidations of various primary and secondary alcohols are studied in an indigenously built stainless steel up-flow photochemical reactor using ultravi...

  14. Two-Phase Phenomena In Wet Flue Gas Desulfurization Process

    Minzer, U.; Moses, E.J.; Toren, M.; Blumenfeld, Y.

    1998-01-01

    In order to reduce sulfur oxides discharge, Israel Electric Corporation (IEC) is building a wet Flue Gas Desulfurization (FGD) facility at Rutenberg B power station. The primary objective of IEC is to minimize the occurrence of stack liquid discharge and avoid the discharge of large droplets, in order to prevent acid rain around the stack. Liquid discharge from the stack is the integrated outcome of two-phase processes, which are discussed in this work. In order to estimate droplets discharge the present investigation employs analytical models, empirical tests, and numerical calculations of two-phase phenomena. The two-phase phenomena are coupled and therefore cannot be investigated separately. The present work concerns the application of Computational Fluid Dynamic (CFD) as an engineering complementary tool in the IEC investigation

  15. FLUIDDYNAMIC ASPECTS OF GAS-PHASE ETHYLENE POLYMERIZATION REACTOR DESIGN

    Guardani R.

    1998-01-01

    Full Text Available The relative importance of design variables affecting the fluiddynamic behavior of a fluidized bed reactor for the gas-phase ethylene polymerization is discussed, based on mathematical modeling. The three-phase bubbling fluidized bed model is based on axially distributed properties for the bubble, cloud and emulsion phases, combined with correlations for population balance and entrainment. Under the operating conditions adopted in most industrial processes, the reactor performance is affected mainly by the reaction rate and solids entrainment. Simulation results indicate that an adequate design of the freeboard and particle collecting equipment is of primary importance in order to produce polymeric particles with the desired size distribution, as well as to keep entrainment and catalyst feed rates at adequate levels.

  16. Energy Demodulation Algorithm for Flow Velocity Measurement of Oil-Gas-Water Three-Phase Flow

    Yingwei Li

    2014-01-01

    Full Text Available Flow velocity measurement was an important research of oil-gas-water three-phase flow parameter measurements. In order to satisfy the increasing demands for flow detection technology, the paper presented a gas-liquid phase flow velocity measurement method which was based on energy demodulation algorithm combing with time delay estimation technology. First, a gas-liquid phase separation method of oil-gas-water three-phase flow based on energy demodulation algorithm and blind signal separation technology was proposed. The separation of oil-gas-water three-phase signals which were sampled by conductance sensor performed well, so the gas-phase signal and the liquid-phase signal were obtained. Second, we used the time delay estimation technology to get the delay time of gas-phase signals and liquid-phase signals, respectively, and the gas-phase velocity and the liquid-phase velocity were derived. At last, the experiment was performed at oil-gas-water three-phase flow loop, and the results indicated that the measurement errors met the need of velocity measurement. So it provided a feasible method for gas-liquid phase velocity measurement of the oil-gas-water three-phase flow.

  17. The Physics of Structural Phase Transitions

    Fujimoto, Minoru

    2005-01-01

    Phase transitions in which crystalline solids undergo structural changes present an interesting problem in the interplay between the crystal structure and the ordering process that is typically nonlinear. Intended for readers with prior knowledge of basic condensed-matter physics, this book emphasizes the physics behind spontaneous structural changes in crystals. Starting with the relevant thermodynamic principles, the text discusses the nature of order variables in collective motion in structural phase transitions, where a singularity in such a collective mode is responsible for lattice instability as revealed by soft phonons. In this book, critical anomalies at second-order structural transitions are first analyzed with the condensate model. Discussions on the nonlinear ordering mechanism are followed with the soliton theory, thereby interpreting the role of long-range order. Relevant details for nonlinear mathematics are therefore given for minimum necessity. The text also discusses experimental methods fo...

  18. Determination of gas phase protein ion densities via ion mobility analysis with charge reduction.

    Maisser, Anne; Premnath, Vinay; Ghosh, Abhimanyu; Nguyen, Tuan Anh; Attoui, Michel; Hogan, Christopher J

    2011-12-28

    We use a charge reduction electrospray (ESI) source and subsequent ion mobility analysis with a differential mobility analyzer (DMA, with detection via both a Faraday cage electrometer and a condensation particle counter) to infer the densities of single and multiprotein ions of cytochrome C, lysozyme, myoglobin, ovalbumin, and bovine serum albumin produced from non-denaturing (20 mM aqueous ammonium acetate) and denaturing (1 : 49.5 : 49.5, formic acid : methanol : water) ESI. Charge reduction is achieved through use of a Po-210 radioactive source, which generates roughly equal concentrations of positive and negative ions. Ions produced by the source collide with and reduce the charge on ESI generated drops, preventing Coulombic fissions, and unlike typical protein ESI, leading to gas-phase protein ions with +1 to +3 excess charges. Therefore, charge reduction serves to effectively mitigate any role that Coulombic stretching may play on the structure of the gas phase ions. Density inference is made via determination of the mobility diameter, and correspondingly the spherical equivalent protein volume. Through this approach it is found that for both non-denaturing and denaturing ESI-generated ions, gas-phase protein ions are relatively compact, with average densities of 0.97 g cm(-3) and 0.86 g cm(-3), respectively. Ions from non-denaturing ESI are found to be slightly more compact than predicted from the protein crystal structures, suggesting that low charge state protein ions in the gas phase are slightly denser than their solution conformations. While a slight difference is detected between the ions produced with non-denaturing and denaturing ESI, the denatured ions are found to be much more dense than those examined previously by drift tube mobility analysis, in which charge reduction was not employed. This indicates that Coulombic stretching is typically what leads to non-compact ions in the gas-phase, and suggests that for gas phase

  19. Gas phase chromatography of halides of elements 104 and 105

    Tuerler, A.; Gregorich, K.E.; Czerwinski, K.R.; Hannink, N.J.; Henderson, R.A.; Hoffman, D.C.; Kacher, C.D.; Kadkhodayan, B.; Kreek, S.A.; Lee, D.M.; Leyba, J.D.; Nurmia, M.J.; Gaeggeler, H.W.; Jost, D.T.; Kovacs, J.; Scherer, U.W.; Vermeulen, D.; Weber, A.; Barth, H.; Gober, M.K.; Kratz, J.V.; Bruechle, W.; Schaedel, M.; Schimpf, E.; Gober, M.K.; Kratz, J.V.; Zimmermann, H.P.

    1991-04-01

    On-line isothermal gas phase chromatography was used to study halides of 261 104 (T 1/2 = 65 s) and 262,263 105 (T 1/2 = 34 s and 27 s) produced an atom-at-a time via the reactions 248 Cm( 18 O, 5n) and 249 Bk( 18 O, 5n, 4n), respectively. Using HBr and HCl gas as halogenating agents, we were able to produce volatile bromides and chlorides of the above mentioned elements and study their behavior compared to their lighter homologs in Groups 4 or 5 of the periodic table. Element 104 formed more volatile bromides than its homolog Hf. In contrast, element 105 bromides were found to be less volatile than the bromides of the group 5 elements Nb and Ta. Both 104 and Hf chlorides were observed to be more volatile than their respective bromides. 31 refs., 8 figs

  20. Measurement of phase interaction in dispersed gas-particle two-phase flow by phase-doppler anemometry

    Mergheni Ali Mohamed

    2008-01-01

    Full Text Available For simultaneous measurement of size and velocity distributions of continuous and dispersed phases in a two-phase flow a technique phase-Doppler anemometry was used. Spherical glass particles with a particle diameter range from 102 up to 212 µm were used. In this two-phase flow an experimental results are presented which indicate a significant influence of the solid particles on the flow characteristics. The height of influence of these effects depends on the local position in the jet. Near the nozzle exit high gas velocity gradients exist and therefore high turbulence production in the shear layer of the jet is observed. Here the turbulence intensity in the two-phase jet is decreased compared to the single-phase jet. In the developed zone the velocity gradient in the shear layer is lower and the turbulence intensity reduction is higher. .

  1. Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

    Khrapkovskii, Grigorii M; Shamov, Alexander G; Nikolaeva, E V; Chachkov, D V

    2009-01-01

    Data on the mechanisms of gas-phase monomolecular decomposition of nitroalkanes, nitroalkenes and nitroarenes obtained using modern quantum chemical methods are described systematically. The attention is focused on the discussion of multistage decomposition of nitro compounds to elementary experimentally observed products. Characteristic features of competition of different mechanisms and the effect of molecular structure on the change in the Arrhenius parameters of the primary reaction step are considered.

  2. Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

    Khrapkovskii, Grigorii M; Shamov, Alexander G; Nikolaeva, E V; Chachkov, D V [Kazan State Technological University, Kazan (Russian Federation)

    2009-10-31

    Data on the mechanisms of gas-phase monomolecular decomposition of nitroalkanes, nitroalkenes and nitroarenes obtained using modern quantum chemical methods are described systematically. The attention is focused on the discussion of multistage decomposition of nitro compounds to elementary experimentally observed products. Characteristic features of competition of different mechanisms and the effect of molecular structure on the change in the Arrhenius parameters of the primary reaction step are considered.

  3. Gas phase spectroscopic study of unstable molecules using FTIR technique

    Allaf, A.W.; Alibrahim, M.; Kassem, M.

    1998-01-01

    A new route has been developed, leading to the production of phosphorus (III) oxycyanide, OPCN and phosphorus (III) oxycyanate, OPOCN by an on-line process using phosphoryl chloride, POCL 3 as a starting material passed over heated silver at 870 Centigrade and then reacted with AgCN and KOCN heated at 270 Centigrade and 590 Centigrade to produce OPCN and OPOCN respectively. The gas phase fourier transform infrared spectra reported for the first time show the two characterized bonds of OPCN and OPOCN at 2165 cm -1 and 2130 cm -1 , assigned to the C≡N stretching fundamentals of OPCN and OPOCN respectively. (Author)

  4. Study of two-phase underexpanded jets by gas jet

    Uchida, Mitsunori; Someya, Satoshi; Okamoto, Koji

    2008-01-01

    When a heat exchange in a Fast Breeder Reactor cracks, a sodium-water reaction occurs. When a tube cracks, highly pressurized water or steam escapes into the surrounding liquid sodium and a sodium-water reaction occurs forming the disodium oxide. The disodium oxide caught in the steam jet strikes other tubes in the reactor. The struck disodium oxide can then cause these tubes to crack. The release of steam into the liquid sodium media is a two-phase flow involving underexpansion. In this paper qualitative measurement of the underexpanded gas jet which injected into water was carried our for the purpose of analyzing the behavior of the two-phase flow. (author)

  5. The Genealogical Tree of Ethanol: Gas-phase Formation of Glycolaldehyde, Acetic Acid, and Formic Acid

    Skouteris, Dimitrios; Balucani, Nadia; Ceccarelli, Cecilia; Vazart, Fanny; Puzzarini, Cristina; Barone, Vincenzo; Codella, Claudio; Lefloch, Bertrand

    2018-02-01

    Despite the harsh conditions of the interstellar medium, chemistry thrives in it, especially in star-forming regions where several interstellar complex organic molecules (iCOMs) have been detected. Yet, how these species are synthesized is a mystery. The majority of current models claim that this happens on interstellar grain surfaces. Nevertheless, evidence is mounting that neutral gas-phase chemistry plays an important role. In this paper, we propose a new scheme for the gas-phase synthesis of glycolaldehyde, a species with a prebiotic potential and for which no gas-phase formation route was previously known. In the proposed scheme, the ancestor is ethanol and the glycolaldehyde sister species are acetic acid (another iCOM with unknown gas-phase formation routes) and formic acid. For the reactions of the new scheme with no available data, we have performed electronic structure and kinetics calculations deriving rate coefficients and branching ratios. Furthermore, after a careful review of the chemistry literature, we revised the available chemical networks, adding and correcting several reactions related to glycolaldehyde, acetic acid, and formic acid. The new chemical network has been used in an astrochemical model to predict the abundance of glycolaldehyde, acetic acid, and formic acid. The predicted abundance of glycolaldehyde depends on the ethanol abundance in the gas phase and is in excellent agreement with the measured one in hot corinos and shock sites. Our new model overpredicts the abundance of acetic acid and formic acid by about a factor of 10, which might imply a yet incomplete reaction network.

  6. Analyses of liquid-gas two-phase flow in fermentation tanks

    Toi, Takashi; Serizawa, Akimi; Takahashi, Osamu; Kawara, Zensaku; Gofuku, Akio; Kataoka, Isao.

    1993-01-01

    The understanding of two-phase flow is one of the important problems for both design and safety analyses of various engineering systems. For example, the flow conditions in beer fermentation tanks have an influence on the quality of production and productivity of tank. In this study, a two-dimensional numerical calculation code based on the one-pressure two-fluid model is developed to understand the circulation structure of low quality liquid-gas two-phase flows induced by bubble plume in a tank. (author)

  7. Flow-pattern identification and nonlinear dynamics of gas-liquid two-phase flow in complex networks.

    Gao, Zhongke; Jin, Ningde

    2009-06-01

    The identification of flow pattern is a basic and important issue in multiphase systems. Because of the complexity of phase interaction in gas-liquid two-phase flow, it is difficult to discern its flow pattern objectively. In this paper, we make a systematic study on the vertical upward gas-liquid two-phase flow using complex network. Three unique network construction methods are proposed to build three types of networks, i.e., flow pattern complex network (FPCN), fluid dynamic complex network (FDCN), and fluid structure complex network (FSCN). Through detecting the community structure of FPCN by the community-detection algorithm based on K -mean clustering, useful and interesting results are found which can be used for identifying five vertical upward gas-liquid two-phase flow patterns. To investigate the dynamic characteristics of gas-liquid two-phase flow, we construct 50 FDCNs under different flow conditions, and find that the power-law exponent and the network information entropy, which are sensitive to the flow pattern transition, can both characterize the nonlinear dynamics of gas-liquid two-phase flow. Furthermore, we construct FSCN and demonstrate how network statistic can be used to reveal the fluid structure of gas-liquid two-phase flow. In this paper, from a different perspective, we not only introduce complex network theory to the study of gas-liquid two-phase flow but also indicate that complex network may be a powerful tool for exploring nonlinear time series in practice.

  8. Periodic orbits and TDHF phase space structure

    Hashimoto, Yukio; Iwasawa, Kazuo [Tsukuba Univ., Ibaraki (Japan). Inst. of Physics; Tsukuma, Hidehiko; Sakata, Fumihiko

    1998-03-01

    The collective motion of atomic nuclei is closely coupled with the motion of nucleons, therefore, it is nonlinear, and the contents of the motion change largely with the increase of its amplitude. As the framework which describes the collective motion accompanied by the change of internal structure, time-dependent Hurtley Fock (TDHF) method is suitable. At present, the authors try to make the method for studying the large region structure in quantum system by utilizing the features of the TDHF phase space. The studies made so far are briefed. In this report, the correspondence of the large region patterns appearing in the band structure chart of three-level model with the periodic orbit group in the TDHF phase space is described. The Husimi function is made, and it possesses the information on the form of respective corresponding intrinsic state. The method of making the band structure chart is explained. There are three kinds of the tendency in the intrinsic state group. The E-T charts are made for the band structure charts to quantitatively express the large region tendency. The E-T chart and the T{sub r}-T chart are drawn for a selected characteristic orbit group. It became to be known that the large region properties of the quantum intrinsic state group of three-level model can be forecast by examining the properties of the periodic orbit group in the TDHF phase space. (K.I.)

  9. Phase transitions and steady-state microstructures in a two-temperature lattice-gas model with mobile active impurities

    Henriksen, Jonas Rosager; Sabra, Mads Christian; Mouritsen, Ole G.

    2000-01-01

    The nonequilibrium, steady-state phase transitions and the structure of the different phases of a two-dimensional system with two thermodynamic temperatures are studied via a simple lattice-gas model with mobile active impurities ("hot/cold spots'') whose activity is controlled by an external drive...... on the temperatures, microstructured phases of both lamellar and droplet symmetry arise, described by a length scale that is determined by the characteristic temperature controlling the diffusive motion of the active impurities....

  10. Gas phase absorption studies of photoactive yellow protein chromophore derivatives.

    Rocha-Rinza, Toms; Christiansen, Ove; Rajput, Jyoti; Gopalan, Aravind; Rahbek, Dennis B; Andersen, Lars H; Bochenkova, Anastasia V; Granovsky, Alexander A; Bravaya, Ksenia B; Nemukhin, Alexander V; Christiansen, Kasper Lincke; Nielsen, Mogens Brøndsted

    2009-08-27

    Photoabsorption spectra of deprotonated trans p-coumaric acid and two of its methyl substituted derivatives have been studied in gas phase both experimentally and theoretically. We have focused on the spectroscopic effect of the location of the two possible deprotonation sites on the trans p-coumaric acid which originate to either a phenoxide or a carboxylate. Surprisingly, the three chromophores were found to have the same absorption maximum at 430 nm, in spite of having different deprotonation positions. However, the absorption of the chromophore in polar solution is substantially different for the distinct deprotonation locations. We also report on the time scales and pathways of relaxation after photoexcitation for the three photoactive yellow protein chromophore derivatives. As a result of these experiments, we could detect the phenoxide isomer within the deprotonated trans p-coumaric acid in gas phase; however, the occurrence of the carboxylate is uncertain. Several computational methods were used simultaneously to provide insights and assistance in the interpretation of our experimental results. The calculated excitation energies S(0)-S(1) are in good agreement with experiment for those systems having a negative charge on a phenoxide moiety. Although our augmented multiconfigurational quasidegenerate perturbation theory calculations agree with experiment in the description of the absorption spectrum of anions with a carboxylate functional group, there are some puzzling disagreements between experiment and some calculational methods in the description of these systems.

  11. Surfactants from the gas phase may promote cloud droplet formation.

    Sareen, Neha; Schwier, Allison N; Lathem, Terry L; Nenes, Athanasios; McNeill, V Faye

    2013-02-19

    Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8-10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas-aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere.

  12. Exploring the Photoreduction of Au(III) Complexes in the Gas-Phase

    Marcum, Jesse C.; Kaufman, Sydney H.; Weber, J. Mathias

    2010-06-01

    We have used photodissociation spectroscopy to probe the electronic structure and photoreduction of Au(III) in gas-phase complexes containing Cl- and OH-. The gas-phase electronic spectrum of [AuCl_4]- closely resembles the aqueous solution spectrum, showing a lack of strong solvatochromic shifts. Substitution of Cl- ligands with OH- results in a strong blue shift, in agreement with ligand-field theory. Upon excitation, [AuCl_4]- can dissociate by loss of either one or two neutral Cl atoms, resulting in the reduction of gold from Au(III) to Au(II) and Au(I) respectively. The hydroxide substituted complex, [AuCl_2(OH)_2]-, demonstrates similar behavior but the only observable fragment channel is the loss of two neutral OH ligands, leading only to Au(I).

  13. Effect of geometric parameters of liquid-gas separator units on phase separation performance

    Mo, Songping; Chen, Xueqing; Chen, Ying [Guangdong University of Technology, Seoul (China); Yang, Zhen [Tsinghua University, Beijing (China)

    2015-07-15

    Five liquid-gas separator units were designed and constructed based on a new concept of a validated high-performance condenser. Each separator unit consists of two united T-junctions and an apertured baffle. The separator units have different header diameters or different baffles with different diameters of the liquid-gas separation hole. The phase separation characteristics of the units were investigated at inlet air superficial velocities from 1.0m/s to 33.0m/s and water superficial velocities from 0.0015 m/s to 0..50 m/s. The experimental results showed that the liquid height, liquid flow rate through the separation hole, and liquid separation efficiency increased with increased header diameter and decreased diameter of the separation hole. The geometric structures of the separator units affected the phase separation characteristics by influencing the liquid height in the header and the liquid flow rate through the separation hole.

  14. Photoelectron spectroscopy an introduction to ultraviolet photoelectron spectroscopy in the gas phase

    Eland, J H D

    2013-01-01

    Photoelectron Spectroscopy: An Introduction to Ultraviolet Photoelectronspectroscopy in the Gas Phase, Second Edition Photoelectron Spectroscopy: An Introduction to Ultraviolet PhotoelectronSpectroscopy in the Gas Phase, Second Edition aims to give practical approach on the subject of photoelectron spectroscopy, as well as provide knowledge on the interpretation of the photoelectron spectrum. The book covers topics such as the principles and literature of photoelectron microscopy; the main features and analysis of photoelectron spectra; ionization techniques; and energies from the photoelectron spectra. Also covered in the book are topics suc as photoelectron band structure and the applications of photoelectron spectroscopy in chemistry. The text is recommended for students and practitioners of chemistry who would like to be familiarized with the concepts of photoelectron spectroscopy and its importance in the field.

  15. Frequency metrology of a photomixing source for gas phase spectroscopy

    Hindle, Francis; Mouret, Gael; Yang, Chun; Cuisset, Arnaud; Bocquet, Robin; Lours, Michel; Rovera, Daniele

    2010-08-01

    The availability of frequency combs has opened new possibilities for the measurement of optical frequencies. Photomixing is an attractive solution for high resolution THz spectroscopy of gases due to the narrow spectral resolution and ability to access the 100 GHz to 3.5 THz range. One limitation of present photomixing spectrometers is the accuracy with which the THz frequency is established. Measurement of the centre frequency gas phase molecular transitions requires an accuracy better than 100 kHz in order to allow spectroscopic constants to be determined. Standard optical techniques like those employed in wavelength meters can only provide accuracies in the order of 50 MHz. We have used a turnkey fibre based frequency comb and a standard photomixing configuration to realize a THz synthesizer with an accuracy of around 50kHz. Two ECDLs used to pump the photomixer are phase locked onto the frequency comb and provide a tuning range of 10 MHz. In order to extend the tuning range an additional phase locked ECLD has been added to obtain a range in excess of 100 MHz. The absorption profiles of many Doppler limited transitions of carbonyl sulphide and formaldehyde have been measured to validate this instrument.

  16. Nucleation and dissociation of nano-particles in gas phase

    Feiden, P.

    2007-09-01

    This work deals with the study of nano-particles formation in gas phase and their dissociation pathways after an optical excitation. The clusters formation decomposes in two steps: a seed is formed (nucleation phase) and sticks atoms during its propagation in a sodium atomic vapor (growth phase). Those two steps have been observed separately for homogeneous Na n and heterogeneous Na n X particles (X = (NaOH) 2 or (Na 2 O) 2 ). The growth mechanism is well interpreted by a Monte Carlo simulation taking into account an accretion mechanism with hard-sphere cross section. The homogeneous nucleation mechanism has been highlighted by a direct comparison with the Classical Nucleation Theory predictions. The clusters fragmentation of ionic Na + (NaOH) p et Na + (NaF) p particles is studied in the second part. The way clusters fragment with size when they are excited optically is compared with theoretical previsions: this highlights the existence of an energetic barrier for special size of clusters. Finally, the fragmentation of doubly charged Na + Na + (NaOH) p clusters shows a competition between the fission into two single charged fragments and the unimolecular evaporation of a neutral fragment. (author)

  17. Phase transitions and structures of methylammonium compounds

    Yamamuro, Osamu; Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi; Kamiyama, Takashi; Asano, Hajime; Ibberson, R.M.; David, W.I.F.

    1993-01-01

    The structures of CD 3 ND 3 Cl, CD 3 ND 3 I, CD 3 ND 3 BF 4 , (CD 3 ND 3 ) 2 SnCl 6 , and CD 3 ND 3 SnBr 3 crystals were studied with time-of-flight type high-resolution powder diffractometers using spallation pulsed neutron sources. The orientations of the CD 3 ND 3 cations, including the positions of the D atoms, were determined at all the room temperature phases and at the low temperature phases of CD 3 ND 3 I and (CD 3N D 3 ) 2 SnCl 6 . The heat capacity experiments were also performed for both protonated and deuterated analogs of these compounds. From both structural and thermodynamic points of view, it was found that the transitions are mainly associated with the order-disorder change of the orientations of the CD 3 ND 3 cations. (author)

  18. Total energy calculations for structural phase transformations

    Ye, Y.Y.; Chan, C.T.; Ho, K.M.; Harmon, B.N.

    1990-01-01

    The structural integrity and physical properties of crystalline solids are frequently limited or enhanced by the occurrence of phase transformations. Martensitic transformations involve the collective displacement of atoms from one ordered state to another. Modern methods to determine the microscopic electronic changes as the atoms move are now accurate enough to evaluate the very small energy differences involved. Extensive first principles calculations for the prototypical martensitic transformation from body-centered cubic (bcc) to closepacked 9R structure in sodium metal are described. The minimum energy coordinate or configuration path between the bcc and 9R structures is determined as well as paths to other competing close-packed structures. The energy barriers and important anharmonic interactions are identified and general conclusions drawn. The calculational methods used to solve the Schrodinger equation include pseudopotentials, fast Fourier transforms, efficient matrix diagnonalization, and supercells with many atoms

  19. Conformational Study of DNA Sugars: from the Gas Phase to Solution

    Uriarte, Iciar; Vallejo-López, Montserrat; Cocinero, Emilio J.; Corzana, Francisco; Davis, Benjamin G.

    2017-06-01

    Sugars are versatile molecules that play a variety of roles in the organism. For example, they are important in energy storage processes or as structural scaffolds. Here, we focus on the monosaccharide present in DNA by addressing the conformational and puckering properties in the gas phase of α- and β-methyl-2-deoxy-ribofuranoside and α- and β-methyl-2-deoxy-ribopiranoside. Other sugars have been previously studied in the gas phase The work presented here stems from a combination of chemical synthesis, ultrafast vaporization methods, supersonic expansions, microwave spectroscopy (both chirped-pulsed and Balle-Flygare cavity-based spectrometers) and NMR spectroscopy. Previous studies in the gas phase had been performed on 2-deoxyribose, but only piranose forms were detected. However, thanks to the combination of these techniques, we have isolated and characterized for the first time the conformational landscape of the sugar present in DNA in its biologically relevant furanose form. Our gas phase study serves as a probe of the conformational preferences of these biomolecules under isolation conditions. Thanks to the NMR experiments, we can characterize the favored conformations in solution and extract the role of the solvent in the structure and puckering of the monosaccharides. E. J. Cocinero, A. Lesarri, P. Écija, F. J. Basterretxea, J.-U. Grabow, J. A. Fernández, F. Castaño, Angew. Chem. Int. Edit. 2012, 51, 3119. P. Écija, I. Uriarte, L. Spada, B. G. Davis, W. Caminati, F. J. Basterretxea, A. Lesarri, E. J. Cocinero, Chem. Commun. 2016, 52, 6241. I. Peña, E. J. Cocinero, C. Cabezas, A. Lesarri, S. Mata, P. Écija, A. M. Daly, Á. Cimas, C. Bermúdez, F. J. Basterretxea, S. Blanco, J. A. Fernández, J. C. López, F. Castaño, J. L. Alonso, Angew. Chem. Int. Edit. 2013, 52, 11840.

  20. Structural phase transitions in niobium oxide nanocrystals

    Yuvakkumar, R.; Hong, Sun Ig

    2015-09-01

    Niobium oxide nanocrystals were successfully synthesized employing the green synthesis method. Phase formation, microstructure and compositional properties of 1, 4 and 7 days incubation treated samples after calcinations at 450 °C were examined using X-ray diffraction, Raman, photoluminescence (PL), infrared, X-ray photoelectron spectra and transmission electron microscopic characterizations. It was observed that phase formation of Nb2O5 nanocrystals was dependent upon the incubation period required to form stable metal oxides. The characteristic results clearly revealed that with increasing incubation and aging, the transformation of cubic, orthorhombic and monoclinic phases were observed. The uniform heating at room temperature (32 °C) and the ligation of niobium atoms due to higher phenolic constituents of utilized rambutan during aging processing plays a vital role in structural phase transitions in niobium oxide nanocrystals. The defects over a period of incubation and the intensities of the PL spectra changing over a period of aging were related to the amount of the defects induced by the phase transition.

  1. Droplet model of pyrocarbon deposition from the gas phase. [HTGR

    Linke, J; Koizlik, K; Luhleich, H; Nickel, H

    1975-01-15

    Based on extensive earlier work a model has been developed to describe the formation of carbon by pyrolysis of gaseous hydrocarbons. One of the central statements of this model is the assumption of the existence of a quasi liquid carbon phase during deposition process.This model is described and is discussed as are the consequences for the material properties and structural parameters which arise from it. To review the droplet model, statically deposited pyrocarbon is examined by characterization methods suitable to analyze just these structural parameters.The results prove the model conceptions to be realistic.

  2. Regenerable Air Purification System for Gas-Phase Contaminant Control

    Constantinescu, Ileana C.; Finn, John E.; LeVan, M. Douglas; Lung, Bernadette (Technical Monitor)

    2000-01-01

    Tests of a pre-prototype regenerable air purification system (RAPS) that uses water vapor to displace adsorbed contaminants from an adsorbent column have been performed at NASA Ames Research Center. A unit based on this design can be used for removing trace gas-phase contaminants from spacecraft cabin air or from polluted process streams including incinerator exhaust. During the normal operation mode, contaminants are removed from the air on the column. Regeneration of the column is performed on-line. During regeneration, contaminants are displaced and destroyed inside the closed oxidation loop. In this presentation we discuss initial experimental results for the performance of RAPS in the removal and treatment of several important spacecraft contaminant species from air.

  3. Synthesis and Gas Phase Thermochemistry of Germanium-Containing Compounds

    Classen, Nathan Robert [Iowa State Univ., Ames, IA (United States)

    2002-01-01

    The driving force behind much of the work in this dissertation was to gain further understanding of the unique olefin to carbene isomerization observed in the thermolysis of 1,1-dimethyl-2-methylenesilacyclobutane by finding new examples of it in other silicon and germanium compounds. This lead to the examination of a novel phenylmethylenesilacyclobut-2-ene, which did not undergo olefin to carbene rearrangement. A synthetic route to methylenegermacyclobutanes was developed, but the methylenegermacyclobutane system exhibited kinetic instability, making the study of the system difficult. In any case the germanium system decomposed through a complex mechanism which may not include olefin to carbene isomerization. However, this work lead to the study of the gas phase thermochemistry of a series of dialkylgermylene precursors in order to better understand the mechanism of the thermal decomposition of dialkylgermylenes. The resulting dialkylgermylenes were found to undergo a reversible intramolecular β C-H insertion mechanism.

  4. Conformational Study of Taurine in the Gas Phase

    Cortijo, Vanessa; Sanz, M. Eugenia; López, Juan C.; Alonso, José L.

    2009-08-01

    The conformational preferences of the amino sulfonic acid taurine (NH2-CH2-CH2-SO3H) have been investigated in the gas phase by laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MB-FTMW) in the 6-14 GHz frequency range. One conformer has been observed, and its rotational, centrifugal distortion, and hyperfine quadrupole coupling constants have been determined from the analysis of its rotational spectrum. Comparison of the experimental constants with those calculated theoretically identifies the detected conformer unambiguously. The observed conformer of taurine is stabilized by an intramolecular hydrogen bond O-H···N between the hydrogen of the sulfonic acid group and the nitrogen atom of the amino group.

  5. Technical Procedures Management in Gas-Phase Detoxification Laboratory

    Cardona Garcia, A. I.; Sanchez Cabrero, B.

    2000-01-01

    The natural cycle of Volatile Organic Compounds (VOCs) has been disturbed by the industrial and socioeconomic activities of human beings. This imbalance in the environment has affected the ecosystems and the human health. Initiatives have been planned to mitigate these adverse effects. In order to minimize the hazardous effects, initiatives have been proposed for the treatment of gaseous emissions. The solar photo catalysis appears as a clear and renewable technology in front of the conventional ones.In CIEMAT this line is being investigated as the base of a future implementation at a pre industrial scale.Technical procedures are written in this document for testing Gas-Phase detoxification at lab scale in the Renewable Energy Department (DER) CIEMAT- Madrid to eliminate the VOCs by using the solar photo catalysis technology. (Author) 34 refs

  6. Gas-phase synthesis of magnetic metal/polymer nanocomposites

    Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

    2014-12-01

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  7. Gas-Phase Thermolysis of a Thioketen-S-Oxide

    Carlsen, Lars; Egsgaard, Helge; Schaumann, Ernst

    1980-01-01

    The unimolecular gas-phase thermolytic decomposition of 1,1,3,3-tetramethyl-2-thiocarbonylcyclohexane S-oxide (3) has been studied as a function of temperature by a flash vacuum thermolysis (f.v.t.) technique. The products detected are the carbenes (4) and (5), the ketone (6), the keten (7......), the thioketone (8), and the thioketen (9). The product ratio is highly dependent on the thermolysis temperature. The thermolysis of (3) is mechanistically rationalized by assuming the existence of only two concurrent primary processes, which are (a) extrusion of atomic oxygen, leading to the thioketen (9...... and CSO leading to the carbenes (5) and (4), respectively, are observed. Owing to an apparently very short half-life of the oxathiiran (10), only the decomposition products of the three-membered ring compound have been detected. These are the thioketone (8), formed by rearrangement of (10) into the α...

  8. Statistical Physics of Nanoparticles in the Gas Phase

    Hansen, Klavs

    2013-01-01

    Thermal processes are ubiquitous and an understanding of thermal phenomena is essential for a complete description of the physics of nanoparticles, both for the purpose of modeling the dynamics of the particles and for the correct interpretation of experimental data. This book has the twofold aim to present coherently the relevant results coming from the recent scientific literature and to guide the readers through the process of deriving results, enabling them to explore the limits of the mathematical approximations and test the power of the method. The book is focused on the fundamental properties of nanosystems in the gas phase. For this reason there is a strong emphasis on microcanonical physics. Each chapter is enriched with exercises and 3 Appendices provide additional useful materials.

  9. Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid.

    Roy, James W; Smith, James E

    2007-01-30

    Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.

  10. Precursor-Less Coating of Nanoparticles in the Gas Phase

    Tobias V. Pfeiffer

    2015-03-01

    Full Text Available This article introduces a continuous, gas-phase method for depositing thin metallic coatings onto (nanoparticles using a type of physical vapor deposition (PVD at ambient pressure and temperature. An aerosol of core particles is mixed with a metal vapor cloud formed by spark ablation by passing the aerosol through the spark zone using a hollow electrode configuration. The mixing process rapidly quenches the vapor, which condenses onto the core particles at a timescale of several tens of milliseconds in a manner that can be modeled as bimodal coagulation. Gold was deposited onto core nanoparticles consisting of silver or polystyrene latex, and silver was deposited onto gold nanoparticles. The coating morphology depends on the relative surface energies of the core and coating materials, similar to the growth mechanisms known for thin films: a coating made of a substance having a high surface energy typically results in a patchy coverage, while a coating material with a low surface energy will normally “wet” the surface of a core particle. The coated particles remain gas-borne, allowing further processing.

  11. Effect of biochar on soil structural characteristics: water retention and gas transport

    Sun, Zhencai; Møldrup, Per; Vendelboe, Anders Lindblad

    Biochar addition to agricultural soil has been reported to reduce climate gas emission, as well as improve soil fertility and crop productivity. Little, however, is known about biochar effects on soil structural characteristics. This study investigates if biochar-application changes soil structural...... characteristics, as indicated from water retention and gas transport measurements on intact soil samples. Soil was sampled from a field experiment on a sandy loam with four control plots (C) without biochar and four plots (B) with incorporated biochar at a rate of 20 tons per hectare (plot size, 6 x 8 m). The C......-gas diffusivity on intact 100cm3 soil samples (5 replicates in each plot). We found that biochar application significantly decreased soil bulk density, hereby creating higher porosity. At the same soil-water matric potential, all the soil-gas phase parameters (air-filled porosity, air permeability and gas...

  12. Phase compensated gas turbine governor for damping oscillatory modes

    Yee, S.K. [Siemens Transmission and Distribution Limited, Manchester (United Kingdom); Milanovic, J.V. [School of Electrical and Electronic Engineering, University of Manchester, PO Box 88, Manchester M60 1 QD (United Kingdom); Hughes, F.M. [Manchester (United Kingdom)

    2009-08-15

    With market deregulation, there is constant pressure to utilise existing assets in more effective ways in order to achieve high levels of performance and as governor technologies mature the ability of governors to achieve much more than the standard power-frequency regulation function increases. Thus, this paper has focused on a more active use of governor control for a gas turbine to provide improved system stabilisation and performance via the inclusion of phase compensation in the governor control loop. Due to the decoupled nature of the mechanical power and excitation control loops, performance improvement via governor control does not interfere with generator voltage regulation, which is a drawback of conventional generator damping provision via a power system stabiliser (PSS). In addition, the mechanical power control loop is also less affected by the operating condition of the power system and is hence more robust. It is shown that inclusion of appropriate phase compensation in the governor control loop can improve dynamic and transient stability, either alone or in conjunction with a PSS in the exciter control loop, without adversely interfering with voltage control or changing steady state power-frequency regulation. (author)

  13. Phase structure of strongly correlated Fermi gases

    Roscher, Dietrich

    2015-01-01

    Strongly correlated fermionic many-body systems are ubiquitous in nature. Their theoretical description poses challenging problems which are further complicated when imbalances in, e.g., the particle numbers of the involved species or their masses are introduced. In this thesis, a number of different approaches is developed and applied in order to obtain predictions for physical observables of such systems that mutually support and confirm each other. In a first step, analytically well-founded mean-field analyses are carried through. One- and three-dimensional ultracold Fermi gases with spin and mass imbalance as well as Gross-Neveu and NJL-type relativistic models at finite baryon chemical potential are investigated with respect to their analytic properties in general and the occurrence of spontaneous breaking of translational invariance in particular. Based on these studies, further methods are devised or adapted allowing for investigations also beyond the mean-field approximation. Lattice Monte Carlo simulations with imaginary imbalance parameters are employed to surmount the infamous sign problem and compute the equation of state of the respective unitary Fermi gases. Moreover, in-medium two-body analyses are used to confirm and explain the characteristics of inhomogeneously ordered phases. Finally, functional RG methods are applied to the unitary Fermi gas with spin and mass imbalance. Besides quantitatively competitive predictions for critical temperatures for the superfluid state, strong hints on the stability of inhomogeneous phases with respect to order parameter fluctuations in the regime of large mass imbalance are obtained. Combining the findings from these different theoretical studies suggests the possibility to find such phases in experiments presently in preparation.

  14. Electron-beam synthesis of fuel in the gas phase

    Ponomarev, A.V.; Holodkova, E.M.; Ershov, B.G.

    2011-01-01

    Complete text of publication follows. Tendencies of world development focus attention on a vegetative biomass as on the major raw resource for future chemistry and a fuel industry. The significant potential for perfection of biomass conversion processes is concentrated in the field of radiation-chemical methods. Both the mode of post-radiation distillation and mode of electron-beam distillation of biomass have been investigated as well as the mode of gas-phase synthesis of liquid engine fuel from of biomass distillation products. Synergistic action of radiation and temperature has been analyzed at use of the accelerated electron beams allowing to combine radiolysis with effective radiation heating of a material without use of additional heaters. At dose rate above 1 kGy/s the electron-beam irradiation results in intensive decomposition of a biomass and evaporation of formed fragments with obtaining of a liquid condensate (∼ 60 wt%), CO 2 and Co gases (13-18 wt%) and charcoal in the residue. Biomass distillation at radiation heating allows to increase almost three times an organic liquid yield in comparison with pyrolysis. The majority of liquid products from cellulose is represented by the furan derivatives considered among the very perspective components for alternative engine fuels. Distilled-off gases and vapors are diluted with gaseous C 1 -C 5 alkanes and again are exposed to an irradiation to produce liquid fuel from a biomass. This transformation is based on a method of electron-beam circulation conversion of gaseous C 1 -C 5 alkanes (Ponomarev, A.V., Radiat. Phys. Chem., 78, 48, 2009) which consists in formation and removal of liquid products with high degree of carbon skeleton branching. The isomers ratio in a liquid may be controlled by means of change of an irradiation condition and initial gas composition. The irradiation of gaseous alkanes together with vaporous products of biomass destruction allows to synthesize the fuel enriched by conventional

  15. Gas-phase Crystallization of Titanium Dioxide Nanoparticles

    Ahonen, P.P.; Moisala, A.; Tapper, U.; Brown, D.P.; Jokiniemi, J.K.; Kauppinen, E.I.

    2002-01-01

    We have investigated the development of crystal morphology and phase in ultrafine titanium dioxide particles. The particles were produced by a droplet-to-particle method starting from propanolic titanium tetraisopropoxide solution, and calcined in a vertical aerosol reactor in air. Mobility size classified 40-nm diameter particles were conveyed to the aerosol reactor to investigate particle size changes at 20-1200 deg. C with 5-1-s residence time. In addition, polydisperse particles were used to study morphology and phase formation by electron microscopy. According to differential mobility analysis, the particle diameter was reduced to 21-23-nm at 600 deg. C and above. Precursor decomposition occurred between 20 deg. C and 500 deg. C. The increased mobility particle size at 700 deg. C and above was observed to coincide with irregular particles at 700 deg. C and 800 deg. C and faceted particles between 900 deg. C and 1200 deg. C, according to transmission electron microscopy. The faceted anatase particles were observed to approach a minimized surface energy by forming {101} and {001} crystallographic surfaces. Anatase phase was observed at 500-1200 deg. C and above 600 deg. C the particles were single crystals. Indications of minor rutile formation were observed at 1200 deg. C. The relatively stable anatase phase vs. temperature is attributed to the defect free structure of the observed particles and a lack of crystal-crystal attachment points

  16. All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

    Lausund, Kristian Blindheim; Nilsen, Ola

    2016-11-01

    Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic-inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios.

  17. Possibilities of gas-phase radio-chromatography application to permanent-gas analysis

    Dupuis, M.C.; Charrier, G.; Alba, C.; Massimino, D.

    1970-01-01

    The gas-phase radio-chromatography technique has been applied to the rapid analysis of permanent gases (H 2 , O 2 , N 2 , A, Kr, Xe, CO, CH 4 ) labelled with radioactive indicators ( 3 H, 37 A, 85 Kr, 133 Xe). After calibration, the components of such a mixture can be identified and their concentrations measured in less than two hours, using a sample volume of from 0.1 to 10 cm 3 . The minimum detectable activity is of the order of 10 -4 μC for each radioactive isotope. The measurements are reproducible to about 2 to 3 per cent. This work has been mainly concerned with the influence of parameters affecting the response of the radioactivity detector (ionization chamber or gas flow proportional counter). The method has very numerous applications both theoretically, for the study of chromatographic phenomena under ideal conditions (infinitesimal concentrations made possible by the use of radioactive tracers), and practically, for rapid and accurate radiochemical analysis of radioactive gas mixtures. (authors) [fr

  18. Gas Phase Chromatography of some Group 4, 5, and 6 Halides

    Sylwester, Eric Robert [Univ. of California, Berkeley, CA (United States)

    1998-10-01

    Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr4, HfBr4, RfBr4, NbBr5, TaOBr3, HaCl5, WBr6, FrBr, and BiBr3. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography. Adsorption Enthalpy (ΔHa) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔHa was observed: RfBr4 > ZrBr4 > HfBr4. The ΔHa values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of 261Rf was performed. 261Rf was produced via the 248Cm(18O, 5n) reaction and observed with a half-life of 74-6+7 seconds, in excellent agreement with the previous measurement of 78-6+11 seconds. We recommend a new half-life of 75±7 seconds for 261Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant

  19. About the dynamics of structural phase transitions

    Medeiros, J.T.N.

    1975-01-01

    The dynamics of structural phase transitions with a fourth order interaction between the soft phonon fields is studied in the 1/n approximation, using many body methods at finite temperatures. Two limits are considered: high transition temperature T sub(c) (classical limit) and T sub(c) = 0 (quantum limit). The dynamical contribution to the critical coefficient eta of the correlation function is calculated in these limits. It is found that there is no dynamical contribution to eta in the classical limit, whereas in the quantum limit eta is non-zero only for dimensions of the system d [pt

  20. Online Measurements of Highly Oxidized Organics in the Gas and Particle phase during SOAS and SENEX

    Lopez-Hilfiker, F.; Lee, B. H.; Mohr, C.; Ehn, M.; Rubach, F.; Mentel, T. F.; Kleist, E.; Thornton, J. A.

    2014-12-01

    We present measurements of a large suite of gas and particle phase organic compounds made with a Filter Inlet for Gas and AEROsol (FIGAERO) coupled to a high resolution time of flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington and with airborne HR-ToF-CIMS measurements. The FIGAERO instrument was deployed on the Jülich Plant Atmosphere Chamber to study α-pinene oxidation, and subsequently at the SMEAR II forest station in Hyytiälä, Finland and the SOAS ground site, in Brent Alabama. During the Southern Atmosphere Study, a gas-phase only version of the HR-ToF-CIMS was deployed on the NOAA WP-3 aircraft as part of SENEX. We focus here on highly oxygenated organic compounds derived from monoterpene oxidation detected both aloft during SENEX and at the ground-based site during SOAS. In both chamber and the atmosphere, many highly oxidized, low volatility compounds were observed in the gas and particles and many of the same compositions detected in the gas-phase were detected in the particles upon temperature programmed thermal desorption. The fraction of a given compound measured in the particle phase follows expected trends with elemental composition such as O/C ratios, but many compounds would not be well described by an absorptive partitioning model assuming unity activity coefficients. The detailed structure in the thermograms reveals a significant contribution from large molecular weight organics and/or oligomers in both chamber and ambient aerosol samples. Approximately 50% of the measured organics in the particle phase are associated with compounds having effective vapour pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. We discuss the implications of these findings for measurements of gas-particle partitioning and for evaluating the contribution of monoterpene oxidation to organic aerosol formation and growth. We also use the aircraft measurements and a

  1. Structural arrest in an ideal gas

    Ketel, W. van; Das, C.; Frenkel, D.

    2005-01-01

    We report a molecular dynamics study of a simple model system that has the static properties of an ideal gas, yet exhibits nontrivial "glassy" dynamics behavior at high densities. The constituent molecules of this system are constructs of three infinitely thin hard rods of length L, rigidly joined

  2. New structures in the European gas market

    Tangen, Kristian

    1997-01-01

    The aim of this study is to provide a background for assessing elements of change in the European gas market that in the long run may produce new framework conditions for Norwegian gas exports. It will also serve as an empirical basis for further studies. The main question is: What can the extension of the pipeline network and the growing number of actors tell us about future competition in spite of the fact that both Russia, Algeria and Norway have non-contracted capacity in the pipelines they are building. A number of uncertainties make it hard to draw any clear conclusions about a totally different competitive situation than only a few years ago. In the Netherlands groups of former distribution companies are threatening Gasunies' monopoly while Ruhrgas' attempt to expand into Austria may lead to gas to gas competition there. Signs of a similar development are seen in Italy and Spain as well. Increasing competition can be explained partly by the growing number of actors downstream in the gas market - in trade, transmission and among the large consumers, the electricity producers, the consequence of direct volumes and of shorter duration which in itself promotes competition. Several large pipeline projects have been carried through in co-operation between several actors which indicates that new types of projects are being developed in order to reduce risks for each actor. These will be easier to realise in the absence of long-term ''take-or-pay'' contracts at company level, what we may call companies rhetoric and argumentation as a result of comprehensive market positioning. Furthermore it seems likely that a kind of spot market will develop. Even if we can expect that only small volumes will be traded through this channel at first. Such a development may have considerable influence on prices in the long run. 5 tabs, 29 refs

  3. Soft modes and structural phase transitions

    Venkataraman, G [Reactor Research Centre, Kalpakkam (India)

    1979-12-01

    A survey of soft modes and their relationship to structural phase transitions is presented. After introducing the concept of a soft mode, the origin of softening is considered from a lattice-dynamical point. The Landau theory approach to structural transitions is then discussed, followed by a generalisation of the soft-mode concept through the use of the dynamic order-parameter susceptibility. The relationship of soft modes to broken symmetry is also examined. Experimental results for several classes of crystals are next presented, bringing out various features such as the co-operative Jahn-Teller effect. The survey concludes with a discussion of the central peak, touching upon both the experimental results and the theoretical speculations.

  4. Heat transfer characteristics of liquid-gas Taylor flows incorporating microencapsulated phase change materials

    Howard, J A; Walsh, P A

    2014-01-01

    This paper presents an investigation on the heat transfer characteristics associated with liquid-gas Taylor flows in mini channels incorporating microencapsulated phase change materials (MPCM). Taylor flows have been shown to result in heat transfer enhancements due to the fluid recirculation experienced within liquid slugs which is attributable to the alternating liquid slug and gas bubble flow structure. Microencapsulated phase change materials (MPCM) also offer significant potential with increased thermal capacity due to the latent heat required to cause phase change. The primary aim of this work was to examine the overall heat transfer potential associated with combining these two novel liquid cooling technologies. By investigating the local heat transfer characteristics, the augmentation/degradation over single phase liquid cooling was quantified while examining the effects of dimensionless variables, including Reynolds number, liquid slug length and gas void fraction. An experimental test facility was developed which had a heated test section and allowed MPCM-air Taylor flows to be subjected to a constant heat flux boundary condition. Infrared thermography was used to record high resolution experimental wall temperature measurements and determine local heat transfer coefficients from the thermal entrance point. 30.2% mass particle concentration of the MPCM suspension fluid was examined as it provided the maximum latent heat for absorption. Results demonstrate a significant reduction in experimental wall temperatures associated with MPCM-air Taylor flows when compared with the Graetz solution for conventional single phase coolants. Total enhancement in the thermally developed region is observed to be a combination of the individual contributions due to recirculation within the liquid slugs and also absorption of latent heat. Overall, the study highlights the potential heat transfer enhancements that are attainable within heat exchange devices employing MPCM

  5. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both

  6. Evidence for α-helices in the gas phase: a case study using Melittin from honey bee venom.

    Florance, Hannah V; Stopford, Andrew P; Kalapothakis, Jason M; McCullough, Bryan J; Bretherick, Andrew; Barran, Perdita E

    2011-09-07

    Gas phase methodologies are increasingly used to study the structure of proteins and peptides. A challenge to the mass spectrometrist is to preserve the structure of the system of interest intact and unaltered from solution into the gas phase. Small peptides are very flexible and can present a number of conformations in solution. In this work we examine Melittin a 26 amino acid peptide that forms the active component of honey bee venom. Melittin is haemolytic and has been shown to form an α-helical tetrameric structure by X-ray crystallography [M. Gribskov et al., The RCSB Protein Data Bank, 1990] and to be helical in high concentrations of methanol. Here we use ion mobility mass spectrometry, molecular dynamics and gas-phase HDX to probe its structure in the gas phase and specifically interrogate whether the helical form can be preserved. All low energy calculated structures possess some helicity. In our experiments we examine the peptide following nano-ESI from solutions with varying methanol content. Ion mobility gives collision cross sections (CCS) that compare well with values found from molecular modelling and from other reported structures, but with inconclusive results regarding the effect of solvent. There is only a slight increase in CCS with charge, showing minimal coloumbically driven unfolding. HDX supports preservation of some helical content into the gas phase and again shows little difference in the exchange rates of species sprayed from different solvents. The [M + 3H](3+) species has two exchanging populations both of which exhibit faster exchange rates than observed for the [M + 2H](2+) species. One interpretation for these results is that the time spent being analysed is sufficient for this peptide to form a helix in the 'ultimate' hydrophobic environment of a vacuum.

  7. Structure analysis of turbulent liquid phase by POD and LSE techniques

    Munir, S., E-mail: shahzad-munir@comsats.edu.pk; Muthuvalu, M. S.; Siddiqui, M. I. [Department of Fundamental and Applied Science, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak Darul Ridzuan (Malaysia); Heikal, M. R., E-mail: morgan.heikal@petronas.com.my; Aziz, A. Rashid A., E-mail: morgan.heikal@petronas.com.my [Department of Mechanical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak Darul Ridzuan (Malaysia)

    2014-10-24

    In this paper, vortical structures and turbulence characteristics of liquid phase in both single liquid phase and two-phase slug flow in pipes were studied. Two dimensional velocity vector fields of liquid phase were obtained by Particle image velocimetry (PIV). Two cases were considered one single phase liquid flow at 80 l/m and second slug flow by introducing gas at 60 l/m while keeping liquid flow rate same. Proper orthogonal decomposition (POD) and Linear stochastic estimation techniques were used for the extraction of coherent structures and analysis of turbulence in liquid phase for both cases. POD has successfully revealed large energy containing structures. The time dependent POD spatial mode coefficients oscillate with high frequency for high mode numbers. The energy distribution of spatial modes was also achieved. LSE has pointed out the coherent structured for both cases and the reconstructed velocity fields are in well agreement with the instantaneous velocity fields.

  8. Structure analysis of turbulent liquid phase by POD and LSE techniques

    Munir, S.; Muthuvalu, M. S.; Siddiqui, M. I.; Heikal, M. R.; Aziz, A. Rashid A.

    2014-01-01

    In this paper, vortical structures and turbulence characteristics of liquid phase in both single liquid phase and two-phase slug flow in pipes were studied. Two dimensional velocity vector fields of liquid phase were obtained by Particle image velocimetry (PIV). Two cases were considered one single phase liquid flow at 80 l/m and second slug flow by introducing gas at 60 l/m while keeping liquid flow rate same. Proper orthogonal decomposition (POD) and Linear stochastic estimation techniques were used for the extraction of coherent structures and analysis of turbulence in liquid phase for both cases. POD has successfully revealed large energy containing structures. The time dependent POD spatial mode coefficients oscillate with high frequency for high mode numbers. The energy distribution of spatial modes was also achieved. LSE has pointed out the coherent structured for both cases and the reconstructed velocity fields are in well agreement with the instantaneous velocity fields

  9. Thin film structures and phase stability

    Clemens, B.M.; Johnson, W.L.

    1990-01-01

    This was a two day symposium, with invited and contributed papers as well as an evening poster session. The first day concentrated on solid state reactions with invited talks by Lindsay Greer from the University of Cambridge, King Tu from IBM Yorktown Heights, and Carl Thompson from MIT. Professor Greer observed that the diffusion of Zr is 10 6 times slower than that of Ni in amorphous NiZr, confirming that Ni is the mobile species in solid state amorphization. King Tu explained the formation of metastable phases in this film diffusion couples by the concept of maximum rate of free energy change. Carl Thompson discussed the formation of amorphous phases in metal silicon systems, and discussed a two stage nucleation and growth process. The contributed papers also generated discussion on topics such as phase segregation, amorphous silicide formation, room temperature oxidation of silicon, and nucleation during ion beam irradiation. There was a lively poster session on Monday evening with papers on a wide variety of topics covering the general area of thin film science. The second day had sessions Epitaxy and Multilayer Structure I and II, with the morning focussing on epitaxial and heteroepitaxial growth of thin films. Robin Farrow of IBM Almaden led off with an invited talk where he reported on some remarkable success he and his co-workers have had in growing single crystal epitaxial thin films and superlattices of silver, iron, cobalt and platinum on GaAs. This was followed by several talks on epitaxial growth and characterization. The afternoon focused on interfaces and structure of multilayered materials. A session on possible stress origins of the supermodulus effect was highlighted by lively interaction from the audience. Most of the papers presented at the symposium are presented in this book

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

    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.

  11. Thiobenzamide: Structure of a free molecule as studied by gas electron diffraction and quantum chemical calculations

    Kolesnikova, Inna N.; Putkov, Andrei E.; Rykov, Anatolii N.; Shishkov, Igor F.

    2018-06-01

    The equilibrium (re) molecular structure of thiobenzamide along with rh1 structure has been determined in gas phase using gas electron-diffraction (GED) at about 127 °C and quantum-chemical calculations (QC). Rovibrational distance corrections to the thermal averaged GED structure have been computed with anharmonic force constants obtained at the MP2/cc-pVTZ level of theory. According to the results of GED and QC thiobenzamide exists as mixture of two non-planar enantiomers of C1 symmetry. The selected equilibrium geometrical parameters of thiobenzamide (re, Å and ∠e, deg) are the following: (Cdbnd S) = 1.641(4), (Csbnd N) = 1.352(2), (Csbnd C) = 1.478(9), (Cdbnd C)av = 1.395(2), CCN = 114.7(5), CCS = 123.4(5), C2C1C7S = 31(4), C6C1C7N = 29(4). The structure of thiobenzamide in the gas phase is markedly different to that in the literature for the single crystal. The differences between the gas and the solid structures are ascribed to the presence of intermolecular hydrogen bonding in the solid phase.

  12. Uptake of Organic Gas Phase Species by 1-Methylnaphthalene

    Zhang, H.; Xia, J.; Davidovits, P.; Jayne, J. T.; Kolb, C. E.; Worsnop, D. R.

    2002-12-01

    Using a droplet train apparatus, the mass accommodation coefficients (α) on 1-methylnapthalene of gas phase m-xylene, ethylbenzene, butylbenzene, α-pinene, γ-terpinene, and 2-methyl-2-hexanol were measured as a function of temperature (265 K to 296 K). 1-methylnapthalene was selected as a surrogate for hydrophobic and aromatic hydrocarbons found in tropospheric aerosols. The mass accommodation coefficients (α) of all the molecules obtained from these measurements exhibit negative temperature dependence. The upper and lower values of α at 265 K and 296 K respectively are: for m-xylene 0.44 and 0.26; for ethylbenzene 0.37 and 0.22; for butylbenzene 0.47 and 0.31; for α-pinene 0.47 and 0.096; for γ-terpinene 0.39 and 0.12; for 2-methyl-2-hexanol 0.44 and 0.26. The uptake measurements also yielded values for the product HDl1/2 for most of the molecules studied (H = Henry's law constant, Dl = liquid phase diffusion coefficient). Using calculated values of Dl the Henry's law constant is obtained, and expressed in the form ln H (M/atm) = -A + B/T. The A and B values for the molecules studied are listed in Table 1. Table 1: A and B values for the Henry's law constant H expressed as ln H (M/atm) = -A + B/T \\ m-xylene: A=7.20, B=4060\\ethylbenzene: A=5.81, B=3660\\butylbenzene: A=16.95, B=7330α-pinene: A=15.69, B=6360\\2-methyl-2-hexanol: A=9.95, B=4760

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

    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

  14. Shape Memory Alloy-Based Periodic Cellular Structures, Phase I

    National Aeronautics and Space Administration — This SBIR Phase I effort will develop and demonstrate an innovative shape memory alloy (SMA) periodic cellular structural technology. Periodic cellular structures...

  15. Molecular structure of tetramethylgermane from gas electron diffraction

    Csákvári, Éva; Rozsondai, Béla; Hargittai, István

    1991-05-01

    The molecular structure of Ge(CH 3) 4 has been determined from gas-phase electron diffraction augmented by a normal coordinate analysis. Assuming tetrahedral symmetry for the germanium bond configuration, the following structural parameters are found: rg(GeC) = 1.958 ± 0.004 Å, rg(CH) = 1.111 ± 0.003 Å and ∠(GeCH) = 110.7 ± 0.2° ( R=4.0%). The methyl torsional barrier V 0 is estimated to be 1.3 kJ mol -1 on the basis of an effective angle of torsion 23.0 ± 1.5°, from the staggered form, yielded directly by the analysis. The GeC bond length of Ge(CH 3) 4 is the same, within experimental error, as that of Ge(C 6H 5) 4 and is in agreement with the prediction of a modified Schomaker-Stevenson relationship.

  16. Numerical simulation for gas-liquid two-phase flow in pipe networks

    Li Xiaoyan; Kuang Bo; Zhou Guoliang; Xu Jijun

    1998-01-01

    The complex pipe network characters can not directly presented in single phase flow, gas-liquid two phase flow pressure drop and void rate change model. Apply fluid network theory and computer numerical simulation technology to phase flow pipe networks carried out simulate and compute. Simulate result shows that flow resistance distribution is non-linear in two phase pipe network

  17. New structural changes in Kazakhstan petroleum and gas industry management

    Nadirov, N.K.; Konaev, Eh.N.

    1998-01-01

    The basic stags of structural changes in Kazakhstan petroleum and gas industry management are considered. It is shown, that in new economic situation the traditional branch scheme of management became out date and does not meet demands up the times. The spent structural changes in petroleum and gas industry management will promote to strengthening of strategic role of hydrocarbon raw material production and processing in prospect. (author)

  18. GAS-PHASE CHEMISTRY OF THE CYANATE ION, OCN−

    Cole, Callie A.; Wang, Zhe-Chen; Bierbaum, Veronica M.; Snow, Theodore P.

    2015-01-01

    Cyanate (OCN − ) is the only ion to date whose presence has been confirmed in the icy mantles that coat interstellar dust grains. Understanding the chemical behavior of cyanate at a fundamental level is therefore integral to the advancement of astrochemistry. We seek to unravel the chemistry of this intriguing anion through a combination of gas-phase experiments and theoretical explorations. Our approach is twofold: first, employing a flowing afterglow-selected ion flow tube apparatus, the reactions between OCN − and three of the most abundant atomic species in the interstellar medium, hydrogen, nitrogen, and oxygen, are examined. Hydrogen atoms readily react by associative detachment, but the remarkable stability of OCN − does not give rise to an observable reaction with either nitrogen or oxygen atoms. To explain these results, the potential energy surfaces of several reactions are investigated at the B3LYP/6-311++G(d,p) level of theory. Second, collision induced dissociation experiments involving deprotonated uracil, thymine, and cytosine in an ion trap mass spectrometer reveal an interesting connection between these pyrimidine nucleobase anions and OCN − . Theoretical calculations at the B3LYP/6-311++G(d,p) level of theory are performed to delineate the mechanisms of dissociation and explore the possible role of OCN − as a biomolecule precursor

  19. Gas phase reactions of nitrogen oxides with olefins

    Altshuller, A P; Cohen, I

    1961-01-01

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

  20. Nanocrystalline AL2 O2 powders produced by laser induced gas phase reactions

    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

  1. Entropy feature extraction on flow pattern of gas/liquid two-phase flow based on cross-section measurement

    Han, J; Dong, F; Xu, Y Y

    2009-01-01

    This paper introduces the fundamental of cross-section measurement system based on Electrical Resistance Tomography (ERT). The measured data of four flow regimes of the gas/liquid two-phase flow in horizontal pipe flow are obtained by an ERT system. For the measured data, five entropies are extracted to analyze the experimental data according to the different flow regimes, and the analysis method is examined and compared in three different perspectives. The results indicate that three different perspectives of entropy-based feature extraction are sensitive to the flow pattern transition in gas/liquid two-phase flow. By analyzing the results of three different perspectives with the changes of gas/liquid two-phase flow parameters, the dynamic structures of gas/liquid two-phase flow is obtained, and they also provide an efficient supplementary to reveal the flow pattern transition mechanism of gas/liquid two-phase flow. Comparison of the three different methods of feature extraction shows that the appropriate entropy should be used for the identification and prediction of flow regimes.

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

    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

  3. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    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.

  4. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    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.

  5. Homolytic iodination and nitration of some benzene derivatives in the gas phase

    Vonk, W.F.M.

    1980-01-01

    Two gas phase reactions, involving the iodination and nitration of benzene derivatives, are described. The experimental techniques of the apparatus and the methods used are outlined. The kinetic H/D isotope effect in the gas phase nitration of benzene with NO 2 is determined. (C.F.)

  6. Structure dynamics. Determination of the coupled relationships in solid-fluid-gas dynamics

    Hofmann, H.; Huber, A.; Naehring, T.; Bonakdarzadeh, S.; Faass, E.; Gaschen, J.P.; Kniffka, K.; Pilz, H.

    1980-06-01

    In the present paper the code concept SAN (Structure ANalysis) is presented. SAN is designed according to the modular principle using describing and coordinating modules. SAN is based on the discreetizing method. It uses compatible forms of description. The method of finite elements is applied. Solid-fluid-gas structures may be described as well as their interrelations in the linear and nonlinear region, including phase transitions with the associated descriptions of material and state. (orig./RW) [de

  7. Delivering Transmembrane Peptide Complexes to the Gas Phase Using Nanodiscs and Electrospray Ionization

    Li, Jun; Richards, Michele R.; Kitova, Elena N.; Klassen, John S.

    2017-10-01

    The gas-phase conformations of dimers of the channel-forming membrane peptide gramicidin A (GA), produced from isobutanol or aqueous solutions of GA-containing nanodiscs (NDs), are investigated using electrospray ionization-ion mobility separation-mass spectrometry (ESI-IMS-MS) and molecular dynamics (MD) simulations. The IMS arrival times measured for (2GA + 2Na)2+ ions from isobutanol reveal three different conformations, with collision cross-sections (Ω) of 683 Å2 (conformation 1, C1), 708 Å2 (C2), and 737 Å2 (C3). The addition of NH4CH3CO2 produced (2GA + 2Na)2+ and (2GA + H + Na)2+ ions, with Ω similar to those of C1, C2, and C3, as well as (2GA + 2H)2+, (2GA + 2NH4)2+, and (2GA + H + NH4)2+ ions, which adopt a single conformation with a Ω similar to that of C2. These results suggest that the nature of the charging agents, imparted by the ESI process, can influence dimer conformation in the gas phase. Notably, the POPC NDs produced exclusively (2GA + 2NH4)2+ dimer ions; the DMPC NDs produced both (2GA + 2H)2+ and (2GA + 2NH4)2+ dimer ions. While the Ω of (2GA + 2H)2+ is similar to that of C2, the (2GA + 2NH4)2+ ions from NDs adopt a more compact structure, with a Ω of 656 Å2. It is proposed that this compact structure corresponds to the ion conducting single stranded head-to-head helical GA dimer. These findings highlight the potential of NDs, combined with ESI, for transferring transmembrane peptide complexes directly from lipid bilayers to the gas phase. [Figure not available: see fulltext.

  8. Molecular structure of the lecithin ripple phase

    de Vries, Alex H.; Yefimov, Serge; Mark, Alan E.; Marrink, Siewert J.

    2005-04-01

    Molecular dynamics simulations of lecithin lipid bilayers in water as they are cooled from the liquid crystalline phase show the spontaneous formation of rippled bilayers. The ripple consists of two domains of different length and orientation, connected by a kink. The organization of the lipids in one domain of the ripple is found to be that of a splayed gel; in the other domain the lipids are gel-like and fully interdigitated. In the concave part of the kink region between the domains the lipids are disordered. The results are consistent with the experimental information available and provide an atomic-level model that may be tested by further experiments. molecular dynamics simulation | structural model

  9. Importance of the gas phase role to the prediction of energetic material behavior: An experimental study

    Ali, A.N.; Son, S.F.; Asay, B.W.; Sander, R.K.

    2005-01-01

    Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6 mm±0.4 mm exists below which ignition by CO 2 laser is not possible at the tested irradiances of 29 W/cm 2 and 38 W/cm 2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials

  10. Importance of the gas phase role to the prediction of energetic material behavior: An experimental study

    Ali, A. N.; Son, S. F.; Asay, B. W.; Sander, R. K.

    2005-03-01

    Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6mm±0.4mm exists below which ignition by CO2 laser is not possible at the tested irradiances of 29W /cm2 and 38W/cm2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials.

  11. Gas holdup in a reciprocating plate bioreactor: Non-Newtonian - liquid phase

    Naseva Olivera S.

    2002-01-01

    Full Text Available The gas holdup was studied in non-newtonian liquids in a gas-liquid and gas-liquid-solid reciprocating plate bioreactor. Aqueous solutions of carboxy methyl cellulose (CMC; Lucel, Lučane, Yugoslavia of different degrees of polymerization (PP 200 and PP 1000 and concentration (0,5 and 1%, polypropylene spheres (diameter 8.3 mm; fraction of spheres: 3.8 and 6.6% by volume and air were used as the liquid, solid and gas phase. The gas holdup was found to be dependent on the vibration rate, the superficial gas velocity, volume fraction of solid particles and Theological properties of the liquid ohase. Both in the gas-liquid and gas-liquid-solid systems studied, the gas holdup increased with increasing vibration rate and gas flow rate. The gas holdup was higher in three-phase systems than in two-phase ones under otter operating conditions being the same. Generally the gas holdup increased with increasing the volume fraction of solid particles, due to the dispersion action of the solid particles, and decreased with increasing non-Newtonian behaviour (decreasing flow index i.e. with increasing degree of polymerization and solution concentration of CMC applied, as a result of gas bubble coalescence.

  12. Nonlinear analysis of gas-water/oil-water two-phase flow in complex networks

    Gao, Zhong-Ke; Wang, Wen-Xu

    2014-01-01

    Understanding the dynamics of multi-phase flows has been a challenge in the fields of nonlinear dynamics and fluid mechanics. This chapter reviews our work on two-phase flow dynamics in combination with complex network theory. We systematically carried out gas-water/oil-water two-phase flow experiments for measuring the time series of flow signals which is studied in terms of the mapping from time series to complex networks. Three network mapping methods were proposed for the analysis and identification of flow patterns, i.e. Flow Pattern Complex Network (FPCN), Fluid Dynamic Complex Network (FDCN) and Fluid Structure Complex Network (FSCN). Through detecting the community structure of FPCN based on K-means clustering, distinct flow patterns can be successfully distinguished and identified. A number of FDCN’s under different flow conditions were constructed in order to reveal the dynamical characteristics of two-phase flows. The FDCNs exhibit universal power-law degree distributions. The power-law exponent ...

  13. Abnormal gas-liquid-solid phase transition behaviour of water observed with in situ environmental SEM.

    Chen, Xin; Shu, Jiapei; Chen, Qing

    2017-04-24

    Gas-liquid-solid phase transition behaviour of water is studied with environmental scanning electron microscopy for the first time. Abnormal phenomena are observed. At a fixed pressure of 450 Pa, with the temperature set to -7 °C, direct desublimation happens, and ice grows continuously along the substrate surface. At 550 Pa, although ice is the stable phase according to the phase diagram, metastable liquid droplets first nucleate and grow to ~100-200 μm sizes. Ice crystals nucleate within the large sized droplets, grow up and fill up the droplets. Later, the ice crystals grow continuously through desublimation. At 600 Pa, the metastable liquid grows quickly, with some ice nuclei floating in it, and the liquid-solid coexistence state exists for a long time. By lowering the vapour pressure and/or increasing the substrate temperature, ice sublimates into vapour phase, and especially, the remaining ice forms a porous structure due to preferential sublimation in the concave regions, which can be explained with surface tension effect. Interestingly, although it should be forbidden for ice to transform into liquid phase when the temperature is well below 0 °C, liquid like droplets form during the ice sublimation process, which is attributed to the surface tension effect and the quasiliquid layers.

  14. CHAOS. III. GAS-PHASE ABUNDANCES IN NGC 5457

    Croxall, Kevin V.; Pogge, Richard W. [Department of Astronomy, The Ohio State University, 140 West 18th Avenue, Columbus, OH 43210 (United States); Berg, Danielle A. [Center for Gravitation, Cosmology and Astrophysics, Department of Physics, University of Wisconsin Milwaukee, 1900 East Kenwood Boulevard, Milwaukee, WI 53211 (United States); Skillman, Evan D. [Minnesota Institute for Astrophysics, University of Minnesota, 116 Church Street SE, Minneapolis, MN 55455 (United States); Moustakas, John [Department of Physics and Astronomy, Siena College, 515 Loudon Road, Loudonville, NY 12211 (United States)

    2016-10-10

    We present Large Binocular Telescope observations of 109 H ii regions in NGC 5457 (M101) obtained with the Multi-Object Double Spectrograph. We have robust measurements of one or more temperature-sensitive auroral emission lines for 74 H ii regions, permitting the measurement of “direct” gas-phase abundances. Comparing the temperatures derived from the different ionic species, we find: (1) strong correlations of T [N ii] with T [S iii] and T [O iii], consistent with little or no intrinsic scatter; (2) a correlation of T [S iii] with T [O iii], but with significant intrinsic dispersion; (3) overall agreement between T [N ii], T [S ii], and T [O ii], as expected, but with significant outliers; (4) the correlations of T [N ii] with T [S iii] and T [O iii] match the predictions of photoionization modeling while the correlation of T [S iii] with T [O iii] is offset from the prediction of photoionization modeling. Based on these observations, which include significantly more observations of lower excitation H ii regions, missing in many analyses, we inspect the commonly used ionization correction factors (ICFs) for unobserved ionic species and propose new empirical ICFs for S and Ar. We have discovered an unexpected population of H ii regions with a significant offset to low values in Ne/O, which defies explanation. We derive radial gradients in O/H and N/O which agree with previous studies. Our large observational database allows us to examine the dispersion in abundances, and we find intrinsic dispersions of 0.074 ± 0.009 in O/H and 0.095 ± 0.009 in N/O (at a given radius). We stress that this measurement of the intrinsic dispersion comes exclusively from direct abundance measurements of H ii regions in NGC 5457.

  15. The properties of gas-phase multiply charged ions

    Newson, K.A.

    1999-01-01

    This thesis presents the results of a series of experiments investigating the reactivity of gas-phase molecular dications with various neutral collision partners, at collision energies between 3 and 13 eV in the laboratory frame, using a crossed-beam apparatus. The experiment involves the measurement of product ion intensities, which are determined by means of time-of-flight mass spectrometry. The experimental apparatus and methodology, together with the areas of theory important to ion chemistry, are described in the thesis. The product ions of greatest interest are those ions formed by bond-forming (chemical) reactivity. The relative intensities of such product ions, and those ions formed as a result of electron-transfer reactions, are, when recorded as a function of the collision energy, a powerful probe of the reaction mechanism. Additionally, where appropriate, the reactions are examined for isotope effects by using the isotopic analogue of the neutral collision partner. The results of the experiments indicate that no intermolecular isotope effects are present in the reactions of CF 2 2+ and CF 3 2+ with H 2 and D 2 neutral targets. In addition, the observed collision energy dependence is symptomatic of the absence of a barrier to reaction. These observations suggest that the reactions proceed via an impulsive direct reaction mechanism. Such a conclusion casts doubt on the applicability of the Landau-Zener model of H - /D - transfer reactivity. Other results presented in this thesis include the first reported observation of a bond-forming reaction between a molecular dication (CF2 2+ ) and a polyatomic neutral species (NH 3 ). Finally, the branching ratio of the products of bond-forming reactions between CF 2 2+ with HD indicates the operation of a strong intramolecular isotope effect, favouring the formation of the deuterated product. This observation points to a reaction mechanism in which the bond-formation is preceded by electron-transfer. (author)

  16. Dissociative electron attachment to the gas-phase nucleobase hypoxanthine

    Dawley, M. Michele [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Tanzer, Katrin; Denifl, Stephan, E-mail: Stephan.Denifl@uibk.ac.at, E-mail: Sylwia.Ptasinska.1@nd.edu [Institut für Ionenphysik und Angewandte Physik, and Center for Molecular Biosciences Innsbruck (CMBI), Leopold-Franzens Universität Innsbruck, Technikerstr. 25, A-6020 Innsbruck (Austria); Carmichael, Ian [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Ptasińska, Sylwia, E-mail: Stephan.Denifl@uibk.ac.at, E-mail: Sylwia.Ptasinska.1@nd.edu [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556 (United States)

    2015-06-07

    We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C{sub 5}H{sub 4}N{sub 4}O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp − H) anion (C{sub 5}H{sub 3}N{sub 4}O{sup −}) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp − NH){sup −}, C{sub 4}H{sub 3}N{sub 4}{sup −}/C{sub 4}HN{sub 3}O{sup −}, C{sub 4}H{sub 2}N{sub 3}{sup −}, C{sub 3}NO{sup −}/HC(HCN)CN{sup −}, OCN{sup −}, CN{sup −}, and O{sup −}. Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA to Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.

  17. Kinetics of the gas-phase tritium oxidation reaction

    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

  18. Dissociative attachment reactions of electrons with gas phase superacids

    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

  19. Gas-Phase Combustion Synthesis of Aluminum Nitride Powder

    Axelbaum, R. L.; Lottes, C. R.; Huertas, J. I.; Rosen, L. J.

    1996-01-01

    Due to its combined properties of high electrical resistivity and high thermal conductivity aluminum nitride (AlN) is a highly desirable material for electronics applications. Methods are being sought for synthesis of unagglomerated, nanometer-sized powders of this material, prepared in such a way that they can be consolidated into solid compacts having minimal oxygen content. A procedure for synthesizing these powders through gas-phase combustion is described. This novel approach involves reacting AlCl3, NH3, and Na vapors. Equilibrium thermodynamic calculations show that 100% yields can be obtained for these reactants with the products being AlN, NaCl, and H2. The NaCl by-product is used to coat the AlN particles in situ. The coating allows for control of AlN agglomeration and protects the powders from hydrolysis during post-flame handling. On the basis of thermodynamic and kinetic considerations, two different approaches were employed to produce the powder, in co-flow diffusion flame configurations. In the first approach, the three reactants were supplied in separate streams. In the second, the AlCl3 and NH3 were premixed with HCl and then reacted with Na vapor. X-ray diffraction (XRD) spectra of as-produced powders show only NaCl for the first case and NaCl and AlN for the second. After annealing at 775 C tinder dynamic vacuum, the salt was removed and XRD spectra of powders from both approaches show only AlN. Aluminum metal was also produced in the co-flow flame by reacting AlCl3 with Na. XRD spectra of as-produced powders show the products to be only NaCl and elemental aluminum.

  20. Nanoparticles from the Gas Phase as Building Blocks for Electrical Devices

    Fissan, H.; Kennedy, M.K.; Krinke, T.J.; Kruis, F.E.

    2003-01-01

    Electrical device development is driven by miniaturization and possibilities to use new chemical and physical effects. Nanotechnology offers both aspects. The structural dimensions of materials and devices are small and because of that large exchange surfaces are provided but also effects like quantum effects may occur and be used to get new or at least improved properties of nanostructured materials and devices.Nanoparticles are of special interest because of their nanodimensions in all three directions, so that nanoeffects become most prominent. They can be synthesized in solid materials, in liquids and in gases. Gas synthesis has several advantages compared to the other phases, especially the high cleanliness which can be achieved. In case of electrical devices the particles have to be deposited onto substrates in a structured way.The substrate may consist out of microelectronic devices in which the deposited nanoparticles are introduced for the basic function. In case of a transistor this would be the gate function, in case of a sensor this would be the sensing layer, where the contact with the measurement object takes place. For two kinds of particles SnO 2 and PbS, synthesized in the gas phase, we demonstrate the way how to create devices with improved sensor properties

  1. Graphene for Expandable Space Structures, Phase I

    National Aeronautics and Space Administration — Graphene's tightly bonded impermeable single atomic layer of carbon offers unrivalled potential for lightweight flexible gas barrier applications. Graphene has been...

  2. Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase (SILP) Rh catalysts

    Riisager, Anders; Wasserscheid, Peter; Van Hal, R.

    2003-01-01

    Continuous flow gas-phase hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1-n-butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1-n-butyl...

  3. Engineered Materials for Advanced Gas Turbine Engine, Phase I

    National Aeronautics and Space Administration — This project will develop innovative composite powders and composites that will surpass the properties of currently identified materials for advanced gas turbine...

  4. Dynamic Modeling Strategy for Flow Regime Transition in Gas-Liquid Two-Phase Flows

    Xia Wang

    2012-12-01

    Full Text Available In modeling gas-liquid two-phase flows, the concept of flow regimes has been widely used to characterize the global interfacial structure of the flows. Nearly all constitutive relations that provide closures to the interfacial transfers in two-phase flow models, such as the two-fluid model, are flow regime dependent. Current nuclear reactor safety analysis codes, such as RELAP5, classify flow regimes using flow regime maps or transition criteria that were developed for steady-state, fully-developed flows. As two-phase flows are dynamic in nature, it is important to model the flow regime transitions dynamically to more accurately predict the two-phase flows. The present work aims to develop a dynamic modeling strategy to determine flow regimes in gas-liquid two-phase flows through introduction of interfacial area transport equations (IATEs within the framework of a two-fluid model. The IATE is a transport equation that models the interfacial area concentration by considering the creation of the interfacial area, fluid particle (bubble or liquid droplet disintegration, boiling and evaporation, and the destruction of the interfacial area, fluid particle coalescence and condensation. For flow regimes beyond bubbly flows, a two-group IATE has been proposed, in which bubbles are divided into two groups based on their size and shapes, namely group-1 and group-2 bubbles. A preliminary approach to dynamically identify the flow regimes is discussed, in which discriminators are based on the predicted information, such as the void fraction and interfacial area concentration. The flow regime predicted with this method shows good agreement with the experimental observations.

  5. Gas phase adsorption technology for nitrogen isotope separation and its feasibility for highly enriched nitrogen gas production

    Inoue, Masaki; Asaga, Takeo

    2000-04-01

    Highly enriched nitrogen-15 gas is favorable to reduce radioactive carbon-14 production in reactor. The cost of highly enriched nitrogen-15 gas in mass production is one of the most important subject in nitride fuel option in 'Feasibility Study for FBR and Related Fuel Cycle'. In this work gas phase adsorption technology was verified to be applicable for nitrogen isotope separation and feasible to produce highly enriched nitrogen-15 gas in commercial. Nitrogen isotopes were separated while ammonia gas flows through sodium-A type zeolite column using pressure swing adsorption process. The isotopic ratio of eight samples were measured by high resolution mass spectrometry and Fourier transform microwave spectroscopy. Gas phase adsorption technology was verified to be applicable for nitrogen isotope separation, since the isotopic ratio of nitrogen-15 and nitrogen-14 in samples were more than six times as high as in natural. The cost of highly enriched nitrogen-15 gas in mass production were estimated by the factor method. It revealed that highly enriched nitrogen-15 gas could be supplied in a few hundred yen per gram in mass production. (author)

  6. Formamidinium iodide: crystal structure and phase transitions

    Andrey A. Petrov

    2017-04-01

    Full Text Available At a temperature of 100 K, CH5N2+·I− (I, crystallizes in the monoclinic space group P21/c. The formamidinium cation adopts a planar symmetrical structure [the r.m.s. deviation is 0.002 Å, and the C—N bond lengths are 1.301 (7 and 1.309 (8 Å]. The iodide anion does not lie within the cation plane, but deviates from it by 0.643 (10 Å. The cation and anion of I form a tight ionic pair by a strong N—H...I hydrogen bond. In the crystal of I, the tight ionic pairs form hydrogen-bonded zigzag-like chains propagating toward [20-1] via strong N—H...I hydrogen bonds. The hydrogen-bonded chains are further packed in stacks along [100]. The thermal behaviour of I was studied by different physicochemical methods (thermogravimetry, differential scanning calorimetry and powder diffraction. Differential scanning calorimetry revealed three narrow endothermic peaks at 346, 387 and 525 K, and one broad endothermic peak at ∼605 K. The first and second peaks are related to solid–solid phase transitions, while the third and fourth peaks are attributed to the melting and decomposition of I. The enthalpies of the phase transitions at 346 and 387 K are estimated as 2.60 and 2.75 kJ mol−1, respectively. The X-ray powder diffraction data collected at different temperatures indicate the existence of I as the monoclinic (100–346 K, orthorhombic (346–387 K and cubic (387–525 K polymorphic modifications.

  7. Structuring strategy and relationships in North American gas markets

    Fisher, J.

    1998-01-01

    Duke Energy's experience in strategy development and structuring relationships with other companies were described. Included was a description of their partnership with PanEnergy and Mobil and a merger between PanEnergy and Duke. In developing their growth strategy, Duke Energy was guided by the following considerations: (1) an assessment of the market, (2) the identification of opportunities, (3) a self-assessment, (4) the establishment of goals, and (5) determining strategic alternatives. The advantages and disadvantages of different structuring relationships were reviewed. Duke Energy's approach to Ontario's residential market and their agreement with Alliance Gas Management were also discussed. The goal of the Alliance Gas management agreement was to simplify Alliance's wholesale gas supply management needs and to allow Alliance access to diverse gas supplies. figs

  8. Financing gas plants using off balance sheet structures

    Best, R.J.; Malcolm, V.

    1999-01-01

    A means by which to finance oil and gas facilities using off balance sheet structures was presented. Off balance sheet facility financing means the sale by an oil and gas producer of a processing and/or transportation facility to a financial intermediary, who under a Management Agreement, appoints the producer as the operator of the facility. The financial intermediary charges a fixed processing fee to the producer and all the benefits and upside of ownership are retained by the producer. This paper deals specifically with a flexible off balance sheet facility financing structure that can be used to make effective use of discretionary capital which is committed to gas processing and to the construction of new gas processing facilities. Off balance sheet financing is an attractive alternative method of ownership that frees up capital that is locked into the facilities while allowing the producer to retain strategic control of the processing facility

  9. Possibility of determining the concentration of the gas phase in a two-phase stream by an acoustical method

    Butenko, A N; Potapenko, A E; Chistyakov, E S

    1976-01-01

    The method is based on the recording of the amplitude-frequency characteristics of a circular piezoelectric resonator (sensor) during movement of a stream of a two-phase medium. It is shown that the electrical voltage drop across the transducer and the natural oscillating frequency of the transducer depend on the concentration of the gas phase in the two-phase mixture, allowing an instrument to be developed for measurement of this concentration.

  10. Two-phase gas bubble-liquid boundary layer flow along vertical and inclined surfaces

    Cheung, F.B.; Epstein, M.

    1985-01-01

    The behavior of a two-phase gas bubble-liquid boundary layer along vertical and inclined porous surfaces with uniform gas injection is investigated experimentally and analytically. Using argon gas and water as the working fluids, a photographical study of the two-phase boundary layer flow has been performed for various angles of inclination ranging from 45 0 to 135 0 and gas injection rates ranging from 0.01 to 0.1 m/s. An integral method has been employed to solve the system of equations governing the two-phase motion. The effects of the gas injection rate and the angle of inclination on the growth of the boundary layer have been determined. The predicted boundary layer thickness is found to be in good agreement with the experimental results. The calculated axial liquid velocity and the void fraction in the two-phase region are also presented along with the observed flow behavior

  11. Evolution of the Normal State of a Strongly Interacting Fermi Gas from a Pseudogap Phase to a Molecular Bose Gas

    Perali, A.; Palestini, F.; Pieri, P.; Strinati, G. C.; Stewart, J. T.; Gaebler, J. P.; Drake, T. E.; Jin, D. S.

    2011-01-01

    Wave-vector resolved radio frequency spectroscopy data for an ultracold trapped Fermi gas are reported for several couplings at T c , and extensively analyzed in terms of a pairing-fluctuation theory. We map the evolution of a strongly interacting Fermi gas from the pseudogap phase into a fully gapped molecular Bose gas as a function of the interaction strength, which is marked by a rapid disappearance of a remnant Fermi surface in the single-particle dispersion. We also show that our theory of a pseudogap phase is consistent with a recent experimental observation as well as with quantum Monte Carlo data of thermodynamic quantities of a unitary Fermi gas above T c .

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

    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.

  13. Single phase and two phase erosion corrosion in broilers of gas-cooled reactors

    Harrison, G.S.; Fountain, M.J.

    1988-01-01

    Erosion-corrosion is a phenomenon causing metal wastage in a variety of locations in water and water-steam circuits throughout the power generation industry. Erosion-corrosion can occur in a number of regions of the once-through boiler designs used in the later Magnox and AGR type of gas cooled nuclear reactor. This paper will consider two cases of erosion-corrosion damage (single and two phase) in once through boilers of gas cooled reactors and will describe the solutions that have been developed. The single phase problem is associated with erosion-corrosion damage of mild steel downstream of a boiler inlet flow control orifice. With metal loss rates of up to 1 mm/year at 150 deg. C and pH in the range 9.0-9.4 it was found that 5 μg/kg oxygen was sufficient to reduce erosion-corrosion rates to less than 0.02 mm/year. A combined oxygen-ammonia-hydrazine feedwater regime was developed and validated to eliminate oxygen carryover and hence give protection from stress corrosion in the austenitic section of the AGR once through boiler whilst still providing erosion-corrosion control. Two phase erosion-corrosion tube failures have occurred in the evaporator of the mild steel once through boilers of the later Magnox reactors operating at pressures in the range 35-40 bar. Rig studies have shown that amines dosed in the feedwater can provide a significant reduction in metal loss rates and a tube lifetime assessment technique has been developed to predict potential tube failure profiles in a fully operational boiler. The solutions identified for both problems have been successfully implemented and the experience obtained following implementation including any problems or other benefits arising from the introduction of the new regimes will be presented. Methods for monitoring and evaluating the efficiency of the solutions have been developed and the results from these exercises will also be discussed. Consideration will also be given to the similarities in the metal loss

  14. Single phase and two phase erosion corrosion in broilers of gas-cooled reactors

    Harrison, G S; Fountain, M J [Operational Engineering Division (Northern Area), Central Electricity Generating Board, Manchester (United Kingdom)

    1988-07-01

    Erosion-corrosion is a phenomenon causing metal wastage in a variety of locations in water and water-steam circuits throughout the power generation industry. Erosion-corrosion can occur in a number of regions of the once-through boiler designs used in the later Magnox and AGR type of gas cooled nuclear reactor. This paper will consider two cases of erosion-corrosion damage (single and two phase) in once through boilers of gas cooled reactors and will describe the solutions that have been developed. The single phase problem is associated with erosion-corrosion damage of mild steel downstream of a boiler inlet flow control orifice. With metal loss rates of up to 1 mm/year at 150 deg. C and pH in the range 9.0-9.4 it was found that 5 {mu}g/kg oxygen was sufficient to reduce erosion-corrosion rates to less than 0.02 mm/year. A combined oxygen-ammonia-hydrazine feedwater regime was developed and validated to eliminate oxygen carryover and hence give protection from stress corrosion in the austenitic section of the AGR once through boiler whilst still providing erosion-corrosion control. Two phase erosion-corrosion tube failures have occurred in the evaporator of the mild steel once through boilers of the later Magnox reactors operating at pressures in the range 35-40 bar. Rig studies have shown that amines dosed in the feedwater can provide a significant reduction in metal loss rates and a tube lifetime assessment technique has been developed to predict potential tube failure profiles in a fully operational boiler. The solutions identified for both problems have been successfully implemented and the experience obtained following implementation including any problems or other benefits arising from the introduction of the new regimes will be presented. Methods for monitoring and evaluating the efficiency of the solutions have been developed and the results from these exercises will also be discussed. Consideration will also be given to the similarities in the metal loss

  15. Ab initio molecular crystal structures, spectra, and phase diagrams.

    Hirata, So; Gilliard, Kandis; He, Xiao; Li, Jinjin; Sode, Olaseni

    2014-09-16

    Conspectus Molecular crystals are chemists' solids in the sense that their structures and properties can be understood in terms of those of the constituent molecules merely perturbed by a crystalline environment. They form a large and important class of solids including ices of atmospheric species, drugs, explosives, and even some organic optoelectronic materials and supramolecular assemblies. Recently, surprisingly simple yet extremely efficient, versatile, easily implemented, and systematically accurate electronic structure methods for molecular crystals have been developed. The methods, collectively referred to as the embedded-fragment scheme, divide a crystal into monomers and overlapping dimers and apply modern molecular electronic structure methods and software to these fragments of the crystal that are embedded in a self-consistently determined crystalline electrostatic field. They enable facile applications of accurate but otherwise prohibitively expensive ab initio molecular orbital theories such as Møller-Plesset perturbation and coupled-cluster theories to a broad range of properties of solids such as internal energies, enthalpies, structures, equation of state, phonon dispersion curves and density of states, infrared and Raman spectra (including band intensities and sometimes anharmonic effects), inelastic neutron scattering spectra, heat capacities, Gibbs energies, and phase diagrams, while accounting for many-body electrostatic (namely, induction or polarization) effects as well as two-body exchange and dispersion interactions from first principles. They can fundamentally alter the role of computing in the studies of molecular crystals in the same way ab initio molecular orbital theories have transformed research practices in gas-phase physical chemistry and synthetic chemistry in the last half century. In this Account, after a brief summary of formalisms and algorithms, we discuss applications of these methods performed in our group as compelling

  16. Detection methods for atoms and radicals in the gas phase

    Hack, W.

    This report lists atoms and free radicals in the gas phase which are of interest for environmental and flame chemistry and have been detected directly. The detection methods which have been used are discussed with respect to their range of application, specificity and sensitivity. In table 1, detection methods for the five atoms of group IV (C, Si, Ge, Sn, Pb) and about 60 radicals containing at least one atom of group IV are summarized (CH, Cd, Cf, CC1, CBr, Cn, Cs, CSe, CH2, CD2, Chf, Cdf, CHC1, CHBr, CF2, CC12, CBr2, CFC1, CFBr, CH3, CD3, CF3, CH2F, CH2C1, CH2Br, CHF2, CHC12, CHBr2, Hco, Fco, CH30, CD30, CH2OH, CH3S, Nco, CH4N, CH302, CF302; C2, C2N, C2H, C20, C2HO, C2H3, C2F3, C2H5, C2HsO, C2H4OH, CH3CO, CD3CO, C2H3O, C2H502, CH3COO2, C2H4N, C2H6N, C3; Si, SiF, SiF2, SiO, SiC, Si2; Ge, GeC, GeO, GeF, GeF2, GeCl2, Sn, SnF, SnO, SnF2, Pb, PbF, PbF2, PbO, PbS). In table 2 detection methods for about 25 other atoms and 60 radicals are listed: (H, D, O, O2, Oh, Od, HO2, DO2, F, Ci, Br, I, Fo, Cio, BrO, Io, FO2, C1O2, Li, Na, K, Rb, Cs, N, N3, Nh, Nd, Nf, Nci, NBr, NH2, ND2, Nhd, Nhf, NF2, NC12, N2H3, No, NO2, NO3, Hno, Dno, P, Ph, Pd, Pf, Pci, PH2, PD2, PF2, Po, As, AsO, AsS, Sb, Bi, S, S2, Sh, Sd, Sf, SF2, So, Hso, Dso, Sn, Se, Te, Se2, SeH, SeD, SeF, SeO, SeS, SeN, TeH, TeO, Bh, BH2, Bo, Bn, B02, Cd, Hg, UF5). The tables also cite some recent kinetic applications of the various methods.

  17. Investigation of the resistive phase in high power gas switching. Research and development report

    O'Rourke, R.C.

    1977-01-01

    A theoretical study was made of the resistive phase in high pressure gas switching with the regime of interest being (10 to 50) kV from (1J, 10ns, 100KHz) to (100J, 10μs, 1KHz). The resistive phase was examined as a function of applied field, gap spacing, inductance, gas type and pressure, and electrode material. The initiating and quenching phases as regards system performance (e.g., the jitter problem) were examined. The cooling and electrode debris removal effects of the vortex gas flow on the operating characteristics of the system were considered

  18. Hot Gas TVC For Planetary Ascent Vehicle, Phase I

    National Aeronautics and Space Administration — A Mars ascent vehicle (MAV) uses solid rocket motors to propel soil samples into orbit, but the motors cannot provide steering. Cold gas thrusters are used for...

  19. Advanced On Board Inert Gas Generation System (OBBIGS), Phase II

    National Aeronautics and Space Administration — Valcor Engineering Corporation proposes to develop an advanced On Board Inert Gas Generation System, OBIGGS, for aircraft fuel tank inerting to prevent hazardous...

  20. Two-stage coal liquefaction without gas-phase hydrogen

    Stephens, H.P.

    1986-06-05

    A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

  1. Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution.

    Comitani, Federico; Rossi, Kevin; Ceriotti, Michele; Sanz, M Eugenia; Molteni, Carla

    2017-04-14

    The conformational free energy landscape of aspartic acid, a proteogenic amino acid involved in a wide variety of biological functions, was investigated as an example of the complexity that multiple rotatable bonds produce even in relatively simple molecules. To efficiently explore such a landscape, this molecule was studied in the neutral and zwitterionic forms, in the gas phase and in water solution, by means of molecular dynamics and the enhanced sampling method metadynamics with classical force-fields. Multi-dimensional free energy landscapes were reduced to bi-dimensional maps through the non-linear dimensionality reduction algorithm sketch-map to identify the energetically stable conformers and their interconnection paths. Quantum chemical calculations were then performed on the minimum free energy structures. Our procedure returned the low energy conformations observed experimentally in the gas phase with rotational spectroscopy [M. E. Sanz et al., Phys. Chem. Chem. Phys. 12, 3573 (2010)]. Moreover, it provided information on higher energy conformers not accessible to experiments and on the conformers in water. The comparison between different force-fields and quantum chemical data highlighted the importance of the underlying potential energy surface to accurately capture energy rankings. The combination of force-field based metadynamics, sketch-map analysis, and quantum chemical calculations was able to produce an exhaustive conformational exploration in a range of significant free energies that complements the experimental data. Similar protocols can be applied to larger peptides with complex conformational landscapes and would greatly benefit from the next generation of accurate force-fields.

  2. Single-step gas phase synthesis of stable iron aluminide nanoparticles with soft magnetic properties

    Vernieres, Jerome, E-mail: Jerome.vernieres@oist.jp; Benelmekki, Maria; Kim, Jeong-Hwan; Grammatikopoulos, Panagiotis; Diaz, Rosa E. [Nanoparticles by Design Unit, Okinawa Institute of Science and Technology (OIST) Graduate University, 1919-1 Tancha, Onna Son, Okinawa 904-0495 (Japan); Bobo, Jean-François [Centre d’Elaboration de Materiaux et d’Etudes Structurales (CEMES), 29 rue Jeanne Marvig, 31055 Toulouse Cedex 4 (France); Sowwan, Mukhles, E-mail: Mukhles@oist.jp [Nanoparticles by Design Unit, Okinawa Institute of Science and Technology (OIST) Graduate University, 1919-1 Tancha, Onna Son, Okinawa 904-0495 (Japan); Nanotechnology Research Laboratory, Al-Quds University, P.O. Box 51000, East Jerusalem, Palestine (Country Unknown)

    2014-11-01

    Soft magnetic alloys at the nanoscale level have long generated a vivid interest as candidate materials for technological and biomedical purposes. Consequently, controlling the structure of bimetallic nanoparticles in order to optimize their magnetic properties, such as high magnetization and low coercivity, can significantly boost their potential for related applications. However, traditional synthesis methods stumble upon the long standing challenge of developing true nanoalloys with effective control over morphology and stability against oxidation. Herein, we report on a single-step approach to the gas phase synthesis of soft magnetic bimetallic iron aluminide nanoparticles, using a versatile co-sputter inert gas condensation technique. This method allowed for precise morphological control of the particles; they consisted of an alloy iron aluminide crystalline core (DO{sub 3} phase) and an alumina shell, which reduced inter-particle interactions and also prevented further oxidation and segregation of the bimetallic core. Remarkably, the as-deposited alloy nanoparticles show interesting soft magnetic properties, in that they combine a high saturation magnetization (170 emu/g) and low coercivity (less than 20 Oe) at room temperature. Additional functionality is tenable by modifying the surface of the particles with a polymer, to ensure their good colloidal dispersion in aqueous environments.

  3. Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

    Comitani, Federico; Rossi, Kevin; Ceriotti, Michele; Sanz, M. Eugenia; Molteni, Carla

    2017-04-01

    The conformational free energy landscape of aspartic acid, a proteogenic amino acid involved in a wide variety of biological functions, was investigated as an example of the complexity that multiple rotatable bonds produce even in relatively simple molecules. To efficiently explore such a landscape, this molecule was studied in the neutral and zwitterionic forms, in the gas phase and in water solution, by means of molecular dynamics and the enhanced sampling method metadynamics with classical force-fields. Multi-dimensional free energy landscapes were reduced to bi-dimensional maps through the non-linear dimensionality reduction algorithm sketch-map to identify the energetically stable conformers and their interconnection paths. Quantum chemical calculations were then performed on the minimum free energy structures. Our procedure returned the low energy conformations observed experimentally in the gas phase with rotational spectroscopy [M. E. Sanz et al., Phys. Chem. Chem. Phys. 12, 3573 (2010)]. Moreover, it provided information on higher energy conformers not accessible to experiments and on the conformers in water. The comparison between different force-fields and quantum chemical data highlighted the importance of the underlying potential energy surface to accurately capture energy rankings. The combination of force-field based metadynamics, sketch-map analysis, and quantum chemical calculations was able to produce an exhaustive conformational exploration in a range of significant free energies that complements the experimental data. Similar protocols can be applied to larger peptides with complex conformational landscapes and would greatly benefit from the next generation of accurate force-fields.

  4. Phase transitions and domain structures in multiferroics

    Vlahos, Eftihia

    2011-12-01

    Thin film ferroelectrics and multiferroics are two important classes of materials interesting both from a scientific and a technological prospective. The volatility of lead and bismuth as well as environmental issues regarding the toxicity of lead are two disadvantages of the most commonly used ferroelectric random access memory (FeRAM) materials such as Pb(Zr,Ti)O3 and SrBi2Ta2O9. Therefore lead-free thin film ferroelectrics are promising substitutes as long as (a) they can be grown on technologically important substrates such as silicon, and (b) their T c and Pr become comparable to that of well established ferroelectrics. On the other hand, the development of functional room temperature ferroelectric ferromagnetic multiferroics could lead to very interesting phenomena such as control of magnetism with electric fields and control of electrical polarization with magnetic fields. This thesis focuses on the understanding of material structure-property relations using nonlinear optical spectroscopy. Nonlinear spectroscopy is an excellent tool for probing the onset of ferroelectricity, and domain dynamics in strained ferroelectrics and multiferroics. Second harmonic generation was used to detect ferroelectricity and the antiferrodistortive phase transition in thin film SrTiO3. Incipient ferroelectric CaTiO3 has been shown to become ferroelectric when strained with a combination of SHG and dielectric measurements. The tensorial nature of the induced nonlinear polarization allows for probing of the BaTiO3 and SrTiO3 polarization contributions in nanoscale BaTiO3/SrTiO3 superlattices. In addition, nonlinear optics was used to demonstrate ferroelectricity in multiferroic EuTiO3. Finally, confocal SHG and Raman microscopy were utilized to visualize polar domains in incipient ferroelectric and ferroelastic CaTiO3.

  5. Conference Proceedings: Structuring oil and gas property transactions

    1999-01-01

    The 12 presentations at this conference dealt with issues concerning the legal aspects of oil and gas property transaction agreements. Several issues regarding sales and purchase negotiations of oil and gas property are reviewed and some of the basic principles of contract law are explained. Advantages, disadvantages and opportunities of structuring oil and gas property acquisitions, as well as their tax consequences are also identified. The issue of risk assessment regarding environmental consequences and how public concerns regarding the state of the environment has had an impact on oil and gas transactions, is addressed. Interest in this topic stems from the fact that improved enforcement of existing laws regarding the environment can potentially make purchasers liable for significant costs associated with remediation or clean-up of contaminated properties. refs., tabs., figs

  6. Crystal-liquid-gas phase transitions and thermodynamic similarity

    Skripov, Vladimir P; Schmelzer, Jurn W P

    2006-01-01

    Professor Skripov obtained worldwide recognition with his monograph ""Metastable liquids"", published in English by Wiley & Sons. Based upon this work and another monograph published only in Russia, this book investigates the behavior of melting line and the properties of the coexisting crystal and liquid phase of simple substances across a wide range of pressures, including metastable states of the coexisting phases. The authors derive new relations for the thermodynamic similarity for liquid-vapour phase transition, as well as describing solid-liquid, liquid-vapor and liquid-liquid phase tra

  7. Gas hydrate inhibition by perturbation of liquid water structure

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Lee, Kun-Hong

    2015-06-01

    Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

  8. Two-phase gas bubble-liquid boundary layer flow along vertical and inclined surfaces

    Cheung, F.B.; Epstein, M.

    1985-01-01

    The behavior of a two-phase gas bubble liquid boundary layer along vertical and inclined porous surfaces with uniform gas injection is investigated experimentally and analytically. Using argon gas and water as the working fluids, a photographical study of the two-phase boundary layer flow has been performed for various angles of inclination ranging from 45 0 to 135 0 and gas injection rates ranging from 0.01 to 0.1 m/s. An integral method has been employed to solve the system of equations governing the two-phase motion. The effects of the gas injection rate and the angle of inclination on the growth of the boundary layer have been determined

  9. Optical processes in the performance and recovery of gas-phase switches

    Gundersen, M.

    1982-01-01

    In this paper several optical processes that may be used to affect gas-phase switch performance and operation are discussed, and approaches using a laser to increase recovery rates of switches are presented. In the latter the laser is used during the recovery phase rather than the conductive or closure phase. This papper suggests that it should be possible to use a low-power laser (e.g., one that is technologically feasible to use as part of a switch) to assist in opening the switch by quenching excited atomic and/or molecular species. The application of laser-induced energy extraction to gas-phase switches is also discussed

  10. Enhanced Membrane System for Recovery of Water from Gas-Liquid Mixtures, Phase I

    National Aeronautics and Space Administration — Gas-Liquid separation is an acute microgravity problem. Existing devices use centrifugal motion on microporous membranes to separate the two phases. Centrifugal...

  11. Infrared spectroscopy of gas-phase clusters using a free-electron laser

    Heijnsbergen, D. van; Helden, G. von; Meijer, G.

    2002-01-01

    Most clusters produced in the gas phase, especially those containing metals, remain largely uncharaterized, among these are transition metal - carbide, -oxide and -nitride clusters. A method for recording IR spectra of strongly bound gas-phase clusters is presented. It is based on a free-electron laser called Felix, characterized by wide wavelength tuning range, covering almost the full 'molecular finger print' region, high power and fluence which make it suited to excite gas-phase species i.e. gas -phase clusters. Neutral clusters were generated by laser vaporization technique, ions that were created after the interaction with the free-electron laser were analyzed in a flight mass spectrometer. Experiments were run with titanium carbide clusters and their IR spectra given. It was shown that this method is suited to strongly bound clusters with low ionization energies, a condition met for many pure metal clusters and metal compound clusters. (nevyjel)

  12. Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

    Axson, Jessica L.; Takahashi, Kaito; De Haan, David O.; Vaida, Veronica

    2010-01-01

    In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, KP, for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, ΔG°, obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry. PMID:20142510

  13. Intrinsic folding of small peptide chains: spectroscopic evidence for the formation of beta-turns in the gas phase.

    Chin, Wutharath; Dognon, Jean-Pierre; Piuzzi, François; Tardivel, Benjamin; Dimicoli, Iliana; Mons, Michel

    2005-01-19

    Laser desorption of model peptides coupled to laser spectroscopic techniques enables the gas-phase observation of genuine secondary structures of biology. Spectroscopic evidence for the formation of beta-turns in gas-phase peptide chains containing glycine and phenylalanine residues establishes the intrinsic stability of these forms and their ability to compete with other stable structures. The precise characterization of local minima on the potential energy surface from IR spectroscopy constitutes an acute assessment for the state-of-the-art quantum mechanical calculations also presented. The observation of different types of beta-turns depending upon the residue order within the sequence is found to be consistent with the residue propensities in beta-turns of proteins, which suggests that the prevalence of glycine in type II and II' turns stems essentially from an energetic origin, already at play under isolated conditions.

  14. Experimental and CFD investigation of gas phase freeboard combustion

    Andersen, Jimmy

    Reliable and accurate modeling capabilities for combustion systems are valuable tools for optimization of the combustion process. This work concerns primary precautions for reducing NO emissions, thereby abating the detrimental effects known as “acid rain”, and minimizing cost for flue gas...... treatment. The aim of this project is to provide validation data for Computational Fluid Dynamic (CFD) models relevant for grate firing combustion conditions. CFD modeling is a mathematical tool capable of predicting fluid flow, mixing and chemical reaction with thermal conversion and transport. Prediction......, but under well-defined conditions. Comprehensive experimental data for velocity field, temperatures, and gas composition are obtained from a 50 kW axisymmetric non-swirling natural gas fired combustion setup under two different settings. Ammonia is added to the combustion setup in order to simulate fuel...

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

    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.)

  16. An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

    Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

    1988-01-01

    A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

  17. Ultrafast electronic relaxation of excited state vitamin B12 in the gas phase

    Shafizadeh, Niloufar; Poisson, Lionel; Soep, Benoit

    2008-01-01

    The time evolution of electronically excited vitamin B 12 (cyanocobalamin) has been observed for the first time in the gas phase. It reveals an ultrafast decay to a state corresponding to metal excitation. This decay is interpreted as resulting from a ring to metal electron transfer. This opens the observation of the excited state of other complex biomimetic systems in the gas phase, the key to the characterisation of their complex evolution through excited electronic states

  18. Two-phase xenon detector with gas amplification and electroluminescent signal detection

    Akimov, D.Yu.; Burenkov, A.A.; Grishkin, Yu.L.; Kovalenko, A.G.; Lebedenko, V.N.; Stekhanov, V.N.

    2008-01-01

    An optical technique for detecting ionization electrons produced during ionization of the liquid phase has been experimentally tested in two-phase (liquid-gas) xenon. The effects of gas and electroluminescent amplifications at the wire anode are simultaneously used for detection. This method allows construction of a supersensitive detector of small ionization signals-down to those corresponding to the detection of single electrons [ru

  19. A new method for determining gas phase heat of formation of aromatic energetic compounds

    Keshavarz, Mohammad H. [Department of Chemistry, Malek-ashtar University of Technology, Shahin-shahr P. O. Box 83145/115 (Iran); Tehrani, Masoud K. [Department of Physics, Malek-ashtar University of Technology, Shahin-shahr P. O. Box 83145/115 (Iran)

    2007-04-15

    A new correlation is introduced for desk calculation of gas phase heat of formation of aromatic energetic compounds that contain the elements of carbon, hydrogen, nitrogen and oxygen. Predicted gas phase heats of formation for 26 energetic compounds have a root mean square of deviation from experiment of 20.67 kJ/mol, which is in good agreement with respect to measured values of oxygen-lean and oxygen-rich aromatic energetic compounds. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  20. Periodic reviews of structural integrity of gas-cooled reactors

    Banks, P.J.; Stokoe, T.Y.; Thomas, D.L.

    1995-01-01

    Nuclear Electric operates 12 gas-cooled reactor power stations which have been in service for between 5 and 30 years. Periodically, comprehensive reviews of the safety cases are carried out for each station. The approach followed in these reviews in respect of structural integrity is outlined with the use of illustrative examples. (author)

  1. Lung Structure and the Intrinsic Challenges of Gas Exchange

    Hsia, Connie C.W.; Hyde, Dallas M.; Weibel, Ewald R.

    2016-01-01

    Structural and functional complexities of the mammalian lung evolved to meet a unique set of challenges, namely, the provision of efficient delivery of inspired air to all lung units within a confined thoracic space, to build a large gas exchange surface associated with minimal barrier thickness and a microvascular network to accommodate the entire right ventricular cardiac output while withstanding cyclic mechanical stresses that increase several folds from rest to exercise. Intricate regulatory mechanisms at every level ensure that the dynamic capacities of ventilation, perfusion, diffusion, and chemical binding to hemoglobin are commensurate with usual metabolic demands and periodic extreme needs for activity and survival. This article reviews the structural design of mammalian and human lung, its functional challenges, limitations, and potential for adaptation. We discuss (i) the evolutionary origin of alveolar lungs and its advantages and compromises, (ii) structural determinants of alveolar gas exchange, including architecture of conducting bronchovascular trees that converge in gas exchange units, (iii) the challenges of matching ventilation, perfusion, and diffusion and tissue-erythrocyte and thoracopulmonary interactions. The notion of erythrocytes as an integral component of the gas exchanger is emphasized. We further discuss the signals, sources, and limits of structural plasticity of the lung in alveolar hypoxia and following a loss of lung units, and the promise and caveats of interventions aimed at augmenting endogenous adaptive responses. Our objective is to understand how individual components are matched at multiple levels to optimize organ function in the face of physiological demands or pathological constraints. PMID:27065169

  2. Dynamic simulation of dispersed gas-liquid two-phase flow using a discrete bubble model.

    Delnoij, E.; Lammers, F.A.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

    1997-01-01

    In this paper a detailed hydrodynamic model for gas-liquid two-phase flow will be presented. The model is based on a mixed Eulerian-Lagrangian approach and describes the time-dependent two-dimensional motion of small, spherical gas bubbles in a bubble column operating in the homogeneous regime. The

  3. DEMONSTRATION BULLETIN: GAS-PHASE CHEMICAL REDUCTION - ECO LOGIC INTERNATIONAL, INC.

    The patented Eco Logic Process employs a gas-phase reduction reaction of hydrogen with organic and chlorinated organic compounds at elevated temperatures to convert aqueous and oily hazardous contaminants into a hydrocarbon-rich gas product. After passing through a scrubber, the ...

  4. Gas phase hydrogen peroxide production in atmospheric pressure glow discharges operating in He - H2O

    Vasko, C.A.; Veldhuizen, van E.M.; Bruggeman, P.J.

    2013-01-01

    The gas phase production of hydrogen peroxide (H2O2) in a RF atmospheric pressure glow discharge with helium and water vapour has been investigated as a function of the gas flow. It is shown that the production of H2O2 is through the recombination of two OH radicals in a three body collision and the

  5. Severe slugging in gas-liquid two-phase pipe flow

    Malekzadeh, R.

    2012-01-01

    transportation facilities. In an offshore oil and gas production facility, pipeline-riser systems are required to transport two-phase hydrocarbons from subsurface oil and gas wells to a central production platform. Severe slugs reaching several thousands pipe diameters may occur when transporting

  6. Formation mechanism of gas bubble superlattice in UMo metal fuels: Phase-field modeling investigation

    Hu, Shenyang, E-mail: shenyang.hu@pnnl.gov; Burkes, Douglas E.; Lavender, Curt A.; Senor, David J.; Setyawan, Wahyu; Xu, Zhijie

    2016-10-15

    Nano-gas bubble superlattices are often observed in irradiated UMo nuclear fuels. However, the formation mechanism of gas bubble superlattices is not well understood. A number of physical processes may affect the gas bubble nucleation and growth; hence, the morphology of gas bubble microstructures including size and spatial distributions. In this work, a phase-field model integrating a first-passage Monte Carlo method to investigate the formation mechanism of gas bubble superlattices was developed. Six physical processes are taken into account in the model: 1) heterogeneous generation of gas atoms, vacancies, and interstitials informed from atomistic simulations; 2) one-dimensional (1-D) migration of interstitials; 3) irradiation-induced dissolution of gas atoms; 4) recombination between vacancies and interstitials; 5) elastic interaction; and 6) heterogeneous nucleation of gas bubbles. We found that the elastic interaction doesn’t cause the gas bubble alignment, and fast 1-D migration of interstitials along 〈110〉 directions in the body-centered cubic U matrix causes the gas bubble alignment along 〈110〉 directions. It implies that 1-D interstitial migration along [110] direction should be the primary mechanism of a fcc gas bubble superlattice which is observed in bcc UMo alloys. Simulations also show that fission rates, saturated gas concentration, and elastic interaction all affect the morphology of gas bubble microstructures.

  7. Propagation characteristics of pulverized coal and gas two-phase flow during an outburst.

    Zhou, Aitao; Wang, Kai; Fan, Lingpeng; Tao, Bo

    2017-01-01

    Coal and gas outbursts are dynamic failures that can involve the ejection of thousands tons of pulverized coal, as well as considerable volumes of gas, into a limited working space within a short period. The two-phase flow of gas and pulverized coal that occurs during an outburst can lead to fatalities and destroy underground equipment. This article examines the interaction mechanism between pulverized coal and gas flow. Based on the role of gas expansion energy in the development stage of outbursts, a numerical simulation method is proposed for investigating the propagation characteristics of the two-phase flow. This simulation method was verified by a shock tube experiment involving pulverized coal and gas flow. The experimental and simulated results both demonstrate that the instantaneous ejection of pulverized coal and gas flow can form outburst shock waves. These are attenuated along the propagation direction, and the volume fraction of pulverized coal in the two-phase flow has significant influence on attenuation of the outburst shock wave. As a whole, pulverized coal flow has a negative impact on gas flow, which makes a great loss of large amounts of initial energy, blocking the propagation of gas flow. According to comparison of numerical results for different roadway types, the attenuation effect of T-type roadways is best. In the propagation of shock wave, reflection and diffraction of shock wave interact through the complex roadway types.

  8. Structural change in Europe's gas markets: three scenarios for the development of the European gas market to 2020

    Ellis, A.; Bowitz, E.; Roland, K.

    2000-01-01

    Against the background of the European Union's Gas Directive, and the emergence of new players and markets in Europe's gas sector, this paper explores how company actions could shape the future for the gas industry. Starting with an examination of company strategies this paper develops three scenarios for the future: a 'Gradual Transformation' scenario where a single European gas market develops that is essentially oligopolistic in nature; a 'Vertical Integration' scenario, where upstream and downstream gas companies merge to form a vertically integrated gas supplier; and a 'Pull the Plug' scenario, where the current market structure decomposes into a competitive market. These scenarios are examined in terms of their impact on gas prices, demand and the distribution of gas rent along the supply chain. The paper highlights the fact that the EU's gas Directive is not sufficient for the introduction of competition into Europe's gas markets, but that company actions will be the key determinant, and they may favour alternative market structures. (Author)

  9. Moisture effects on greenhouse gases generation in nitrifying gas-phase compost biofilters.

    Maia, Guilherme D N; Day, George B; Gates, Richard S; Taraba, Joseph L; Coyne, Mark S

    2012-06-01

    Gas-phase compost biofilters are extensively used in concentrated animal feeding operations to remove odors and, in some cases, ammonia from air sources. The expected biochemical pathway for these predominantly aerobic systems is nitrification. However, non-uniform media with low oxygen levels can shift biofilter microbial pathways to denitrification, a source of greenhouse gases. Several factors contribute to the formation of anoxic/anaerobic zones: media aging, media and particle structure, air velocity distribution, compaction, biofilm thickness, and moisture content (MC) distribution. The present work studies the effects of media moisture conditions on ammonia (NH(3)) removal and greenhouse gas generation (nitrous oxide, N(2)O and methane, CH(4)) for gas-phase compost biofilters subject to a 100-day controlled drying process. Continuous recordings were made for the three gases and water vapor (2.21-h sampling cycle, each cycle consisted of three gas species, and water vapor, for a total of 10,050 data points). Media moisture conditions were classified into three corresponding media drying rate (DR) stages: Constant DR (wetter media), falling DR, and stable-dry system. The first-half of the constant DR period (0-750 h; MC=65-52%, w.b.) facilitated high NH(3) removal rates, but higher N(2)O generation and no CH(4) generation. At the drier stages of the constant DR (750-950 h; MC=52-48%, w.b.) NH(3) removal remained high but N(2)O net generation decreased to near zero. In the falling DR stage (1200-1480 h; MC=44-13%) N(2)O generation decreased, CH(4) increased, and NH(3) was no longer removed. No ammonia removal or greenhouse gas generation was observed in the stable-dry system (1500-2500 h; MC=13%). These results indicate that media should remain toward the drier region of the constant DR (in close proximity to the falling DR stage; MC=50%, approx.), to maintain high levels of NH(3) removal, reduced levels of N(2)O generation, and nullify levels of CH(4

  10. Shape Memory Alloy Adaptive Structures, Phase I

    National Aeronautics and Space Administration — This SBIR Phase I effort will demonstrate and scale up an innovative manufacturing process that yields aerospace grade shape memory alloy (SMA) solids and periodic...

  11. Phase transitions in vector quantization and neural gas

    Witoelar, Aree; Biehl, Michael

    The statistical physics of off-learning is applied to winner-takes-all (WTA) and rank-based vector quantization (VQ), including the neural gas (NG). The analysis is based on the limit of high training temperatures and the annealed approximation. The typical learning behavior is evaluated for systems

  12. Gas phase dispersion in a small rotary kiln

    Spencer, B.B.

    1981-07-01

    A study was made of nonideal flow of gas in a rotary kiln reactor. A rotating tube 0.165 m in diameter by 2.17 m long, with internal lifting flights, was operated at room temperature. Rotational speeds from 2.0 to 7.0 rpm, air flow rates from 0.351 to 4.178 m 3 /h, and solid contents of 0.0, 5.1, and 15.3% of tube volume were studied. Residence time distribution of the gas was measured by means of the pulse injection technique using a helium tracer. A model was developed based on dispersive flow that exchanges with a deadwater region. Two parameters, a dispersion number describing bulk gas flow and an interchange factor describing exchange between the flow region and the gas trapped in the solids bed, were sufficient to correlate the data, but these parameters are sensitive to experimental error. The model is applicable to analysis of other flow systems, such as packed beds

  13. Oriented xenon hydride molecules in the gas phase

    Buck, U.; Fárník, Michal

    2006-01-01

    Roč. 25, č. 4 (2006), s. 583-612 ISSN 0144-235X Grant - others:Deutsche Forschungsgemeinschaft(DE) SFB 357 Institutional research plan: CEZ:AV0Z40400503 Keywords : photofragment translational spectroscopy * charge transfer molecules * low temperature matrices * neutral rare-gas Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.036, year: 2006

  14. Ceramic stationary gas turbine development. Final report, Phase 1

    NONE

    1994-09-01

    This report summarizes work performed by Solar Turbines Inc. and its subcontractors during the period September 25, 1992 through April 30, 1993. The objective of the work is to improve the performance of stationary gas turbines in cogeneration through implementation of selected ceramic components.

  15. Conformational reduction of DOPA in the gas phase studied by laser desorption supersonic jet laser spectroscopy.

    Ishiuchi, Shun-ichi; Mitsuda, Haruhiko; Asakawa, Toshiro; Miyazaki, Mitsuhiko; Fujii, Masaaki

    2011-05-07

    The conformational reduction in catecholamine neurotransmitters was studied by resonance enhanced multi photon ionization (REMPI), ultraviolet-ultraviolet (UV-UV) hole burning and infrared (IR) dip spectroscopy with applying a laser desorption supersonic jet technique to DOPA, which is one of the catecholamine neurotransmitters and has one more phenolic OH group than tyrosine. It is concluded that DOPA has a single observable conformer in the gas phase at low temperature. Quantum chemical calculations at several levels with or without the dispersion correction were also carried out to study stable conformations. From the comparison between the computational IR spectra and the experimental ones, the most stable structure was determined. It is strongly suggested that the conformational reduction is caused by electrostatic interactions, such as a dipole-dipole interaction, between the chain and OH groups. This journal is © the Owner Societies 2011

  16. Gas phase enthalpies of formation of nitrobenzamides using combustion calorimetry and thermal analysis

    Ximello, Arturo; Flores, Henoc; Rojas, Aarón; Adriana Camarillo, E.; Patricia Amador, M.

    2014-01-01

    Graphical abstract: - Highlights: • Formation enthalpies of the nitrobenzamides were derived from combustion calorimetry. • Enthalpies of vaporisation and sublimation were calculated by thermogravimetry. • From gas phase enthalpies of formation the stability of the isomers is studied. • Stability of isomers is not driven by a steric hindrance between functional groups. - Abstract: The standard molar energies of combustion of 2-nitrobenzamide, 3-nitrobenzamide and 4-nitrobenzamide were determined with an isoperibolic, static-bomb, combustion calorimeter. From the combustion results, the standard molar enthalpies of combustion and formation for these compounds in the condensed phase at T = 298.15 K were derived. Subsequently, to determine the enthalpies of sublimation, the vapour pressure data as a function of the temperature for the compounds under investigation were estimated using thermogravimetry by applying Langmuir’s equation, and the enthalpies of vaporisation were derived. Standard enthalpies of fusion were measured by differential scanning calorimetry then added to those of vaporisation to obtain reliable results for the enthalpy of sublimation. From the combustion and sublimation data, the gas phase enthalpies of formation were determined to be (−138.9 ± 3.5) kJ · mol −1 , (−122.9 ± 2.9) kJ · mol −1 and (−108.5 ± 3.7) kJ · mol −1 for the ortho, meta and para isomers of nitrobenzamide, respectively. The meaning of these results with regard to the enthalpic stability of these molecular structures is discussed herein

  17. Numerical simulation of gas-solid two-phase flow in U-beam separator

    Zhou, X Y; Chen, X P; Dou, H S; Zhang, H Z; Ruan, J M

    2015-01-01

    Numerical simulation is carried out for gas-solid two-phase flow in a U-beam separator. In this study, the U-beam is altered with the inlet fins in order to improve the performance of the separator. The inlet fin angle of the separator are 30°, 35°, 40°, 45°, 50°, 55 ° and 60°. The governing equations are the Reynolds-Averaged Navier-Stokes equation with the standard k-ε model and the discrete phase model (DPM) describing the discrete two - phase flow as well as stochastic tracking model. Results show that the pressure drop deviation with fins is within 3% from those without fins. It is found that there is a maximum separation efficiency at the fin angle of 35°. Fin induces generation of a stagnation region which could collect particles and lead to change of vortical structures. The fin induced flow also causes the turbulent intensity inside the baffle to decrease to facilitate separation

  18. Structural Changes of PVDF Membranes by Phase Separation Control

    Lee, Semin; Kim, Sung Soo

    2016-01-01

    Thermally induced phase separation (TIPS) and nonsolvent induced phase separation (NIPS) were simultaneously induced for the preparation of flat PVDF membranes. N-methyl-2-pyrrolidone (NMP) was used as a solvent and dibutyl-phthlate (DBP) was used as a diluent for PVDF. When PVDF was melt blended with NMP and DBP, crystallization temperature was lowered for TIPS and unstable region was expanded for NIPS. Ratio of solvent to diluent changed the phase separation mechanism to obtain the various membrane structures. Contact mode of dope solution with nonsolvent determined the dominant phase separation behavior. Since heat transfer rate was greater than mass transfer rate, surface structure was formed by NIPS and inner structure was by TIPS. Quenching temperature of dope solution also affected the phase separation mechanism and phase separation rate to result in the variation of structure

  19. Fission gas release of MOX with heterogeneous structure

    Nakae, N.; Akiyama, H.; Kamimura, K; Delville, R.; Jutier, F.; Verwerft, M.; Miura, H.; Baba, T.

    2015-01-01

    It is very useful for fuel integrity evaluation to accumulate knowledge base on fuel behavior of uranium and plutonium mixed oxide (MOX) fuel used in light water reactors (LWRs). Fission gas release is one of fuel behaviors which have an impact on fuel integrity evaluation. Fission gas release behavior of MOX fuels having heterogeneous structure is focused in this study. MOX fuel rods with a heterogeneous fuel microstructure were irradiated in Halden reactor (IFA-702) and the BR-3/BR-2 CALLISTO Loop (CHIPS program). The 85 Kr gamma spectrometry measurements were carried out in specific cycles in order to examine the concerned LHR (Linear Heat Rate) for fission gas release in the CHIPS program. The concerned LHR is defined in this paper to be the LHR at which a certain additional fission gas release thermally occurs. Post-irradiation examination was performed to understand the fission gas release behavior in connection with the pellet microstructure. The followings conclusions can be made from this study. First, the concerned LHR for fission gas release is estimated to be in the range of 20-23 kW/m with burnup over 37 GWd/tM. It is moreover guessed that the concerned LHR for fission gas release tends to decrease with increasing burnup. Secondly It is observed that FGR (fission gas release rate) is positively correlated with LHR when the LHR exceeds the concerned value. Thirdly, when burnup dependence of fission gas release is discussed, effective burnup should be taken into account. The effective burnup is defined as the burnup at which the LHR should be exceed the concerned value at the last time during all the irradiation period. And fourthly, it appears that FGR inside Pu spots is higher than outside and that retained (not released) fission gases mainly exist in the fission gas bubbles. Since fission gases in bubbles are considered to be easily released during fuel temperature increase, this information is very important to estimate fission gas release behavior

  20. Liquid-gas phase transition and isospin fractionation in intermediate energy heavy ion collisions

    Xing Yongzhong; Liu Jianye; Guo Wenjun

    2004-01-01

    The liquid-gas phase transition in the heavy ion collisions and nuclear matter has been an important topic and got achievements, such as, based on the studies by H.Q. Song et al the critical temperature of liquid-gas phase transition enhances with increasing the mass of system and reduces as the increase of the neutron proton ratio of system. As authors know that both the liquid-gas phase transition and the isospin fractionation occur in the spinodal instability region at the nuclear density below the normal nuclear density. In particular, these two dynamical processes lead to the separation of nuclear matter into the liquid phase and gas phase. In this case to compare their dynamical behaviors is interested. The authors investigate the dependence of isospin fractionation degree on the mass and neutron proton ratio of system by using the isospin dependent quantum molecular dynamics model. The authors found that the degree of isospin fractionation (N/Z) n /(N/Z) imf decreases with increasing the mass of the system. This is just similar to the enhance of the critical temperature of liquid-gas phase transition T c as the increase of system mass. Because the enhance of T c is not favorable for the liquid-gas transition taking place, which reduces the isospin fractionation process and leads to decrease of (N/Z) n /(N/Z) imf . However the degree of isospin fractionation enhances with increasing the neutron proton ratio of the system. It is just corresponding to the reduce of T c of the liquid-gas phase transition as the increase of the isospin fractionation of the system. Because the reduce of T c enhances the liquid-gas phase transition process and also prompts the isospin fractionation process leading the increase of the isospin fractionation degree. To sum up, there are very similar dynamical behaviors for the degree of isospin fractionation and the critical temperature of the liquid-gas phase transition. So dynamical properties of the liquid-gas phase transition can

  1. Infrared multiple photon dissociation action spectroscopy of alkali metal cation-cyclen complexes: Effects of alkali metal cation size on gas-phase conformation

    Austin, C.A.; Chen, Y.; Kaczan, C.M.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cationized complexes of cyclen (1,4,7,10-tetraazacyclododecane) are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and electronic structure theory calculations. The measured IRMPD action spectra of four M+(cyclen) complexes are

  2. Experimental and numerical investigation of gas phase freeboard combustion

    Andersen, J.; Jensen, Peter Arendt; Meyer, K.E.

    2009-01-01

    Experimental data for velocity field, temperatures, and gas composition have been obtained from a 50 kW axisymmetric non-swirling natural gas fired combustion setup under two different settings. The reactor was constructed to simulate the conditions in the freeboard of a grate-fired boiler...... but under well-defined conditions. The experimental results are compared to computational fluid dynamics (CFD) modeling predictions, using the eddy dissipation model (EDM) its well as the eddy dissipation concept (EDC). The use of EDC allows for implementation of more advanced combustion schemes; we have...... tested the four-step global mechanism by Jones and Lindstedt (Combust. Flame 1988, 73, 233-249), and the 16 species and 41 reaction skeletal mechanism by Yang and Pope (Combust. Flame 1998, 112 16-32). The CFD model captured the main features of the combustion process and flow patterns. The application...

  3. Experimental and numerical investigation of gas phase freeboard combustion

    Andersen, Jimmy; Jensen, Peter Arendt; Hvid, S.L.

    2009-01-01

    In part 1 of the present work (10.1021/ef900752a), experimental data and computational fluid dynamics (CFD) modeling predictions for velocity field, temperatures, and major species were compared fora 50 kW axisymmetric, non-swirling natural gas Fired combustion setup, constructed to simulate...... the conditions in the freeboard of it grate-fired boiler. Here, in part 2, the ability of CFD to predict volatile N oxidation to NO and N(2) is evaluated. Trace amounts of ammonia were added to the natural gas, and local measurements of NH(3) and NO in the reactor were compared to modeling predictions. Different...... modeling approaches, including global schemes and analytically reduced mechanisms, were tested in the CFD calculations. In addition, the simplified schemes were compared to reference calculations with a detailed mechanism under isothermal plug flow reactor conditions. While none of the global ammonia...

  4. The crystal structure and the phase transitions of pyridinium trifluoromethanesulfonate

    Jesariew, Dominik; Ilczyszyn, Maria M; Pietraszko, Adam

    2014-01-01

    The calorimetric and optical studies and the structural properties of pyridinium trifluoromethanesulfonate (abbreviated as PyHOTf) are reported. A sequence of four fully reversible solid–solid phase transitions, at 223.0, 309.0, 359.9 and 394.3 K, has been discovered. The phase transition sequence was confirmed by x-ray diffraction data. The crystal structures of three phases (V, IV and III) have been determined from the single crystal x-ray diffraction data. Structural properties of the high temperature phases are characterized using powder x-ray diffraction data measured in the 290–425 K temperature range. The structural changes triggered by the temperature change are discussed in relation to the phase transitions. Two low temperature phases (V and IV) belong to the P4 3 2 1 2 space group of the tetragonal system. The intermediate phases (III and II) are monoclinic and the prototype high temperature phase (I) is a pseudo-cubic (tetragonal) one. The low temperature phases (V and IV) are well ordered. The crystal structure of intermediate (III and II) and prototype (I) phases are characterized by high disorder of the pyridinium cations and triflate anions. (papers)

  5. Phases of a polar spin-1 Bose gas in a magnetic field

    Kis-Szabo, Krisztian; Szepfalusy, Peter; Szirmai, Gergely

    2007-01-01

    The two Bose-Einstein condensed phases of a polar spin-1 gas at nonzero magnetizations and temperatures are investigated. The Hugenholtz-Pines theorem is generalized to this system. Crossover to a quantum phase transition is also studied. Results are discussed in a mean field approximation

  6. Gas-phase polynuclear aromatic hydrocarbons (PAH) in vehicle exhaust: A method for collection and analysis

    Seigl, W.O.; Chladek, E.

    1990-01-01

    Gas-phase polynuclear aromatic hydrocarbons (PAH) are emitted at low levels in vehicle exhaust compared to other hydrocarbon emissions. A method has been developed involving the trapping of gas phase emissions on Tenax, a macrorecticular porous polymer, followed by thermal desorption onto a capillary gas chromatography column. Gas chromatography/mass spectrometry (GC/MS) was used for the chemical analysis. A detection limit of 0.05 ng was achieved for several gas-phase PAH. This high sensitivity enables the speciation and quantitation of gas-phase PAH collected from a dilution tube during standard driving (test) cycles. The method was demonstrated for the analysis of 9 PAH in the exhaust from a 1987 vehicle (with and without catalyst) during the hot start transient phase of the EPA urban dynamometer driving schedule. The PAH measured include naphthalene, 2-methyl- and 1-methylnaphthalene, biphenyl, fluorene, phenanthrene, anthracene, fluoranthene and pyrene. The four most abundant PAH observed are naphthalene, 2-methyl and 1-methylnaphthalene, and biphenyl, in that order

  7. Electronic structure theory of alloy phase stability

    Turchi, P.E.A.; Sluiter, M.

    1992-01-01

    We present a brief overview of the advanced methodology which has been developed and applied to the study of phase stability properties in substitutional alloys. The approach is based on the real space version of the Generalized Perturbation Method within the Korringa-Kohn-Rostoker multiple scattering formulation of the Coherent Potential Approximation. Temperature effects are taken into account with a generalized meanfield approach, namely the Cluster Variation Method, or with Monte-Carlo simulations. We show that this approach is well suited for studying ground state properties of substitutional alloys, for calculating energies of idealized interfaces and antiphase boundaries, and finally to compute alloy phase diagrams

  8. Maxwell's Law Based Models for Liquid and Gas Phase Diffusivities in Variably-Saturated Soil

    Mamamoto, Shoichiro; Møldrup, Per; Kawamoto, Ken

    2012-01-01

    -s,D-l). Different percolation threshold terms adopted from recent studies for gas (D-s,D-g) and solute (D-s,D-l) diffusion were applied. For gas diffusion, epsilon(th) was a function of bulk density (total porosity), while for solute diffusion theta(th) was best described by volumetric content of finer soil...... particles (clay and organic matter), FINESvol. The resulting LIquid and GAs diffusivity and tortuosity (LIGA) models were tested against D-s,D-g and D-s,D-l data for differently-textured soils and performed well against the measured data across soil types. A sensitivity analysis using the new Maxwell's Law...... based LIGA models implied that the liquid phase but not the gaseous-phase tortuosity was controlled by soil type. The analyses also suggested very different pathways and fluid-phase connectivity for gas and solute diffusion in unsaturated soil...

  9. Technology assessment of long distance liquid natural gas pipelines. Phase 8. Cold utilization and rural service

    1977-02-01

    This phase of the investigation presents a summary of material relating to: (1) actual or potential applications for the very large refrigeration effects inherent in the vaporization of liquid natural gas; and (2) rural service gas supplies adjacent to the route of a trunk liquid natural gas line. A variety of concepts for cold utilization are discussed. The Canadian prospects for cold utilization include: electric power generation; oxygen production for integration with a coal gasification project; and the use of refrigeration stages in the petrochemical processing of natural gas, for example, ethane separation and processing to produce ethylene and ammonia.

  10. Microfluidic and nanofluidic phase behaviour characterization for industrial CO2, oil and gas.

    Bao, Bo; Riordon, Jason; Mostowfi, Farshid; Sinton, David

    2017-08-08

    Microfluidic systems that leverage unique micro-scale phenomena have been developed to provide rapid, accurate and robust analysis, predominantly for biomedical applications. These attributes, in addition to the ability to access high temperatures and pressures, have motivated recent expanded applications in phase measurements relevant to industrial CO 2 , oil and gas applications. We here present a comprehensive review of this exciting new field, separating microfluidic and nanofluidic approaches. Microfluidics is practical, and provides similar phase properties analysis to established bulk methods with advantages in speed, control and sample size. Nanofluidic phase behaviour can deviate from bulk measurements, which is of particular relevance to emerging unconventional oil and gas production from nanoporous shale. In short, microfluidics offers a practical, compelling replacement of current bulk phase measurement systems, whereas nanofluidics is not practical, but uniquely provides insight into phase change phenomena at nanoscales. Challenges, trends and opportunities for phase measurements at both scales are highlighted.

  11. Spectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phases

    Tokatli, A.; Ucun, F.; Sütçü, K.; Osmanoğlu, Y. E.; Osmanoğlu, Ş.

    2018-02-01

    In this study the conformational behavior of cycloheximide in the gas and solution (CHCl3) phases has theoretically been investigated by spectroscopic and quantum chemical properties using density functional theory (wB97X-D) method with 6-31++G(d,p) basis set, for the first time. The calculated IR results reveal that in the ground state the molecule exits as a mixture of the chair and twist-boat conformers in the gas phase, while the calculated NMR results reveal that it only exits as the chair conformer in the solution phase. In order to obtain the contributions coming from intramolecular interactions to the stability of the conformers in the gas and solution phases, the quantum theory of atoms in molecules (QTAIM), noncovalent interactions (NCI) method, and natural bond orbital analysis (NBO) have been employed. The QTAIM and NCI methods indicated that by intramolecular interactions with bond critical point (BCP) the twist-boat conformer is more stabilized than the chair conformer, while by steric interactions it is more destabilized. Considering that these interactions balance each other, the stabilities of the conformers are understood to be dictated by the van der Waals interactions. The NBO analyses show that the hyperconjugative and steric effects play an important role in the stabilization in the gas and solution phases. Furthermore, to get a better understanding of the chemical behavior of this important antibiotic drug we have evaluated and, commented the global and local reactivity descriptors of the both conformers. Finally, the EPR analysis of γ-irradiated cycloheximide has been done. The comparison of the experimental and calculated data have showed the inducement of a radical structure of (CH2)2ĊCH2 in the molecule. The experimental EPR spectrum has also confirmed that the molecule simultaneously exists in the chair and twist-boat conformers in the solid phase.

  12. The electron spectrum of UF6 recorded in the gas phase

    Mârtensson, N.; Malmquist, P.-Å.; Svensson, S.; Johansson, B.

    1984-06-01

    Gas phase core and valence electron spectra from UF6, excited by AlKα monochromatized x rays, in the binding energy range 0-1000 eV are presented. It is shown that the AlKα excited valence electron spectrum can be used to reassign the highest occupied molecular orbital (HOMO) in UF6. Many-body effects on the core levels are discussed and core level lifetimes are determined. The shift between solid phase and gas phase electron binding energies for core lines is used to discuss the U5 f population in UF6.

  13. Problem of phase transitions in nuclear structure

    Scharff-Goldhaber, G.

    1980-01-01

    Phase transitions between rotational and vibrational nuclei are discussed from the point of view of the variable moment of inertia model. A three-dimensional plot of the ground-state moments of inertia of even-even nuclei vs N and Z is shown. 3 figures

  14. On the structure of phase synchronized chaos

    Mosekilde, Erik; Zhusubaliyev, Zhanybai T.; Laugesen, Jakob L.

    2013-01-01

    It is well-known that the transition to chaotic phase synchronization for a periodically driven chaotic oscillator of spiral type involves a dense set of saddle-node bifurcations. However, the way of formation and precise organization of these saddle node bifurcation curves have only recently bee...

  15. Molecular structure of the lecithin ripple phase

    de Vries, AH; Yefimov, S; Mark, AE; Marrink, SJ

    2005-01-01

    Molecular dynamics simulations of lecithin lipid bilayers in water as they are cooled from the liquid crystalline phase show the spontaneous formation of rippled bilayers. The ripple consists of two domains of different length and orientation, connected by a kink. The organization of the lipids in

  16. Topological phase transition in the quench dynamics of a one-dimensional Fermi gas

    Wang, Pei; Yi, Wei; Xianlong, Gao

    2014-01-01

    We study the quench dynamics of a one-dimensional ultracold Fermi gas in an optical lattice potential with synthetic spin-orbit coupling. At equilibrium, the ground state of the system can undergo a topological phase transition and become a topological superfluid with Majorana edge states. As the interaction is quenched near the topological phase boundary, we identify an interesting dynamical phase transition of the quenched state in the long-time limit, characterized by an abrupt change of t...

  17. Phase diagram of a polarized Fermi gas across a Feshbach resonance in a potential trap

    Yi, W.; Duan, L.-M.

    2006-01-01

    We map out the detailed phase diagram of a trapped ultracold Fermi gas with population imbalance across a wide Feshbach resonance. We show that under the local density approximation, the properties of the atoms in any (anisotropic) harmonic traps are universally characterized by three dimensionless parameters: the normalized temperature, the dimensionless interaction strength, and the population imbalance. We then discuss the possible quantum phases in the trap, and quantitatively characterize their phase boundaries in various typical parameter regions

  18. Static Structural and Modal Analysis of Gas Turbine Blade

    Ranjan Kumar, Ravi; Pandey, K. M., Prof.

    2017-08-01

    Gas turbine is one of the most versatile items of turbo machinery nowadays. It is used in different modes such as power generation, oil and gas, process plants, aviation, domestic and related small industries. This paper is based on the problems concerning blade profile selection, material selection and turbine rotor blade vibration that seriously impact the induced stress-deformation and structural functioning of developmental gas turbine engine. In this paper for generating specific power by rotating blade at specific RPM, blade profile and material has been decided by static structural analysis. Gas turbine rotating blade RPM is decided by Modal Analysis so that the natural frequency of blade should not match with the excitation frequency. For the above blade profile has been modeled in SOLIDWORKS and analysis has been done in ANSYS WORKBENCH 14. Existing NACA6409 profile has been selected as base model and then it is modified by bending it through 72.5° and 145°. Hence these three different blade profiles have been analyzed for three different materials viz. Super Alloy X, Nimonic 80A and Inconel 625 at three different speed viz. 20000, 40000 and 60000RPM. It is found that NACA6409 with 72.5° bent gives best result for all material at all speed. Among all the material Inconel 625 gives best result. Hence Blade of Inconel 625 having 72.5° bent profile is the best combination for all RPM.

  19. Flow measurement in two-phase (gas-liquid) systems

    Hewitt, G.F.; Whalley, P.B.

    1980-01-01

    The main methods of measuring mass flow and quality in gas-liquid flows in industrial situations are reviewed. These include gamma densitometry coupled with differential pressure devices such as crifice plates, turbine flow meters and drag screens. For each method the principle of operation, and the advantages and disadvantages, are given. Some further techniques which are currently being investigated and developed for routine use are also described briefly. Finally the detailed flow measurements possible on a particular flow pattern - annular flow - is examined. (author)

  20. Synthesis of refractory organic matter in the ionized gas phase of the solar nebula.

    Kuga, Maïa; Marty, Bernard; Marrocchi, Yves; Tissandier, Laurent

    2015-06-09

    In the nascent solar system, primitive organic matter was a major contributor of volatile elements to planetary bodies, and could have played a key role in the development of the biosphere. However, the origin of primitive organics is poorly understood. Most scenarios advocate cold synthesis in the interstellar medium or in the outer solar system. Here, we report the synthesis of solid organics under ionizing conditions in a plasma setup from gas mixtures (H2(O)-CO-N2-noble gases) reminiscent of the protosolar nebula composition. Ionization of the gas phase was achieved at temperatures up to 1,000 K. Synthesized solid compounds share chemical and structural features with chondritic organics, and noble gases trapped during the experiments reproduce the elemental and isotopic fractionations observed in primitive organics. These results strongly suggest that both the formation of chondritic refractory organics and the trapping of noble gases took place simultaneously in the ionized areas of the protoplanetary disk, via photon- and/or electron-driven reactions and processing. Thus, synthesis of primitive organics might not have required a cold environment and could have occurred anywhere the disk is ionized, including in its warm regions. This scenario also supports N2 photodissociation as the cause of the large nitrogen isotopic range in the solar system.

  1. Silica, alumina and aluminosilicates as solid stationary phases in gas chromatography

    S. Faramawy

    2016-09-01

    Full Text Available Silica, alumina and Aluminosilicates of different Si/Al ratios were prepared by conventional precipitation or co-precipitation methods and then subjected to thermal treatment at 800 °C. The parent and thermally treated materials were characterized by means of FTIR, SEM and thermal analysis (DTA and TGA in order to elucidate the main structural properties. Surface textural characteristics were investigated by means of nitrogen adsorption–desorption isotherms at −196 °C. Pore size distribution curves indicated the presence of mesopores (10–150 Å exhibiting maxima at 35 Å. The maxima were shifted toward higher values by increasing the alumina content. Thermodynamic parameters, ΔH, ΔG and ΔS, were determined by means of inverse gas chromatography using n-hexane as a probe. The untreated and thermally treated materials were tested as solid stationary phases in gas chromatography. The separation efficiency of various non polar and polar compounds was explained in terms of surface texture and thermodynamic parameters.

  2. THE COUPLED PHYSICAL STRUCTURE OF GAS AND DUST IN THE IM Lup PROTOPLANETARY DISK

    Cleeves, L. Ilsedore; Öberg, Karin I.; Wilner, David J.; Huang, Jane; Loomis, Ryan A.; Andrews, Sean M.; Czekala, Ian, E-mail: ilse.cleeves@cfa.harvard.edu [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

    2016-12-01

    The spatial distribution of gas and solids in protoplanetary disks determines the composition and formation efficiency of planetary systems. A number of disks show starkly different distributions for the gas and small grains compared to millimeter–centimeter-sized dust. We present new Atacama Large Millimeter/Submillimeter Array observations of the dust continuum, CO, {sup 13}CO, and C{sup 18}O in the IM Lup protoplanetary disk, one of the first systems where this dust–gas dichotomy was clearly seen. The {sup 12}CO is detected out to a radius of 970 au, while the millimeter continuum emission is truncated at just 313 au. Based upon these data, we have built a comprehensive physical and chemical model for the disk structure, which takes into account the complex, coupled nature of the gas and dust and the interplay between the local and external environment. We constrain the distributions of gas and dust, the gas temperatures, the CO abundances, the CO optical depths, and the incident external radiation field. We find that the reduction/removal of dust from the outer disk exposes this region to higher stellar and external radiation and decreases the rate of freeze-out, allowing CO to remain in the gas out to large radial distances. We estimate a gas-phase CO abundance of 5% of the interstellar medium value and a low external radiation field ( G {sub 0} ≲ 4). The latter is consistent with that expected from the local stellar population. We additionally find tentative evidence for ring-like continuum substructure, suggestions of isotope-selective photodissociation, and a diffuse gas halo.

  3. Neutrino opacities and the pasta phase structure

    Menezes, D.P.; Alloy, M.D.

    2011-01-01

    The diffusion coefficients that are related to the neutrino opacities are calculated in such a way that the formation of nuclear pasta and homogeneous matter at low densities are taken into account. Two methods are developed to build the pasta phase and their differences are outlined. One of them is chosen as part of a complete equation of state used in the calculation of the diffusion coefficients. Our results show that the mean free paths are significantly altered by the presence of nuclear pasta in stellar matter when compared with the results obtained with pure homogeneous matter. These differences in neutrino opacities will have consequences in the calculation of the Kelvin-Helmholtz phase of protoneutron stars. (author)

  4. Tuning of Preparational Factors Affecting the Morphological Structure and Gas Separation Property of Asymmetric Polysulfone Membranes

    Yuenyao, C.; Ruangdit, S.; Chittrakarn, T.

    2017-09-01

    The aim of this work was to study the effect of preparational factors such as solvent type, evaporation time (ET) and non-solvent additive, on the morphological structure, physical and gas separation properties of the prepared membrane samples by tuning of these parameters. Flat sheet asymmetric polysulfone (PSF) membranes were prepared by the dry/wet phase inversion process combined with the double coagulation bath method. The alteration of the prepared membranes were analyzed through scientific techniques such as Scanning Electron Microscope (SEM) and Dynamic Mechanical Thermal Analysis (DMTA). Furthermore, gas separation performance of membrane samples was measured in term of gas permeation and ideal selectivity of CO2/CH4. Experimental results showed that the change of preparational factors affected to the gas permeation of asymmetric PSF membranes. For example, the selective layer thickness increased with increasing of ET. This lead to increase significantly of ideal selectivity of CO2/CH4. The CO2/CH4 ideal selectivity was also increased with increase of ethanol (non-solvent additive) concentration in casting solution. In summary, the tuning of preparational factors affected to morphological structure, physical and gas separation properties of PSF membranes.

  5. Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

    Nguyen, Luan; Tao, Franklin Feng

    2018-02-01

    Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

  6. Structural isotopic effect of the α/β-phase transition in the vanadium hydride and its influence on the equilibrium coefficient of separation of hydrogen isotopes in the gas-solid system

    Magomedbekov, Eh.P.; Bochkarev, A.V.

    1999-01-01

    Equilibrium coefficient of hydrogen isotope separation (α H-D ) in the system of vanadium hydride VH n (solid, n ∼ 0.7)-H 2 (g) is measured by the counterbalancing method in a circulation facility and by the method of laser desorption at 298, 373, and 437 K. It is shown that the combination of highly anharmonic potential in the lattice octahedral sites and in significant difference in the energy of hydrogen atom coordination for tetra- and octahedral sites is the reason for unusual behaviour of the hydrogen isotope separation coefficient and the difference in crystal structures of vanadium hydride and deuteride [ru

  7. Exceptionally High Proton and Lithium Cation Gas-Phase Basicity of the Anti-Diabetic Drug Metformin.

    Raczyńska, Ewa D; Gal, Jean-François; Maria, Pierre-Charles; Michalec, Piotr; Zalewski, Marcin

    2017-11-16

    Substituted biguanides are known for their biological effect, and a few of them are used as drugs, the most prominent example being metformin (1,1-dimethylbiguanide, IUPAC name: N,N-dimethylimidodicarbonimidic diamide). Because of the presence of hydrogen atoms at the amino groups, biguanides exhibit a multiple tautomerism. This aspect of their structures was examined in detail for unsubstituted biguanide and metformin in the gas phase. At the density functional theory (DFT) level {essentially B3LYP/6-311+G(d,p)}, the most stable structures correspond to the conjugated, push-pull, system (NR 2 )(NH 2 )C═N-C(═NH)NH 2 (R = H, CH 3 ), further stabilized by an internal hydrogen bond. The structural and energetic aspects of protonation and lithium cation adduct formation of biguanide and metformin was examined at the same level of theory. The gas-phase protonation energetics reveal that the more stable tautomer is protonated at the terminal imino C═NH site, still with an internal hydrogen bond maintaining the structure of the neutral system. The calculated proton affinity and gas-phase basicity of the two molecules reach the domain of superbasicity. By contrast, the lithium cation prefers to bind the less stable, not fully conjugated, tautomer (NR 2 )C(═NH)-NH-C(═NH)NH 2 of biguanides, in which the two C═NH groups are separated by NH. This less stable form of biguanides binds Li + as a bidentate ligand, in agreement with what was reported in the literature for other metal cations in the solid phase. The quantitative assessment of resonance in biguanide, in metformin and in their protonated forms, using the HOMED and HOMA indices, reveals an increase in electron delocalization upon protonation. On the contrary, the most stable lithium cation adducts are less conjugated than the stable neutral biguanides, because the metal cation is better coordinated by the not-fully conjugated bidentate tautomer.

  8. Lightweight Structures Utilizing CNFs, Phase I

    National Aeronautics and Space Administration — AxNano proposes a novel method for producing robust, high-volume, cost-effective carbon fibers in support of next-generation materials for structural composite space...

  9. Expandable Habitat Outfit Structures, Phase I

    National Aeronautics and Space Administration — Topic H3.01 captures the need for robust, multipurpose deployable structures with high packing efficiencies for next generation orbital habitats. Multiple launch and...

  10. NONA Cure of Prepreg Structures, Phase II

    National Aeronautics and Space Administration — CRG's no-oven, no-autoclave (NONA) cure of OoA or autoclave prepreg materials allows the manufacture of large composite structures without the expensive and...

  11. Nano-Engineered Structural Joints, Phase I

    National Aeronautics and Space Administration — A versatile class of high-performance structural joints is proposed where massive interatomic bonds over the large surface areas of nanostructured surfaces...

  12. Lung Structure and the Intrinsic Challenges of Gas Exchange.

    Hsia, Connie C W; Hyde, Dallas M; Weibel, Ewald R

    2016-03-15

    Structural and functional complexities of the mammalian lung evolved to meet a unique set of challenges, namely, the provision of efficient delivery of inspired air to all lung units within a confined thoracic space, to build a large gas exchange surface associated with minimal barrier thickness and a microvascular network to accommodate the entire right ventricular cardiac output while withstanding cyclic mechanical stresses that increase several folds from rest to exercise. Intricate regulatory mechanisms at every level ensure that the dynamic capacities of ventilation, perfusion, diffusion, and chemical binding to hemoglobin are commensurate with usual metabolic demands and periodic extreme needs for activity and survival. This article reviews the structural design of mammalian and human lung, its functional challenges, limitations, and potential for adaptation. We discuss (i) the evolutionary origin of alveolar lungs and its advantages and compromises, (ii) structural determinants of alveolar gas exchange, including architecture of conducting bronchovascular trees that converge in gas exchange units, (iii) the challenges of matching ventilation, perfusion, and diffusion and tissue-erythrocyte and thoracopulmonary interactions. The notion of erythrocytes as an integral component of the gas exchanger is emphasized. We further discuss the signals, sources, and limits of structural plasticity of the lung in alveolar hypoxia and following a loss of lung units, and the promise and caveats of interventions aimed at augmenting endogenous adaptive responses. Our objective is to understand how individual components are matched at multiple levels to optimize organ function in the face of physiological demands or pathological constraints. Copyright © 2016 John Wiley & Sons, Inc.

  13. Gas Phase Thz Spectroscopy of Organosulfide and Organophosphorous Compounds Using a Synchrotron Source

    Cuisset, Arnaud; Smirnova, Irina; Bocquet, Robin; Hindle, Francis; Mouret, Gael; Sadovskii, Dmitrii A.; Pirali, Olivier; Roy, Pascale

    2011-06-01

    This study concerns the gas phase rovibrational spectroscopy of organosulfide and organophosphorous which are considered as non toxic model compounds in the analysis of chemical weapon materials, high pathogenic and mutagenic agents, and other environmentally interesting air-borne species. The coupling of the synchrotron radiation with multipass cells and the FTIR spectrometer allowed to obtain very conclusive results in term of sensitivity and resolution and improved the previous results obtained with classical sources. For DMSO, using an optical path of 150 m the spectra have been recorded at the ultimate resolution of 0.001 Cm-1 allowing to fully resolve the rotational structure of the lowest vibrational modes observed in the THz region. In the 290 - 420 Cm-1 region, the rovibrational spectrum of the "perpendicular" and "parallel" vibrational bands associated with, respectively, the asymmetric ν23 and symmetric ν11 bending modes of DMSO have been recorded with a resolution of 1.5× 10-3 Cm-1. The gas phase vibrational spectra of organophosphorous compounds were measured by FTIR spectroscopy using the vapor pressure of the compounds. Except for TBP, the room temperature vapor pressure was sufficient to detect all active vibrational modes from THz to NIR domain. Contrary to DMSO, the rotational patterns of alkyl phosphates and alkyl phosphonates could not be resolved; only a vibrational analysis may be performed. Nevertheless, the spectral fingerprints observed in the THz region allowed a clear discrimination between the molecules and between the different molecular conformations. A. Cuisset, G. Mouret, O. Pirali, P. Roy, F. Cazier, H. Nouali, J. Demaison, J. Phys. Chem. B, 2008, 112:, 12516-12525 A. Cuisset, L. Nanobashvili, I. Smirnova, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy and D. A. Sadovskií, Chem. Phys. Lett., 2010, 492: 30-34 I. Smirnova, A. Cuisset, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy, J. Phys. Chem. B, 2010, 114: 16936-16947.

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

    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.

  15. Gas-phase chemistry of element 114, flerovium

    Yakushev Alexander

    2016-01-01

    Full Text Available Element 114 was discovered in 2000 by the Dubna-Livermore collaboration, and in 2012 it was named flerovium. It belongs to the group 14 of the periodic table of elements. A strong relativistic stabilisation of the valence shell 7s27p21/2 is expected due to the orbital splitting and the contraction not only of the 7s2 but also of the spherical 7p21/2 closed subshell, resulting in the enhanced volatility and inertness. Flerovium was studied chemically by gas-solid chromatography upon its adsorption on a gold surface. Two experimental results on Fl chemistry have been published so far. Based on observation of three atoms, a weak interaction of flerovium with gold was suggested in the first study. Authors of the second study concluded on the metallic character after the observation of two Fl atoms deposited on gold at room temperature.

  16. Fixing arsenic contained in a gas phase using solid hematite

    Balladares, E.; Gonzalez, A.; Rarra, R.; Sanchez, M.

    2004-01-01

    Feasibility to obtain ferric arsenate starting from arsenic containing gas in contact with Fe 3 O 3 has been studied. Thermodynamic stability of the system Fe-As-O was analysed in order to verify conditions to form Fe x As y O z type compounds. Experiments were made using a hematite sample suspended in a thermogravimetric device. As 4 O 6 was generated starting from solid As 2 O 3 which was circulating through the iron oxide. Final samples were analysed chemically and by means of DRX, verifying the formation of FeAsO 4 , FeAsO 4 .2h 2 O and FeAsO 4 .(H 2 O) 2 in small quantities. Tests in porous bed and pellets were carried out, studying the effect of: porosity, temperature and oxygen potential. The largest conversion obtained was 10% at 800 degree centigrade, pO 2 =50% and porosity=0.883. (Author) 9 refs

  17. Modelling gas migration in compacted bentonite: GAMBIT Club Phase 2. Final report

    Swift, B.T.; Hoch, A.R.; Rodwell, W.R. [AEA Technology (United Kingdom)

    2001-01-01

    This report describes the second phase of a programme of work to develop a computational model of gas migration through highly compacted bentonite. Experimental data that have appeared since the earlier report are reviewed for the additional information they might provide on the mechanism of gas migration in bentonite. Experiments carried out by Horseman and Harrigton (British Geological Survey) continued to provide the main data sets used in model evaluation. The earlier work (POSIVA Report 98-08) had resulted in a preliminary model of gas migration whose main features are gas invasion by microcrack propagation, and dilation of the pathways formed with increasing gas pressure. New work was carried out to further explore the capabilities of this model. In addition, a feature was added to the model to simulate gas pathway creation by water displacement rather than crack propagation. The development of a new alternative gas migration model is described. This is based on a volume-averaged representation of gas migration rather than on a description of flow in discrete pathways. Evaluation of this alternative model showed that it can produce similar agreement with experimental results to the other models examined. The implications of flow geometry, confining conditions and flow boundary conditions on gas migration behaviour in bentonite are reviewed. Proposals are made for the development of the new model into a tool for simulating gas migration through a bentonite buffer around a waste canister, and for possible enhancements to the model that might remove some of its currently perceived deficiencies. (orig.)

  18. Two-phase behavior and compression effects in the PEFC gas diffusion medium

    Mukherjee, Partha P [Los Alamos National Laboratory; Kang, Qinjun [Los Alamos National Laboratory; Schulz, Volker P [APL-LANDAU GMBH; Wang, Chao - Yang [PENN STATE UNIV; Becker, Jurgen [NON LANL; Wiegmann, Andreas [NON LANL

    2009-01-01

    A key performance limitation in the polymer electrolyte fuel cell (PEFC), manifested in terms of mass transport loss, originates from liquid water transport and resulting flooding phenomena in the constituent components. A key contributor to the mass transport loss is the cathode gas diffusion layer (GDL) due to the blockage of available pore space by liquid water thus rendering hindered oxygen transport to the active reaction sites in the electrode. The GDL, therefore, plays an important role in the overall water management in the PEFC. The underlying pore-morphology and the wetting characteristics have significant influence on the flooding dynamics in the GDL. Another important factor is the role of cell compression on the GDL microstructural change and hence the underlying two-phase behavior. In this article, we present the development of a pore-scale modeling formalism coupled With realistic microstructural delineation and reduced order compression model to study the structure-wettability influence and the effect of compression on two-phase behavior in the PEFC GDL.

  19. Modelling gas migration in compacted bentonite: gambit club phase 3. Final report

    Hoch, A.R.; Cliffe, K.A.; Swift, B.T.; Rodwell, W.R.

    2004-04-01

    This report describes the third phase of a programme of work to develop a computational model of gas migration through highly compacted water-saturated bentonite. One difficulty with this endeavour is the definitive determination of the mechanism of the gas migration from the available experimental data. The report contains a brief review of the experimental data and their interpretation. The model development work reported involves the investigation of two ways of enhancing a model proposed in the previous phase of the programme. This model was based on the concept that gas migration pathways were created by consolidating the clay fabric by application of gas pressure to create porosity through which the gas could flow. The two developments of this model that are separately explored in this work are: (a) The incorporation of a proper treatment of the stress-strain behaviour of the clay in (b) response to gas migration. The previous model had only considered stress effects through simple volume changes to the clay fabric. The inclusion of a dual-porosity feature into the model in an attempt to address the role that the clay fabric might play in gas migration through the clay, in particular the role that pre-existing interstack voids might have in gas migration. The consideration of hysteresis effects was also included in this study. As in previous GAMBIT Club work, the models are tested against the results of laboratory experiments. (orig.)

  20. Discontinuous structural phase transition of liquid metal and alloys (2)

    Wang, Li; Liu, Jiantong

    2004-01-01

    The diameter (d f ) of diffusion fluid cluster before and after phase transition has been calculated in terms of the paper ''Discontinuous structural phase transition of liquid metal and alloy (1)'' Physics Letters. A 326 (2004) 429-435, to verify quantitatively the discontinuity of structural phase transition; the phenomena of thermal contraction and thermal expansion during the phase transition, together with the evolution model of discontinuous structural phase transition are also discussed in this Letter to explore further the nature of structural transition; In addition, based on the viscosity experimental result mentioned in paper [Y. Waseda, The Structure of Non-Crystalline Materials--Liquids and Amorphous Solids, McGraw-Hill, New York, 1980], we present an approach to draw an embryo of the liquid-liquid (L-L) phase diagram for binary alloys above liquidus in the paper, expecting to guide metallurgy process so as to improve the properties of alloys. The idea that controls amorphous structure and its properties by means of the L-L phase diagram for alloys and by the rapid cooling technique to form the amorphous alloy has been brought forward in the end

  1. Structural decomposition analysis of Australia's greenhouse gas emissions

    Wood, Richard

    2009-01-01

    A complex system of production links our greenhouse gas emissions to our consumer demands. Whilst progress may be made in improving efficiency, other changes in the production structure may easily annul global improvements. Utilising a structural decomposition analysis, a comparative-static technique of input-output analysis, over a time period of around 30 years, net greenhouse emissions are decomposed in this study into the effects, due to changes in industrial efficiency, forward linkages, inter-industry structure, backward linkages, type of final demand, cause of final demand, population affluence, population size, and mix and level of exports. Historically, significant competing forces at both the whole of economy and industrial scale have been mitigating potential improvements. Key sectors and structural influences are identified that have historically shown the greatest potential for change, and would likely have the greatest net impact. Results clearly reinforce that the current dichotomy of growth and exports are the key problems in need of address.

  2. Market chances for innovative natural gas applications. The determination of market potential by means of a phase model

    Hoelen, Q.E.J.J.M.; Klootwijk, M.

    2000-01-01

    Innovative applications of natural gas can increase the sale of natural gas, support energy companies in the development of commercial activities, and contribute to energy efficiency measures. The Dutch natural gas trading company Gasunie supports those developments by investigating the market potential of innovative gas appliances. Use is made of the so-called Phase Model for Market Introduction, developed by Kea Consult

  3. Phase structure rewrite systems in information retrieval

    Klingbiel, P. H.

    1985-01-01

    Operational level automatic indexing requires an efficient means of normalizing natural language phrases. Subject switching requires an efficient means of translating one set of authorized terms to another. A phrase structure rewrite system called a Lexical Dictionary is explained that performs these functions. Background, operational use, other applications and ongoing research are explained.

  4. Reactions of OH radicals with 2-methyl-1-butyl, neopentyl and 1-hexyl nitrates. Structure-activity relationship for gas-phase reactions of OH with alkyl nitrates: An update

    Bedjanian, Yuri; Morin, Julien; Romanias, Manolis N.

    2018-05-01

    The kinetics of the reactions 2-methyl-1-butyl (2M1BNT), neopentyl (NPTNT) and 1-hexyl nitrates (1HXNT) with OH radicals has been studied using a low pressure flow tube reactor combined with a quadrupole mass spectrometer. The rate constants of the title reactions were determined under pseudo-first order conditions from kinetics of OH consumption in excess of nitrates. The overall rate coefficients, k2M1BNT = 1.54 × 10-14 (T/298)4.85 exp (1463/T) (T = 278-538 K), kNPTNT = 1.39 × 10-14 (T/298)4.89 exp (1189/T) (T = 278-500 K) and k1HXNT = 2.23 × 10-13 (T/298)2.83 exp (853/T) cm3molecule-1s-1 (T = 306-538 K) (with conservative 15% uncertainty), were determined at a total pressure of 1 Torr of helium. The yield of trimethylacetaldehyde ((CH3)3CCHO), resulting from the abstraction by OH of an α-hydrogen atom in neopentyl nitrate, followed by α-substituted alkyl radical decomposition, was determined as 0.31 ± 0.06 at T = 298 K. The calculated tropospheric lifetimes of 2M1BNT, NPTNT and 1HXNT indicate that reaction of these nitrates with OH represents an important sink of these compounds in the atmosphere. Based on the available kinetic data, we have updated the structure-activity relationship (SAR) for reactions of alkyl nitrates with OH at T = 298 K. Good agreement (within 20%) is obtained between experimentally measured rate constants (total and that for H-atom abstraction from α carbon) and those calculated from SAR using new substituents factors for almost all the experimental data available.

  5. Identification of dominant structures and their flow dynamics in the turbulent two-phase flow using POD technique

    Munir, Shahzad; Siddiqui, Muhammad Israr; Heikal, Morgan; Aziz, Abdul Rashid Abdul [Universiti Teknologi PETRONAS, Bander Seri Iskandar (Malaysia); Sercey, Guillaume de [University of Brighton, Brighton (United Kingdom)

    2015-11-15

    The Proper orthogonal decomposition (POD) method has seen increasingly used in the last two decades and has a lot of applications for the comparison of experimental and numerically simulated data. The POD technique is often used to extract information about coherent structures dominating the flow. The two-dimensional and two-component instantaneous velocity fields of both liquid and gas phases of a slug flow were obtained by Particle image velocimetry (PIV) combined with Laser induced fluorescence (LIF). POD was applied to the velocity fields of both phases separately to identify the coherent flow structures. We focused on POD eigenmodes and their corresponding energy contents of both liquid and gas phases. The sum of first few eigenmodes that contain maximum turbulent kinetic energy of the flow represents the coherent structures. In the case of liquid phase the first eigenmode contained 42% of the total energy, while in the gas phase the decaying energy distribution was flat. The POD results showed that the coefficient of mode 1 for the liquid phase oscillated between positive and negative values and had the highest amplitude. For the visualization of coherent motion different linear combinations of eigenmodes for liquid and gas phases were used. The phenomena of turbulent bursting events associated with Q2 events (low momentum fluid moving away from the wall) and Q4 events (high momentum flow moving towards the wall) were also discussed to assess its contribution in turbulence production.

  6. Gas-phase nitrosation of ethylene and related events in the C2H4NO+ landscape.

    Gerbaux, Pascal; Dechamps, Noemie; Flammang, Robert; Nam, Pham Cam; Nguyen, Minh Tho; Djazi, Fayçal; Berruyer, Florence; Bouchoux, Guy

    2008-06-19

    The C2H4NO(+) system has been examined by means of quantum chemical calculations using the G2 and G3B3 approaches and tandem mass spectrometry experiments. Theoretical investigation of the C2H4NO(+) potential-energy surface includes 19 stable C2H4NO(+) structures and a large set of their possible interconnections. These computations provide insights for the understanding of the (i) addition of the nitrosonium cation NO(+) to the ethylene molecule, (ii) skeletal rearrangements evidenced in previous experimental studies on comparable systems, and (iii) experimental identification of new C2H4NO(+) structures. It is predicted from computation that gas-phase nitrosation of ethylene may produce C2H4(*)NO(+) adducts, the most stable structure of which is a pi-complex, 1, stabilized by ca. 65 kJ/mol with respect to its separated components. This complex was produced in the gas phase by a transnitrosation process involving as reactant a complex between water and NO(+) (H2O.NO(+)) and the ethylene molecule and fully characterized by collisional experiments. Among the other C 2H 4NO (+) structures predicted by theory to be protected against dissociation or isomerization by significant energy barriers, five were also experimentally identified. These finding include structures CH3CHNO(+) (5), CH 3CNOH (+) ( 8), CH3NHCO(+) (18), CH3NCOH(+) (19), and an ion/neutral complex CH2O...HCNH(+) (12).

  7. Theoretical modeling and design of photonic structures in zeolite nanocomposites for gas sensing. Part I: surface relief gratings.

    Cody, D; Naydenova, I

    2017-12-01

    The suitability of holographic structures fabricated in zeolite nanoparticle-polymer composite materials for gas sensing applications has been investigated. Theoretical modeling of the sensor response (i.e., change in hologram readout due to a change in refractive index modulation or thickness as a result of gas adsorption) of different sensor designs was carried out using Raman-Nath theory and Kogelnik's coupled wave theory. The influence of a range of parameters on the sensor response of holographically recorded surface and volume photonic grating structures has been studied, namely the phase difference between the diffracted and probe beam introduced by the grating, grating geometry, thickness, spatial frequency, reconstruction wavelength, and zeolite nanoparticle refractive index. From this, the optimum fabrication conditions for both surface and volume holographic gas sensor designs have been identified. Here, in part I, results from theoretical modeling of the influence of design on the sensor response of holographically inscribed surface relief structures for gas sensing applications is reported.

  8. Photoresponse of the protonated Schiff-base retinal chromophore in the gas phase

    Toker, Jonathan; Rahbek, Dennis Bo; Kiefer, H V

    2013-01-01

    The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse. The sel......The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse...... modifications of the chromophore. We propose that isomerizations play an important role in the photoresponse of gas-phase retinal chromophores and guide internal conversion through conical intersections. The role of protein interactions is then to control the specificity of the photoisomerization in the primary...

  9. Measurement of pressure fluctuation in gas-liquid two-phase vortex street

    Sun Zhiqiang; Sang Wenhui; Zhang Hongjian

    2009-01-01

    The pressure fluctuation in the wake is an important parameter to characterize the shedding process of gas-liquid two-phase Karman vortex street. This paper investigated such pressure fluctuations in a horizontal pipe using air and water as the tested fluid media. The dynamic signal representing the pressure fluctuation was acquired by the duct-wall differential pressure method. Results show that in the wake of the gas-liquid two-phase Karman vortex street, the frequency of the pressure fluctuation is linear with the Reynolds number when the volume void fraction is within the range of 18%. Moreover, the mean amplitude of the pressure fluctuation decreases with the volume void fraction, and the mean amplitude is larger at higher water flowrates under the same volume void fraction. These findings contribute to an in-depth understanding of the gas-liquid two-phase Karman vortex street.

  10. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    Read, Douglas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sillerud, Colin Halliday [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  11. The Stability of CI02 as a Product of Gas Phase Decontamination Treatments

    Simmons, D. W.

    1994-01-01

    The gas phase decontamination project is investigating the use of chlorine trifluoride (ClF 3 ) to fluorinate nonvolatile uranium deposits to produce uranium hexafluoride (UF 6 ) gas. The potential existence of chlorine dioxide (ClO 2 ) during gas phase decontamination with ClF 3 has been the subject of recent safety discussions. Some of the laboratory data collected during feasibility studies of the gas phase process has been evaluated for the presence of ClO 2 in the product gas stream. The preliminary evidence to date can be summarized as follows: (1) ClO 2 was not detected in the flow loop in the absence of ClF 3 ; (2) ClO 2 was not detected in the static reactors in the absence of both ClF 3 and ClF; and (3) ClO 2 was detected in a static reactor in the absence of all fluorinating gases. The experimental evidence suggests that ClO 2 will not exist in the presence of ClF 3 , ClF, or UF 6 . The data analyzed to date is insufficient to determine the stability of ClO 2 in the presence of ClO 2 F. Thermodynamic calculations of the ClF 3 + H 2 O system support the experimental evidence, and suggest that ClO 2 will not exist in the presence of ClO 2 F. Additional experimental efforts are needed to provide a better understanding of the gas phase ClF 3 treatments and the product gases. However, preliminary evidence to date suggests that ClO 2 should not be present as a product during the normal operations of the gas phase decontamination project

  12. The Stability of CI02 as a Product of Gas Phase Decontamination Treatments

    D. W. Simmons

    1994-09-01

    The gas phase decontamination project is investigating the use of chlorine trifluoride (ClF{sub 3}) to fluorinate nonvolatile uranium deposits to produce uranium hexafluoride (UF{sub 6}) gas. The potential existence of chlorine dioxide (ClO{sub 2}) during gas phase decontamination with ClF{sub 3} has been the subject of recent safety discussions. Some of the laboratory data collected during feasibility studies of the gas phase process has been evaluated for the presence of ClO{sub 2} in the product gas stream. The preliminary evidence to date can be summarized as follows: (1) ClO{sub 2} was not detected in the flow loop in the absence of ClF{sub 3}; (2) ClO{sub 2} was not detected in the static reactors in the absence of both ClF{sub 3} and ClF; and (3) ClO{sub 2} was detected in a static reactor in the absence of all fluorinating gases. The experimental evidence suggests that ClO{sub 2} will not exist in the presence of ClF{sub 3}, ClF, or UF{sub 6}. The data analyzed to date is insufficient to determine the stability of ClO{sub 2} in the presence of ClO{sub 2}F. Thermodynamic calculations of the ClF{sub 3} + H{sub 2}O system support the experimental evidence, and suggest that ClO{sub 2} will not exist in the presence of ClO{sub 2}F. Additional experimental efforts are needed to provide a better understanding of the gas phase ClF{sub 3} treatments and the product gases. However, preliminary evidence to date suggests that ClO{sub 2} should not be present as a product during the normal operations of the gas phase decontamination project.

  13. Single-phase and two-phase gas-liquid turbulent mixing between subchannels in a simulated rod bundle

    Sadatomi, Michio; Kawahara, Akimaro; Sato, Yoshifusa; Tomino, Takayoshi.

    1996-01-01

    This study is concerned with turbulent mixing which is one of the three mechanisms of cross flows between subchannels in a nuclear fuel rod bundle. The channel used in this experiments was a vertical simulated rod bundle having two subchannels connected through 1 to 3 gaps between two rods and/or rod and channel wall. The number of the gaps was changed to investigate the effect of the number on the turbulent mixing. Turbulent mixing rates of air and water and fluctuations of pressure difference between the subchannels were measured for single-phase and two-phase gas-liquid flows under hydrodynamic equilibrium flow conditions. It has been confirmed that the turbulent mixing rate is affected strongly by the fluctuations especially for liquid phase in two-phase slug or churn flow. (author)

  14. Composite Structure Monitoring using Direct Write Sensors, Phase II

    National Aeronautics and Space Administration — This NASA SBIR Phase II project seeks to develop and demonstrate a suite of sensor products to monitor the health of composite structures. Sensors will be made using...

  15. Structural Integrity Inspection and Visualization System, Phase II

    National Aeronautics and Space Administration — Based on the successful feasibility demonstration in Phase I, Physical Optics Corporation (POC) proposes to continue the development of a novel Structural Integrity...

  16. Higher Strength, Lighter Weight Aluminum Spacecraft Structures, Phase I

    National Aeronautics and Space Administration — This SBIR Phase I program proposes to develop a bulk processing technology for producing ultra fine grain (UFG) aluminum alloy structures. The goal is to demonstrate...

  17. Shape Memory Alloy-Based Periodic Cellular Structures, Phase II

    National Aeronautics and Space Administration — This SBIR Phase II effort will continue to develop and demonstrate an innovative shape memory alloy (SMA) periodic cellular structural technology. Periodic cellular...

  18. Structure determination at room temperature and phase transition ...

    Unknown

    Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India. MS received 9 May 2002 ... exhibit a ferroelectric–paraelectric phase transition at ele- ..... The pattern decomposition and peak extraction methods ...

  19. Simulating Nonlinear Dynamics of Deployable Space Structures, Phase I

    National Aeronautics and Space Administration — To support NASA's vital interest in developing much larger solar array structures over the next 20 years, MotionPort LLC's Phase I SBIR project will strengthen...

  20. Phase relations, crystal structures and physical properties of nuclear fuels

    Tagawa, Hiroaki; Fujino, Takeo; Tateno, Jun

    1975-07-01

    Phase relations, crystal structures and physical properties of the compounds for nuclear fuels are presented, including melting point, thermal expansion, diffusion and magnetic and electric properties. Emphasis is on oxides, carbides and nitrides of thorium, uranium and plutonium. (auth.)

  1. Gas adsorption/absorption heat switch, phase 1

    Chan, C. K.

    1987-01-01

    The service life and/or reliability of far-infrared sensors on surveillance satellites is presently limited by the cryocooler. The life and/or reliability, however, can be extended by using redundant cryocoolers. To reduce parasitic heat leak, each stage of the inactive redundant cryocooler must be thermally isolated from the optical system, while each stage of the active cryocooler must be thermally connected to the system. The thermal break or the thermal contact can be controlled by heat switches. Among different physical mechanisms for heat switching, mechanically activated heat switches tend to have low reliability and, furthermore, require a large contact force. Magnetoresistive heat switches are, except at very low temperatures, of very low efficiency. Heat switches operated by the heat pipe principle usually require a long response time. A sealed gas gap heat switch operated by an adsorption pump has no mechanical motion and should provide the reliability and long lifetime required in long-term space missions. Another potential application of a heat switch is the thermal isolation of the optical plane during decontamination.

  2. Synthesis gas demonstration plant program, Phase I. Site confirmation report

    1978-12-01

    With few reservations, the Baskett, Kentucky site exhibits the necessary characteristics to suggest compatibility with the proposed Synthesis Gas Demonstration Plant Project. An evaluation of a broad range of technical disciplinary criteria in consideration of presently available information indicated generally favorable conditions or, at least, conditions which could be feasibly accommodated in project design. The proximity of the Baskett site to market areas and sources of raw materials as well as a variety of transportation facilities suggests an overall favorable impact on Project economic feasibility. Two aspects of environmental engineering, however, have been identified as areas where the completion or continuation of current studies are required before removing all conditions on site suitability. The first aspect involves the current contradictory status of existing land use and planning ordinances in the site area. Additional investigation of the legality of, and local attitudes toward, these present plans is warranted. Secondly, terrestrial and aquatic surveys of plant and animal life species in the site area must be completed on a seasonal basis to confirm the preliminary conclusion that no exclusionary conditions exist.

  3. Structure of anode plasma of gas discharge taking into account gas ionization burnout

    Zharinov, A.V.; Shumilin, V.P.

    2006-01-01

    One deals with a structure of an anode plasma of a gas discharge with intensive ionization ( b urnout ) of neutral atoms (neutrals). One derived analytical solutions of the quasi-neutrality equation for potential distribution, as well as, a condition of anode plasma existence in a unidimensional case at the arbitrary dependences of neutral burnout frequency and of electron concentration on the potential. One studied particular cases of the level frequency of neutral burnout, of ionization by the Maxwell electrons and of ionization by the intensive beam at collision-free motion of ions and the Boltzmann distribution of thermal electrons. Solutions for the first two cases at zero parameter of burnout, that is, at the level concentration of a gas coincide with the solutions obtained [1] by the power series expansion. It is shown that in case of ionization by the Maxwell electrons, anode plasma at the rational flow rates of a working gas may be produced under rather high temperature of electrons (if, for example, xenon serves as a working gas, so T e ≥5 eV). The stationary solutions of the quasi-neutrality at ionization by the intensive electron beam are found exclusively when the ratio between the electron beam density and the maximum density of thermal neutrons does not exceed a certain limiting value [ru

  4. A gas-phase reactor powered by solar energy and ethanol for H2 production

    Ampelli, Claudio; Genovese, Chiara; Passalacqua, Rosalba; Perathoner, Siglinda; Centi, Gabriele

    2014-01-01

    In the view of H 2 as the future energy vector, we presented here the development of a homemade photo-reactor working in gas phase and easily interfacing with fuel cell devices, for H 2 production by ethanol dehydrogenation. The process generates acetaldehyde as the main co-product, which is more economically advantageous with respect to the low valuable CO 2 produced in the alternative pathway of ethanol photoreforming. The materials adopted as photocatalysts are based on TiO 2 substrates but properly modified with noble (Au) and not-noble (Cu) metals to enhance light harvesting in the visible region. The samples were characterized by BET surface area analysis, Transmission Electron Microscopy (TEM) and UV–visible Diffusive Reflectance Spectroscopy, and finally tested in our homemade photo-reactor by simulated solar irradiation. We discussed about the benefits of operating in gas phase with respect to a conventional slurry photo-reactor (minimization of scattering phenomena, no metal leaching, easy product recovery, etc.). Results showed that high H 2 productivity can be obtained in gas phase conditions, also irradiating titania photocatalysts doped with not-noble metals. - Highlights: • A gas-phase photoreactor for H 2 production by ethanol dehydrogenation was developed. • The photocatalytic behaviours of Au and Cu metal-doped TiO 2 thin layers are compared. • Benefits of operating in gas phase with respect to a slurry reactor are presented. • Gas phase conditions and use of not-noble metals are the best economic solution

  5. Probing the nuclear liquid-gas phase transition

    Pochodzalla, J.; Moehlenkamp, T.; Rubehn, T.; Schuettauf, A.; Zude, E.; Begemann-Blaich, M.; Blaich, T.; Emling, H.; Ferrero, A.; Kunze, W.D.; Lindenstruth, V.; Lynen, U.; Moroni, W.; Ocker, B.; Schwarz, C.; Seidel, W.; Serfling, V.; Trzcinski, A.; Tucholski, A.; Verde, G.

    1995-02-01

    Fragment distributions resulting from Au+Au collisions at an incident energy of E/A=600 MeV are studied. From the measured fragment and neutron distributions the mass and the excitation energy of the decaying pre-fragments were determined. A temperature scale was derived from observed yield ratios of He and Li isotopes. The relation between this isotope temperature and the excitation energy of the system exhibits a behavior which is expected for a phase transition. The nuclear vapor regime takes over at an excitation energy of 10 MeV per nucleon, a temperature of 5 MeV and may be characterized by a density of 0.15-0.3 normal nuclear density. (orig.)

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

    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.

  7. Traveling wave accelerating structures with a large phase advance

    Paramonov, V.V.

    2012-01-01

    The cells RF parameters for the well known Disk Loaded Waveguide (DLW) are considered in higher pass bands of TM01 wave, providing operating phase advance between 180 o - 1230 o per cell. With an appropriate shape optimization and some additional elements proposed traveling wave structures with such large phase advance overlap the classical first band DLW in RF efficiency. Examples of proposed structures together with RF and dispersion properties are presented.

  8. DFT Study of dimers of dimethyl sulfoxide in gas phase

    Reza Fazaeli

    2014-10-01

    Full Text Available Density functional (DFT calculations at M05-2x/aug-cc-pVDZ level were used to analyze the interactions between dimethyl sulfoxide (DMSO dimers. The structures obtained have been ana-lyzed with the Atoms in Molecules (AIMs and Natural Bond Orbital (NBO methodologies. Four minima were located on the potential energy surface of the dimers. Three types of interac-tions are observed, CH•••O, CH•••S hydrogen bonds and orthogonal interaction between the lone pair of the oxygen with the electron-deficient region of the sulfur atom. Stabilization energies of dimers including BSSE and ZPE are in the range 27–40 kJmol-1. The most stable conformers of dimers at DFT level is cyclic structure with antiparallel orientation of S=O groups pairing with three C–H∙∙∙O and a S∙∙∙O interactions.

  9. Research in Korea on Gas Phase Synthesis and Control of Nanoparticles

    Choi, Mansoo

    2001-01-01

    Research activity into the gas phase synthesis of nanoparticles has witnessed rapid growth on a worldwide basis, which is also reflected by Korean research efforts. Nanoparticle research is inherently a multi-disciplinary activity involving both science and engineering. In this paper, the recent studies undertaken in Korea on the gas phase synthesis and control of nanoparticles are reviewed. Studies on the synthesis of various kinds of nanoparticles are first discussed with a focus on the different types of reactors used. Recent experimental and theoretical studies and newly developed methods of measuring and modeling nanoparticle growth are also reviewed

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

    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.

  11. Acrolein Production by Gas-Phase Glycerol Dehydration Using PO₄/Nb₂O5 Catalysts.

    Lee, Kyu Am; Ryoo, HeeKyoung; Ma, Byung Chol; Kim, Youngchul

    2018-02-01

    In this study, modified niobium oxide were prepared to study the addictive effects on the catalytic performance for gas-phase glycerol dehydration. The catalysts were characterized by N2 adsorption/desorption, XRD, NH3-TPD, FT-IR. The amount of phosphoric acid was up to 50 wt% in niobium. As a result, the highest glycerol conversion was achieved over 20 wt% PO4/Nb2O5. It indicates that the optimal amount of phosphoric acid leads the catalyst to have appropriate acidity which is an important factor for gas-phase glycerol dehydration.

  12. Gas phase THz spectroscopy of toxic agent simulant compounds using the AILES synchrotron beamline

    Cuisset, A.; Smirnova, I.; Bocquet, R.; Hindle, F.; Mouret, G.; Yang, C.; Pirali, O.; Roy, P.

    2010-02-01

    A new study is currently underway aiming at recording and assigning the gas phase rovibrational spectra of several organophosphorus and organosulphur compounds in the THz frequency domain. Thanks to the exceptional properties of flux, brilliance and spectral range of the AILES beamline coupled to the FTIR spectrometer, the gas phase vibrational spectra of low volatility organophosphorous compounds have been recorded across the entire THz frequency range. High resolution FTIR spectroscopy was used to record the pure rotational and the low-frequency rovibrational spectrum of DMSO. A comparison between the spectra measured with the AILES beamline and the spectra obtained with optoelectronic THz sources is possible.

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

    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.)

  14. Tandem differential mobility analysis-mass spectrometry reveals partial gas-phase collapse of the GroEL complex.

    Hogan, Christopher J; Ruotolo, Brandon T; Robinson, Carol V; Fernandez de la Mora, Juan

    2011-04-07

    A parallel-plate differential mobility analyzer and a time-of-flight mass spectrometer (DMA-MS) are used in series to measure true mobility in dry atmospheric pressure air for mass-resolved electrosprayed GroEL tetradecamers (14-mers; ~800 kDa). Narrow mobility peaks are found (2.6-2.9% fwhm); hence, precise mobilities can be obtained for these ions without collisional activation, just following their generation by electrospray ionization. In contrast to previous studies, two conformers are found with mobilities (Z) differing by ~5% at charge state z ~ 79. By extrapolating to small z, a common mobility/charge ratio Z(0)/z = 0.0117 cm(2) V(-1) s(-1) is found for both conformers. When interpreted as if the GroEL ion surface were smooth and the gas molecule-protein collisions were perfectly elastic and specular, this mobility yields an experimental collision cross section, Ω, 11% smaller than in an earlier measurement, and close to the cross section, A(C,crystal), expected for the crystal structure (determined by a geometric approximation). However, the similarity between Ω and A(C,crystal) does not imply a coincidence between the native and gas-phase structures. The nonideal nature of protein-gas molecule collisions introduces a drag enhancement factor, ξ = 1.36, with which the true cross section A(C) is related to Ω via A(C) = Ω/ξ. Therefore, A(C) for GroEL 14-mer ions determined by DMA measurements is 0.69A(C,crystal). The factor 1.36 used here is based on the experimental Stokes-Millikan equation, as well as on prior and new numerical modeling accounting for multiple scattering events via exact hard-sphere scattering calculations. Therefore, we conclude that the gas-phase structure of the GroEL complex as electrosprayed is substantially more compact than the corresponding X-ray crystal structure.

  15. Isomers and conformational barriers of gas phase nicotine, nornicotine and their protonated forms

    Yoshida, Tomoki; Farone, William A.; Xantheas, Sotiris S.

    2014-07-17

    We report extensive conformational searches of the neutral nicotine, nornicotine and their protonated analogs that are based on ab-initio second order Møller-Plesset perturbation (MP2) electronic structure calculations. Initial searches were performed with the 6-31G(d,p) and the energetics of the most important structures were further refined from geometry optimizations with the aug-cc-pVTZ basis set. Based on the calculated free energies at T=298 K for the gas phase molecules, neutral nicotine has two dominant trans conformers, whereas neutral nornicotine is a mixture of several conformers. For nicotine, the protonation on both the pyridine and the pyrrolidine sites is energetically competitive, whereas nornicotine prefers protonation on the pyridine nitrogen. The protonated form of nicotine is mainly a mixture of two pyridine-protonated trans conformers and two pyrrolidine-protonated trans conformers, whereas the protonated form of nornicotine is a mixture of four pyridine-protonated trans conformers. Nornicotine is conformationally more flexible than nicotine, however it is less protonated at the biologically important pyrrolidine nitrogen site. The lowest energy isomers for each case were found to interconvert via low (< 6 kcal/mol) rotational barriers around the pyridine-pyrrolidine bond.

  16. Resonant x-ray emission from gas-phase TiCl{sub 4}

    Hague, C.F.; Tronc, M. [Universite Pierre et Marie Curie, Paris (France); De Groot, F. [Univ. of Groningen (Netherlands)] [and others

    1997-04-01

    Resonant x-ray emission spectroscopy (RXES) has proved to be a powerful tool for studying the electronic structure of condensed matter. Over the past few years it has been used mainly for studying the valence bands of solids and condensed molecules. Very recently the advent of high brightness photon beams provided by third generation synchrotron radiation source undulators, associated with efficient x-ray emission spectrometers has made it possible to perform experiments on free diatomic molecular systems. RXE spectra of free molecules are of prime importance to gain insight into their electronic structure and bonding as they reflect the symmetry of orbitals engaged in the two-electron, two-step process with the l = 0, {+-}2 parity-conserving selection rule, and are free from solid state effects which can introduce difficulties in the interpretation. They provide information (more so than XAS) on the core excited states, and, when performed at fixed incident photon energy as a function of the emitted photon energy, on the electronic excitation (charge transfer, multiplet states). Moreover the anisotropy of the angular distribution of resonant x-ray emission affects the relative intensity of the emission peaks and provides information concerning the symmetries of final states. This is a preliminary report on what are the first RXE spectra of a 3d transition metal complex in the gas phase. The experiment concerns the Ti 3d {yields}2p emission spectrum of TiCl{sub 4} over the 450 to 470 eV region.

  17. Resonant x-ray emission from gas-phase TiCl4

    Hague, C.F.; Tronc, M.; De Groot, F.

    1997-01-01

    Resonant x-ray emission spectroscopy (RXES) has proved to be a powerful tool for studying the electronic structure of condensed matter. Over the past few years it has been used mainly for studying the valence bands of solids and condensed molecules. Very recently the advent of high brightness photon beams provided by third generation synchrotron radiation source undulators, associated with efficient x-ray emission spectrometers has made it possible to perform experiments on free diatomic molecular systems. RXE spectra of free molecules are of prime importance to gain insight into their electronic structure and bonding as they reflect the symmetry of orbitals engaged in the two-electron, two-step process with the l = 0, ±2 parity-conserving selection rule, and are free from solid state effects which can introduce difficulties in the interpretation. They provide information (more so than XAS) on the core excited states, and, when performed at fixed incident photon energy as a function of the emitted photon energy, on the electronic excitation (charge transfer, multiplet states). Moreover the anisotropy of the angular distribution of resonant x-ray emission affects the relative intensity of the emission peaks and provides information concerning the symmetries of final states. This is a preliminary report on what are the first RXE spectra of a 3d transition metal complex in the gas phase. The experiment concerns the Ti 3d →2p emission spectrum of TiCl 4 over the 450 to 470 eV region

  18. Soft X-ray photoemission spectroscopy of selected neurotransmitters in the gas phase

    Maris, Assimo; Melandri, Sonia; Evangelisti, Luca; Caminati, Walther [Dipartimento di Chimica ' G. Ciamician' dell' Universita, Via Selmi 2, I-40126 Bologna (Italy); Giuliano, Barbara M. [Departamento de Quimica da Universidade de Coimbra, 3004-535 Coimbra (Portugal); Plekan, Oksana [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Feyer, Vitaliy [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Electronic Properties (PGI-6), Peter Gruenberg Institute, Forschungszentrum Juelich GmbH, Leo-Brandt-Strasse, 52428 Juelich (Germany); Richter, Robert [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Coreno, Marcello [CNR-IMIP, Montelibretti, I-00016 Rome (Italy); Prince, Kevin C., E-mail: kevin.prince@elettra.trieste.it [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); CNR-IOM, Laboratorio TASC, I-34149 Basovizza, Trieste (Italy)

    2012-09-15

    Highlights: Black-Right-Pointing-Pointer Neurotransmitter molecules. Black-Right-Pointing-Pointer Photoelectron spectroscopy. Black-Right-Pointing-Pointer Electronic structure. Black-Right-Pointing-Pointer Weak hydrogen bonding. -- Abstract: The valence molecular orbitals and core levels of tyramine, tryptamine and tryptophol in the gas phase have been studied using X-ray photoelectron spectroscopy (XPS) and theoretical methods. The energies of the outer valence region spectrum are found to be in agreement with previously reported He I spectra, while new data on the inner valence molecular orbitals are reported. The structures in the carbon, nitrogen and oxygen core level spectra of these molecules have been identified and assigned. These compounds are characterised by conformers with hydrogen bonding in which the {pi} systems of the phenol and indole groups act as hydrogen acceptors, but a spectroscopic signature of this hydrogen bond was not observed. This is in contrast with our previous spectra of amino acids, where conformers with specific hydrogen bonding showed strong effects in core level spectra. We attribute the difference to the weaker strength of the {pi}-hydrogen bonding.

  19. Parents of two-phase flow and theory of “gas-lift”

    Zitek Pavel

    2014-03-01

    Full Text Available This paper gives a brief overview of types of two-phase flow. Subsequently, it deals with their mutual division and problems with accuracy boundaries among particular types. It also shows the case of water flow through a pipe with external heating and the gradual origination of all kinds of flow. We have met it in solution of safety condition of various stages in pressurized and boiling water reactors. In the MSR there is a problem in the solution of gas-lift using helium as a gas and its secondary usage for clearing of the fuel mixture from gaseous fission products. Theory of gas-lift is described.

  20. Parents of two-phase flow and theory of "gas-lift"

    Zitek, Pavel; Valenta, Vaclav

    2014-03-01

    This paper gives a brief overview of types of two-phase flow. Subsequently, it deals with their mutual division and problems with accuracy boundaries among particular types. It also shows the case of water flow through a pipe with external heating and the gradual origination of all kinds of flow. We have met it in solution of safety condition of various stages in pressurized and boiling water reactors. In the MSR there is a problem in the solution of gas-lift using helium as a gas and its secondary usage for clearing of the fuel mixture from gaseous fission products. Theory of gas-lift is described.

  1. [Study of the phase transformation of TiO2 with in-situ XRD in different gas].

    Ma, Li-Jing; Guo, Lie-Jin

    2011-04-01

    TiO2 sample was prepared by sol-gel method from chloride titanium. The phase transformation of the prepared TiO2 sample was studied by in-situ XRD and normal XRD in different gas. The experimental results showed that the phase transformation temperatures of TiO2 were different under in-situ or normal XRD in different kinds of gas. The transformation of amorphous TiO2 to anatase was controlled by kinetics before 500 degrees C. In-situ XRD showed that the growth of anatase was inhibited, but the transformation of anatase to rutile was accelerated under inactive nitrogen in contrast to air. Also better crystal was obtained under hydrogen than in argon. These all showed that external oxygen might accelerate the growth of TiO2, but reduced gas might partly counteract the negative influence of lack of external oxygen. The mechanism of phase transformation of TiO2 was studied by in-situ XRD in order to control the structure in situ.

  2. Phase space structure of triatomic molecules

    Lu, Z.; Kellman, M.E.

    1997-01-01

    The bifurcation structure is investigated for a Hamiltonian for the three coupled nonlinear vibrations of a highly excited triatomic molecule. The starting point is a quantum Hamiltonian used to fit experimental spectra. This Hamiltonian includes 1:1 Darling endash Dennison resonance coupling between the stretches, and 2:1 Fermi resonance coupling between the stretches and bend. A classical Hamiltonian is obtained using the Heisenberg correspondence principle. Surfaces of section show a pronounced degree of chaos at high energies, with a mixture of chaotic and regular dynamics. The large-scale bifurcation structure is found semianalytically, without recourse to numerical solution of Hamilton close-quote s equations, by taking advantage of the fact that the spectroscopic Hamiltonian has a conserved polyad quantum number, corresponding to an approximate constant of the motion of the molecule. Bifurcation diagrams are analyzed for a number of molecules including H 2 O, D 2 O, NO 2 , ClO 2 , O 3 , and H 2 S. copyright 1997 American Institute of Physics

  3. Universal structure of a strongly interacting Fermi gas

    Kuhnle, Eva; Dyke, Paul; Hoinka, Sascha; Mark, Michael; Hu Hui; Liu Xiaji; Drummond, Peter; Hannaford, Peter; Vale, Chris, E-mail: cvale@swin.edu.au [ARC Centre of Excellence for Quantum Atom Optics, Swinburne University of Technology, Hawthorn 3122 (Australia)

    2011-01-10

    This paper presents studies of the universal properties of strongly interacting Fermi gases using Bragg spectroscopy. We focus on pair-correlations, their relationship to the contact C introduced by Tan, and their dependence on both the momentum and temperature. We show that short-range pair correlations obey a universal law, first derived by Tan through measurements of the static structure factor, which displays a universal scaling with the ratio of the contact to the momentum C/q. Bragg spectroscopy of ultracold {sup 6}Li atoms is employed to measure the structure factor for a wide range of momenta and interaction strengths, providing broad confirmation of this universal law. We show that calibrating our Bragg spectra using the f-sum rule leads to a dramatic improvement in the accuracy of the structure factor measurement. We also measure the temperature dependence of the contact in a unitary gas and compare our results to calculations based on a virial expansion.

  4. Two phases of the anyon gas and broken T symmetry

    Canright, G.S.; Rojo, A.G.

    1991-01-01

    This paper reports the first exact finite-temperature study of anyons. The authors' method is an extension to finite T of earlier numerical work with small numbers of anyons on a lattice. We study the spontaneous magnetization M 0 (T), since the signature has been identified as a key signature of broken T symmetry for anyon models. Our results confirm the two-phase picture suggested by earlier work: The authors find a low-temperature regime where M 0 is very small or zero, and a high-temperature regime where M 0 is of O(0.1 μ B ) per particle. In the high-temperature regime the authors can obtain an excellent estimate of M 0 (T) in the thermodynamic limit (which we call M 0 ∞ ). since our finite-size results extrapolate smoothly with little scatter. The authors' values for M 0 ∞ can then be compared with the results of μSR experiments on high-temperature superconductors, which set an upper experimental bound on the internal fields from such moments. The authors find that M 0 ∞ in a bulk material of many planes will almost certainly give a signal well above this threshold if (and only if) the planes are ordered ferromagnetically. In the antiferromagnetic case (which is strongly favored energetically) the signal from M 0 ∞ is probably undetectable. Finally, we estimate the transition temperature T c from our finite-size studies, obtaining a value on the order of a few hundred Kelvins

  5. Neutron scattering studies of pretransitional phenomena in structural phase transformations

    Shapiro, S.M.

    1979-03-01

    Materials exhibiting structural phase transformations are well known to possess pretransitional phenomena. Below the transition temperature, T/sub c/, an order parameter appears and the pretransitional effects are associated with the fluctuations of the order parameter. Neutron scattering techniques have proved invaluable in studying the temporal and spatial dependence of these fluctuations. SrTiO 3 is the prototypical example of a structural phase transformation exhibiting features observable in other transformations such as martensitic and order-disorder. The experimental evolution of the understanding of the phase transformation in SrTiO 3 will be reviewed and the features observed will be shown to typify other systems

  6. Theoretical description of the properties of magnetization fluctuations in the vicinity of phase transition from paramagnetic phase to ferromagnetic phase with domain structure

    Wasilewski, W.

    1983-08-01

    This paper presents a theoretical description of the phase transition from a paramagnetic phase P to the homogeneous and domain structure ferromagnetic phases within the phenomenological theory of phase transitions

  7. Loading and stress analysis of gas pipeline structures; Analise de esforcos e tensoes em estruturas de gasodutos durante despressurizacoes

    Frisoli, Caetano [TRANSPETRO - PETROBRAS Transporte S.A., Rio de Janeiro, RJ (Brazil); Frota, Cristiane Souto [TBG - Transportadora Brasileira Gasoduto Bolivia Brasil S.A., Rio de Janeiro, RJ (Brazil); Silva, Luis Fernando Figueira da; Carvalho, Marcio da Silveira [Pontificia Univ. Catolica do Rio de Janeiro, RJ (Brazil). Dept. de Engenharia Mecanica; Savi, Marcelo Amorim [Universidade Federal, Rio de Janeiro, RJ (Brazil). Coordenacao dos Programas de Pos-graduacao de Engenharia. Dept. de Engenharia Mecanica; Pacheco, Pedro Manuel Calas Lopes [Centro Federal de Educacao Tecnologica do Rio de Janeiro (CEFET-RJ), Rio de Janeiro, RJ (Brazil)

    2003-07-01

    Repairing and maintenance activities on Bolivia-Brazil gas pipeline often need blow down lines. During the blow down process, the high speed of discharging gases imposes great efforts to the structures. A detailed analysis of this situation is essential for a safe operation. This paper describes two phases of a project, developed under TBG coordination. It consists in analyzing the stress and forces involved in this operation, in order to design facilities to blow down pipes and develop a safe blow down procedure for the gas pipeline. The first phase consists of a supersonic flowing simulation in the blow down gas pipeline device. The pressure behavior, mass flow and the speed at the device's ending point are calculated for different operational conditions. In the second phase, the equivalent loading caused by blow down operations is used as input in a stress analysis program to determine stress, critical sessions evaluation and material recommendations for blow down devices. (author)

  8. Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

    Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.

    2018-02-01

    Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

  9. Experimental and numerical investigation of shock wave propagation through complex geometry, gas continuous, two-phase media

    Chien-Chih Liu, James [Univ. of California, Berkeley, CA (United States)

    1993-01-01

    The work presented here investigates the phenomenon of shock wave propagation in gas continuous, two-phase media. The motivation for this work stems from the need to understand blast venting consequences in the HYLIFE inertial confinement fusion (ICF) reactor. The HYLIFE concept utilizes lasers or heavy ion beams to rapidly heat and compress D-T targets injected into the center of a reactor chamber. A segmented blanket of falling molten lithium or Li2BeF4 (Flibe) jets encircles the reactor`s central cavity, shielding the reactor structure from radiation damage, absorbing the fusion energy, and breeding more tritium fuel. X-rays from the fusion microexplosion will ablate a thin layer of blanket material from the surfaces which face toward the fusion site. This generates a highly energetic vapor, which mostly coalesces in the central cavity. The blast expansion from the central cavity generates a shock which propagates through the segmented blanket - a complex geometry, gas-continuous two-phase medium. The impulse that the blast gives to the liquid as it vents past, the gas shock on the chamber wall, and ultimately the liquid impact on the wall are all important quantities to the HYLIFE structural designers.

  10. The nuclear liquid-gas phase transition: Present status and future perspectives

    Pochodzalla, J.; Imme, G.; Maddalena, V.

    1996-07-01

    More than two decades ago, the van der Waals behavior of the nucleon -nucleon force inspired the idea of a liquid-gas phase transition in nuclear matter. Heavy-ion reactions at relativistic energies offer the unique possibility for studying this phase transition in a finite, hadronic system. A general overview of this subject is given emphasizing the most recent results on nuclear calorimetry. (orig.)

  11. Isospin and momentum dependence of liquid-gas phase transition in hot asymmetric nuclear matter

    Xu, Jun; Ma, Hongru; Chen, Liewen; Li, Baoan

    2008-01-01

    The liquid-gas phase transition in hot neutron-rich nuclear matter is investigated within a self-consistent thermal model using different interactions with or without isospin and/or momentum dependence. The boundary of the phase-coexistence region is shown to be sensitive to the density dependence of the nuclear symmetry energy as well as the isospin and momentum dependence of the nuclear interaction. (author)

  12. Quantitation of anticonvulsant drugs in serum by gas-chromatography on the stationary phase SP-2510.

    Godolphin, W; Thoma, J

    1978-03-01

    A new column packing, SP-2510 DA (Supelco, Inc., Bellefonte, Pa. 16823), is an excellent stationary phase for the determination of a wide variety of anticonvulsant drugs by gas--liquid chromatography without derivatization. However, when uncomplicated extraction procedures are used, serum cholesterol interferes with the determination of primidone. By the simple expedient of adding a short "pre-column" containing another phase (SP-2250 DA) the problem is overcome.

  13. Gas-phase spectra of MgO molecules: a possible connection from gas-phase molecules to planet formation

    Kloska, Katherine A.; Fortenberry, Ryan C.

    2018-02-01

    A more fine-tuned method for probing planet-forming regions, such as protoplanetary discs, could be rovibrational molecular spectroscopy observation of particular premineral molecules instead of more common but ultimately less related volatile organic compounds. Planets are created when grains aggregate, but how molecules form grains is an ongoing topic of discussion in astrophysics and planetary science. Using the spectroscopic data of molecules specifically involved in mineral formation could help to map regions where planet formation is believed to be occurring in order to examine the interplay between gas and dust. Four atoms are frequently associated with planetary formation: Fe, Si, Mg and O. Magnesium, in particular, has been shown to be in higher relative abundance in planet-hosting stars. Magnesium oxide crystals comprise the mineral periclase making it the chemically simplest magnesium-bearing mineral and a natural choice for analysis. The monomer, dimer and trimer forms of (MgO)n with n = 1-3 are analysed in this work using high-level quantum chemical computations known to produce accurate results. Strong vibrational transitions at 12.5, 15.0 and 16.5 μm are indicative of magnesium oxide monomer, dimer and trimer making these wavelengths of particular interest for the observation of protoplanetary discs and even potentially planet-forming regions around stars. If such transitions are observed in emission from the accretion discs or absorptions from stellar spectra, the beginning stages of mineral and, subsequently, rocky body formation could be indicated.

  14. Revealing the hidden structural phases of FeRh

    Kim, Jinwoong; Ramesh, R.; Kioussis, Nicholas

    2016-11-01

    Ab initio electronic structure calculations reveal that tetragonal distortion has a dramatic effect on the relative stability of the various magnetic structures (C-, A-, G-, A'-AFM, and FM) of FeRh giving rise to a wide range of novel stable/metastable structures and magnetic phase transitions between these states. We predict that the cubic G-AFM structure, which was believed thus far to be the ground state, is metastable and that the tetragonally expanded G-AFM is the stable structure. The low energy barrier separating these states suggests phase coexistence at room temperature. We propose an A'-AFM phase to be the global ground state among all magnetic phases which arises from the strain-induced tuning of the exchange interactions. The results elucidate the underlying mechanism for the recent experimental findings of electric-field control of magnetic phase transition driven via tetragonal strain. The magnetic phase transitions open interesting prospects for exploiting strain engineering for the next-generation memory devices.

  15. Two-phase flow structure in large diameter pipes

    Smith, T.R.; Schlegel, J.P.; Hibiki, T.; Ishii, M.

    2012-01-01

    Highlights: ► Local profiles of various quantities measured in large diameter pipe. ► Database for interfacial area in large pipes extended to churn-turbulent flow. ► Flow regime map confirms previous models for flow regime transitions. ► Data will be useful in developing interfacial area transport models for large pipes. - Abstract: Flow in large pipes is important in a wide variety of applications. In the nuclear industry in particular, understanding of flow in large diameter pipes is essential in predicting the behavior of reactor systems. This is especially true of natural circulation Boiling Water Reactor (BWR) designs, where a large-diameter chimney above the core provides the gravity head to drive circulation of the coolant through the reactor. The behavior of such reactors during transients and during normal operation will be predicted using advanced thermal–hydraulics analysis codes utilizing the two-fluid model. Essential to accurate two-fluid model calculations is reliable and accurate computation of the interfacial transfer terms. These interfacial transfer terms can be expressed as the product of one term describing the potential driving the transfer and a second term describing the available surface area for transfer, or interfacial area concentration. Currently, the interfacial area is predicted using flow regime dependent empirical correlations; however the interfacial area concentration is best computed through the use of the one-dimensional interfacial area transport equation (IATE). To facilitate the development of IATE source and sink term models in large-diameter pipes a fundamental understanding of the structure of the two-phase flow is essential. This understanding is improved through measurement of the local void fraction, interfacial area concentration and gas velocity profiles in pipes with diameters of 0.102 m and 0.152 m under a wide variety of flow conditions. Additionally, flow regime identification has been performed to

  16. Financial structure of Korea Gas Corporation's LNG projects

    Jeongsoo Ko

    1991-01-01

    When an Indonesian LNG tanker arrived in Korea for the first time in October 1986, Korea became the seventh LNG-consuming nation in the world. The imported LNG has contributed greatly to solving pollution problems and ensuring a stable supply of energy to Korea through the diversification of energy sources. So far, the LNG supply has been confined to the Metropolitan area. The Korea Gas Corporation now plans to expand the LNG supply to cover the entire nation. This paper introduces the experience and future plan of Korea's LNG projects with a special reference to their financial structure

  17. Graphites and composites irradiations for gas cooled reactor core structures

    Van der Laan, J.G.; Vreeling, J.A.; Buckthorpe, D.E.; Reed, J.

    2008-01-01

    Full text of publication follows. Material investigations are undertaken as part of the European Commission 6. Framework Programme for helium-cooled fission reactors under development like HTR, VHTR, GCFR. The work comprises a range of activities, from (pre-)qualification to screening of newly designed materials. The High Flux Reactor at Petten is the main test bed for the irradiation test programmes of the HTRM/M1, RAPHAEL and ExtreMat Integrated Projects. These projects are supported by the European Commission 5. and 6. Framework Programmes. To a large extent they form the European contribution to the Generation-IV International Forum. NRG is also performing a Materials Test Reactor project to support British Energy in preparing extended operation of their Advanced Gas-cooled Reactors (AGR). Irradiations of commercial and developmental graphite grades for HTR core structures are undertaken in the range of 650 to 950 deg C, with a view to get data on physical and mechanical properties that enable engineering design. Various C- and SiC-based composite materials are considered for support structures or specific components like control rods. Irradiation test matrices are chosen to cover commercial materials, and to provide insight on the behaviour of various fibre and matrix types, and the effects of architecture and manufacturing process. The programme is connected with modelling activities to support data trending, and improve understanding of the material behaviour and micro-structural evolution. The irradiation programme involves products from a large variety of industrial and research partners, and there is strong interaction with other high technology areas with extreme environments like space, electronics and fusion. The project on AGR core structures graphite focuses on the effects of high dose neutron irradiation and simultaneous radiolytic oxidation in a range of 350 to 450 deg C. It is aimed to provide data on graphite properties into the parameter space

  18. Oxidative potential of gas phase combustion emissions - An underestimated and potentially harmful component of air pollution from combustion processes

    Stevanovic, S.; Vaughan, A.; Hedayat, F.; Salimi, F.; Rahman, M. M.; Zare, A.; Brown, R. A.; Brown, R. J.; Wang, H.; Zhang, Z.; Wang, X.; Bottle, S. E.; Yang, I. A.; Ristovski, Z. D.

    2017-06-01

    The oxidative potential (OP) of the gas phase is an important and neglected aspect of environmental toxicity. Whilst prolonged exposure to particulate matter (PM) associated reactive oxygen species (ROS) have been shown to lead to negative health effects, the potential for compounds in gas phase to cause similar effects is yet to be understood. In this study we describe: the significance of the gas phase OP generated through vehicle emissions; discuss the origin and evolution of species contributing to measured OP; and report on the impact of gas phase OP on human lung cells. The model aerosol for this study was exhaust emitted from a Euro III Common-rail diesel engine fuelled with different blends of diesel and biodiesel. The gas phase of these emissions was found to be potentially as hazardous as the particle phase. Fuel oxygen content was found to negatively correlate with the gas phase OP, and positively correlate with particle phase OP. This signifies a complex interaction between reactive species present in gas and particle phase. Furthermore, this interaction has an overarching effect on the OP of both particle and gas phase, and therefore the toxicity of combustion emissions.

  19. Aqueous-gas phase partitioning and hydrolysis of organic iodides

    Glowa, G.A.; Wren, J.C.

    2003-01-01

    The volatility and decomposition of organic iodides in a reactor containment building are important parameters to consider when assessing the potential consequences of a nuclear reactor accident. However, there are few experimental data available for the volatilities (often reported as partition coefficients) or few rate constants regarding the decomposition (via hydrolysis) of organic iodides. The partition coefficients and hydrolysis rate constants of eight organic iodides, having a range of molecular structures, have been measured in the current studies. This data, and data accumulated in the literature, have been reviewed and discussed to provide guidelines for appropriate organization of organic iodides for the purpose of modelling iodine behaviour under postulated nuclear reactor accident conditions. After assessment of the partition coefficients and their temperature dependences of many classes of organic compounds, it was found that organic iodides could be divided into two categories based upon their volatility relative to molecular iodine. Similarly, hydrolysis rates and their temperature dependences are assigned to the two categories of organic iodides. (author)

  20. Magnetic resonance velocity imaging of liquid and gas two-phase flow in packed beds.

    Sankey, M H; Holland, D J; Sederman, A J; Gladden, L F

    2009-02-01

    Single-phase liquid flow in porous media such as bead packs and model fixed bed reactors has been well studied by MRI. To some extent this early work represents the necessary preliminary research to address the more challenging problem of two-phase flow of gas and liquid within these systems. In this paper, we present images of both the gas and liquid velocities during stable liquid-gas flow of water and SF(6) within a packing of 5mm spheres contained within columns of diameter 40 and 27 mm; images being acquired using (1)H and (19)F observation for the water and SF(6), respectively. Liquid and gas flow rates calculated from the velocity images are in agreement with macroscopic flow rate measurements to within 7% and 5%, respectively. In addition to the information obtained directly from these images, the ability to measure liquid and gas flow fields within the same sample environment will enable us to explore the validity of assumptions used in numerical modelling of two-phase flows.

  1. A modeling and experimental study of flue gas desulfurization in a dense phase tower

    Chang, Guanqin; Song, Cunyi; Wang, Li

    2011-01-01

    We used a dense phase tower as the reactor in a novel semi-dry flue gas desulfurization process to achieve a high desulfurization efficiency of over 95% when the Ca/S molar ratio reaches 1.3. Pilot-scale experiments were conducted for choosing the parameters of the full-scale reactor. Results show that with an increase in the flue gas flow rate the rate of the pressure drop in the dense phase tower also increases, however, the rate of the temperature drop decreases in the non-load hot gas. We chose a water flow rate of 0.6 kg/min to minimize the approach to adiabatic saturation temperature difference and maximize the desulfurization efficiency. To study the flue gas characteristics under different processing parameters, we simulated the desulfurization process in the reactor. The simulated data matched very well with the experimental data. We also found that with an increase in the Ca/S molar ratio, the differences between the simulation and experimental data tend to decrease; conversely, an increase in the flue gas flow rate increases the difference; this may be associated with the surface reactions caused by collision, coalescence and fragmentation between the dispersed phases.

  2. Photocatalytic Activity of Nanotubular TiO2 Films Obtained by Anodic Oxidation: A Comparison in Gas and Liquid Phase

    Beatriz Eugenia Sanabria Arenas

    2018-03-01

    Full Text Available The availability of immobilized nanostructured photocatalysts is of great importance in the purification of both polluted air and liquids (e.g., industrial wastewaters. Metal-supported titanium dioxide films with nanotubular morphology and good photocatalytic efficiency in both environments can be produced by anodic oxidation, which avoids release of nanoscale materials in the environment. Here we evaluate the effect of different anodizing procedures on the photocatalytic activity of TiO2 nanostructures in gas and liquid phases, in order to identify the most efficient and robust technique for the production of TiO2 layers with different morphologies and high photocatalytic activity in both phases. Rhodamine B and toluene were used as model pollutants in the two media, respectively. It was found that the role of the anodizing electrolyte is particularly crucial, as it provides substantial differences in the oxide specific surface area: nanotubular structures show remarkably different activities, especially in gas phase degradation reactions, and within nanotubular structures, those produced by organic electrolytes lead to better photocatalytic activity in both conditions tested.

  3. Ultra-Lightweight Nanocomposite Foams and Sandwich Structures for Space Structures Applications, Phase I

    National Aeronautics and Space Administration — Space structures that are ultra-lightweight, and have gas barrier property, space durability, radiation resistance and high impact resistance are desirable to...

  4. Ultra-Lightweight Nanocomposite Foams and Sandwich Structures for Space Structures Applications, Phase II

    National Aeronautics and Space Administration — Space structures that are ultra-lightweight, and have gas barrier property, space durability, radiation resistance, EMI shielding, and high impact resistance are...

  5. A New Void Fraction Measurement Method for Gas-Liquid Two-Phase Flow in Small Channels.

    Li, Huajun; Ji, Haifeng; Huang, Zhiyao; Wang, Baoliang; Li, Haiqing; Wu, Guohua

    2016-01-27

    Based on a laser diode, a 12 × 6 photodiode array sensor, and machine learning techniques, a new void fraction measurement method for gas-liquid two-phase flow in small channels is proposed. To overcome the influence of flow pattern on the void fraction measurement, the flow pattern of the two-phase flow is firstly identified by Fisher Discriminant Analysis (FDA). Then, according to the identification result, a relevant void fraction measurement model which is developed by Support Vector Machine (SVM) is selected to implement the void fraction measurement. A void fraction measurement system for the two-phase flow is developed and experiments are carried out in four different small channels. Four typical flow patterns (including bubble flow, slug flow, stratified flow and annular flow) are investigated. The experimental results show that the development of the measurement system is successful. The proposed void fraction measurement method is effective and the void fraction measurement accuracy is satisfactory. Compared with the conventional laser measurement systems using standard laser sources, the developed measurement system has the advantages of low cost and simple structure. Compared with the conventional void fraction measurement methods, the proposed method overcomes the influence of flow pattern on the void fraction measurement. This work also provides a good example of using low-cost laser diode as a competent replacement of the expensive standard laser source and hence implementing the parameter measurement of gas-liquid two-phase flow. The research results can be a useful reference for other researchers' works.

  6. Measurement of phase interaction in dispersed gas-particle two-phase flow by phase-doppler anemometry

    Mergheni Ali Mohamed; Ben Ticha Hmaied; Sautet Jen-Charles; Godard Gille; Ben Nasrallah Sassi

    2008-01-01

    For simultaneous measurement of size and velocity distributions of continuous and dispersed phases in a two-phase flow a technique phase-Doppler anemometry was used. Spherical glass particles with a particle diameter range from 102 up to 212 µm were used. In this two-phase flow an experimental results are presented which indicate a significant influence of the solid particles on the flow characteristics. The height of influence of these effects depends on the local position in the jet. Near t...

  7. Order from the disorder: hierarchical nanostructures self-assembled from the gas phase (Conference Presentation)

    Di Fonzo, Fabio

    2017-02-01

    The assembly of nanoscale building blocks in engineered mesostructures is one of the fundamental goals of nanotechnology. Among the various processes developed to date, self-assembly emerges as one of the most promising, since it relays solely on basic physico-chemical forces. Our research is focused on a new type of self-assembly strategy from the gas-phase: Scattered Ballistic Deposition (SBD). SBD arises from the interaction of a supersonic molecular beam with a static gas and enables the growth of quasi-1D hierarchical mesostructures. Overall, they resemble a forest composed of individual, high aspect-ratio, tree-like structures, assembled from amorphous or crystalline nanoparticles. SBD is a general occurring phenomenon and can be obtained with different vapour or cluster sources. In particular, SBD by Pulsed Laser Deposition is a convenient physical vapor technique that allows the generation of supersonic plasma jets from any inorganic material irrespective of melting temperature, preserving even the most complex stoichiometries. One of the advantages of PLD over other vapour deposition techniques is extremely wide operational pressure range, from UHV to ambient pressure. These characteristics allowed us to develop quasi-1D hierarchical nanostructures from different transition metal oxides, semiconductors and metals. The precise control offered by the SBD-PLD technique over material properties at the nanoscale allowed us to fabricate ultra-thin, high efficiency hierarchical porous photonic crystals with Bragg reflectivity up to 85%. In this communication we will discuss the application of these materials to solar energy harvesting and storage, stimuli responsive photonic crystals and smart surfaces with digital control of their wettability behaviour.

  8. Do medium heavy fragments give evidence for a liquid-gas phase transition

    Trockel, R.; Hildenbrand, K.D.; Lynen, U.; Mueller, W.F.J.; Rabe, H.J.; Sann, H.; Stelzer, H.; Wada, R.; Brummund, N.; Glasow, R.; Kampert, K.H.; Santo, R.; Pelte, D.; Pochodzalla, J.; Eckert, E.

    1985-09-01

    Light and medium heavy fragments have been measured in light ion induced reactions at intermediate energies. The energy spectra have been parametrized with moving source fits. The resulting temperatures and yields do not confirm the expectations of a liquid-gas phase transition. (orig.)

  9. Electron Attachment to the Gas Phase DNA Bases Cytosine and Thymine

    Denifl, S.; Ptasiňska, S.; Probst, M.; Hrušák, Jan; Scheier, P.; Märk, T. D.

    2004-01-01

    Roč. 108, č. 31 (2004), s. 6562-6569 ISSN 1089-5639 R&D Projects: GA ČR GA203/02/0737 Institutional research plan: CEZ:AV0Z4040901 Keywords : gas-phase * cytosine * thymine Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.639, year: 2004

  10. How Pt nanoparticles affect TiO2-induced gas-phase photocatalytic oxidation reactions

    Fraters, B.D.; Amrollahi Buky, Rezvaneh; Mul, Guido

    2015-01-01

    The effect of Pt nanoparticles on the gas-phase photocatalytic oxidation activity of TiO2 is shown to be largely dependent on the molecular functionality of the substrate. We demonstrate that Pt nanoparticles decrease rates in photocatalytic oxidation of propane, whereas a strong beneficial effect

  11. A gas phase work station for the Brazilian National Synchrotron Laboratory

    Souza, G.G.B. de

    1988-01-01

    A gas phase work station which has been proposed to the Brazilian National Synchrotron Laboratory is described with emphasis on the broad spectrum of physical and chemical processes which can be studied with the incorporated instrumentation. (A.C.A.S.) [pt

  12. The constitutive distributed parameter model of multicomponent chemical processes in gas, fluid and solid phase

    Niemiec, W.

    1985-01-01

    In the literature of distributed parameter modelling of real processes is not considered the class of multicomponent chemical processes in gas, fluid and solid phase. The aim of paper is constitutive distributed parameter physicochemical model, constructed on kinetics and phenomenal analysis of multicomponent chemical processes in gas, fluid and solid phase. The mass, energy and momentum aspects of these multicomponent chemical reactions and adequate phenomena are utilized in balance operations, by conditions of: constitutive invariance for continuous media with space and time memories, reciprocity principle for isotropic and anisotropic nonhomogeneous media with space and time memories, application of definitions of following derivative and equation of continuity, to the construction of systems of partial differential constitutive state equations, in the following derivative forms for gas, fluid and solid phase. Couched in this way all physicochemical conditions of multicomponent chemical processes in gas, fluid and solid phase are new form of constitutive distributed parameter model for automatics and its systems of equations are new form of systems of partial differential constitutive state equations in sense of phenomenal distributed parameter control

  13. Role of isospin in nuclear-matter liquid-gas phase transition

    Ducoin, C.

    2006-10-01

    Nuclear matter presents a phase transition of the liquid-gas type. This well-known feature is due to the nuclear interaction profile (mean-range attractive, short-range repulsive). Symmetric-nuclear-matter thermodynamics is thus analogous to that of a Van der Waals fluid. The study shows up to be more complex in the case of asymmetric matter, composed of neutrons and protons in an arbitrary proportion. Isospin, which distinguishes both constituents, gives a measure of this proportion. Studying asymmetric matter, isospin is an additional degree of freedom, which means one more dimension to consider in the space of observables. The nuclear liquid-gas transition is associated with the multi-fragmentation phenomenon observed in heavy-ion collisions, and to compact-star physics: the involved systems are neutron rich, so they are affected by the isospin degree of freedom. The present work is a theoretical study of isospin effects which appear in the asymmetric nuclear matter liquid-gas phase transition. A mean-field approach is used, with a Skyrme nuclear effective interaction. We demonstrate the presence of a first-order phase transition for asymmetric matter, and study the isospin distillation phenomenon associated with this transition. The case of phase separation at thermodynamic equilibrium is compared to spinodal decomposition. Finite size effects are addressed, as well as the influence of the electron gas which is present in the astrophysical context. (author)

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

    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

  15. ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE THERMAL DESORPTION UNIT - APPLICATIONS ANALYSIS REPORT

    ELI ECO Logic International, Inc.'s Thermal Desorption Unit (TDU) is specifically designed for use with Eco Logic's Gas Phase Chemical Reduction Process. The technology uses an externally heated bath of molten tin in a hydrogen atmosphere to desorb hazardous organic compounds fro...

  16. Gas-phase infrared spectrum of the anionic GFP-chromophore

    Almasian, M.; Grzetic, J.; G. Berden,; Bakker, B.; Buma, W. J.; Oomens, J.

    2012-01-01

    The gas-phase IR spectrum of the anionic chromophore of the green fluorescent protein (p-hydroxy-benzylidene-2,3-dimethylimidazolidinone, HBDI) is recorded in the 800–1800 cm−1 frequency range using the free electron laser FELIX in combination with an electrospray ionization (ESI) Fourier

  17. Gas-phase salt bridge interactions between glutamic acid and arginine

    Jaeqx, S.; Oomens, J.; Rijs, A.M.

    2013-01-01

    The gas-phase side chain-side chain (SC-SC) interaction and possible proton transfer between glutamic acid (Glu) and arginine (Arg) residues are studied under low-temperature conditions in an overall neutral peptide. Conformation-specific IR spectra, obtained with the free electron laser FELIX, in

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

    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.

  19. Ab initio study of gas phase and water-assisted tautomerization of ...

    WINTEC

    Water-assisted tautomerization in maleimide and formamide showed that difference in energy barrier reduces to 2⋅83 kcal/mol from 10⋅41 kcal/mol (in gas phase) at B3LYP level, which resulted that maleimide readily undergoes tautomerization in water molecule. Keywords. Ab Initio calculations; maleimide; formamide; ...

  20. Gas-phase UF6 enrichment monitor for enrichment plant safeguards

    Strittmatter, R.B.; Tape, J.W.

    1980-03-01

    An in-line enrichment monitor is being developed to provide real-time enrichment data for the gas-phase UF 6 feed stream of an enrichment plant. The nondestructive gamma-ray assay method can be used to determine the enrichment of natural UF 6 with a relative precision of better than 1% for a wide range of pressures

  1. Mid-IR spectra of different conformers of phenylalanine in the gas phase

    von Helden, G.; Compagnon, I.; Blom, M. N.; Frankowski, M.; Erlekam, U.; Oomens, J.; Brauer, B.; Gerber, R. B.; Meijer, G.

    2008-01-01

    The experimental mid- and far-IR spectra of six conformers of phenylalanine in the gas phase are presented. The experimental spectra are compared to spectra calculated at the B3LYP and at the MP2 level. The differences between B3LYP and MP2 IR spectra are found to be small. The agreement between

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

    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.

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

    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

  4. Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

    Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas

    2009-01-01

    The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V2O5/TiO2 catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near...

  5. Study of Iodine Behavior in the Gas Phase during a Severe Accident

    Kim, Hanchul; Cho, Yeonghun; Ryu, Myunghyun

    2014-01-01

    Among the iodine species, the organic iodides produced from the reaction between iodine and organics such as paint, are not easily trapped by the filters during the containment venting following a severe accident. Korea Institute of Nuclear Safety (KINS) has been studying this issue, joining international research programs such as ISTP-EPICUR, OECDBIP and OECD-STEM. In the course of this study, a simple iodine model, RAIM (Radio-Active Iodine chemistry Model) has been developed (Oh et al., 2011), based on the IMOD methodology, and other previous studies. This paper deals with our recent activities on this study, including the development of the model for the iodine reactions in gas phase. Iodine reactions in gas phase were modeled and added to the RAIM code, taking into account several relevant reactions such as formation of ARP, iodine oxide, and organic iodides in gas phase. RAIM was then applied to analyze the S2-6-5-2 test for which iodine-loaded coupons were tested in gas phase. The analysis results show a reasonable estimation of volatile iodine concentration with the desorption rate constant of about 10 -6 s -1 , while those of the other iodine species overestimated for the whole period of the test. It reveals the need to determine appropriate values for the rate constants for formation of iodine oxides and organic iodides

  6. Integration of phase change materials in compressed hydrogen gas systems: Modelling and parametric analysis

    Mazzucco, Andrea; Rothuizen, Erasmus; Jørgensen, Jens-Erik

    2016-01-01

    to the phase change material, mainly occurs after the fueling is completed, resulting in a hydrogen peak temperature higher than 85 C and a lower fueled mass than a gas-cooled system. Such a mass reduction accounts for 12% with respect to the case of a standard tank system fueled at 40 C. A parametric analysis...

  7. Gas-phase synthesis of magnesium nanoparticles : A high-resolution transmission electron microscopy study

    Kooi, B.J.; Palasantzas, G.; de Hosson, J.T.M.

    2006-01-01

    Magnesium nanoparticles with size above 10 nm, prepared by gas-phase syntheses, were investigated by high-resolution transmission electron microscopy. The dominant particle shape is a hexagonal prism terminated by Mg(0002) and Mg{1010} facets. Oxidation of Mg yields a MgO shell (similar to 3 nm

  8. Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

    Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie

    2014-01-01

    Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic...

  9. Hydrocarbon fuels from gas phase decarboxylation of hydrolyzed free fatty acid

    Wang, Weicheng; Roberts, William L.; Stikeleather, Larry F.

    2012-01-01

    Gas phase decarboxylation of hydrolyzed free fatty acid (FFA) from canola oil has beeninvestigated in two fix-bed reactors by changing reaction parameters such as temperatures,FFA feed rates, and H 2-to-FFA molar ratios. FFA, which contains mostly C

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

    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

  11. Why do disk galaxies present a common gas-phase metallicity gradient?

    Chang, R.; Zhang, Shuhui; Shen, Shiyin; Yin, Jun; Hou, Jinliang

    2017-03-01

    CALIFA data show that isolated disk galaxies present a common gas-phase metallicity gradient, with a characteristic slope of -0.1dex/re between 0.3 and 2 disk effective radius re (Sanchez et al. 2014). Here we construct a simple model to investigate which processes regulate the formation and evolution.

  12. Gas-phase photoemission with soft x-rays: cross sections and angular distributions

    Shirley, D.A.; Kobrin, P.H.; Truesdale, C.M.; Lindle, D.W.; Ferrett, T.A.; Heimann, P.A.; Becker, U.; Kerkhoff, H.G.; Southworth, S.H.

    1983-09-01

    A summary is presented of typical gas-phase photoemission studies based on synchrotron radiation in the 50-5000 eV range, using beam lines at the Stanford Synchrotron Radiation Laboratory. Three topics are addressed: atomic inner-shell photoelectron cross sections and asymmetries, correlation peaks in rare gases, and core-level shape resonances in molecules

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

    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

  14. Corundum-to-spinel structural phase transformation in alumina

    Adachi, Shogo [Department of Materials Science and Engineering, Kyushu Institute of Technology, Fukuoka 804-8550 (Japan); Ishimaru, Manabu, E-mail: ishimaru@post.matsc.kyutech.ac.jp [Department of Materials Science and Engineering, Kyushu Institute of Technology, Fukuoka 804-8550 (Japan); Sina, Younes; McHargue, Carl J.; Sickafus, Kurt E. [Materials Science and Engineering Department, University of Tennessee, Knoxville, TN 37996-2200 (United States); Alves, Eduardo [Unit of Physics and Accelerators, Ion Beam Laboratory, Instituto Superior Técnico/Instituto Tecnológico e Nuclear, EN. 10 2686-953 Sacavém (Portugal)

    2015-09-01

    Several polymorphs exist in alumina (Al{sub 2}O{sub 3}), and they transform to a stable α-phase with a hexagonal corundum structure on thermal annealing. This structural change is irreversible as a function of temperature, and transformation of corundum to another metastable crystalline phase has never been observed by heat treatments. In this study, we irradiated single crystals of Al{sub 2}O{sub 3} with Zr ions and obtained an irradiated microstructure consisting of a buried α-Al{sub 2}O{sub 3} layer surrounded on top and bottom by layers of a defect cubic spinel Al{sub 2}O{sub 3} phase. We examined the thermal stability of this microstructure using transmission electron microscopy and X-ray diffraction. We found that the corundum phase completely transforms to the spinel phase following annealing at 1173 K for 1 h: the thermodynamically stable phase transforms to the metastable phase by heat treatments. We discuss this unusual structural change within the context of our results as well as previous observations.

  15. Summary on experimental methods for statistical transient analysis of two-phase gas-liquid flow

    Delhaye, J.M.; Jones, O.C. Jr.

    1976-06-01

    Much work has been done in the study of two-phase gas-liquid flows. Although it has been recognized superficially that such flows are not homogeneous in general, little attention has been paid to the inherent discreteness of the two-phase systems. Only relatively recently have fluctuating characteristics of two-phase flows been studied in detail. As a result, new experimental devices and techniques have been developed for use in measuring quantities previously ignored. This report reviews and summarizes most of these methods in an effort to emphasize the importance of the fluctuating nature of these flows and as a guide to further research in this field

  16. Quantum phase space for an ideal relativistic gas in d spatial dimensions

    Hayashi, M.; Vera Mendoza, H.

    1992-01-01

    We present the closed formula for the d-dimensional invariant phase-space integral for an ideal relativistic gas in an exact integral form. In the particular cases of the nonrelativistic and the extreme relativistic limits the phase-space integrals are calculated analytically. Then we consider the d-dimensional invariant phase space with quantum statistic and derive the cluster decomposition for the grand canonical and canonical partition functions as well as for the microcanonical and grand microcanonical densities of states. As a showcase, we consider the black-body radiation in d dimensions (Author)

  17. Holographic entanglement entropy and the extended phase structure of STU black holes

    Caceres, Elena; Nguyen, Phuc H.; Pedraza, Juan F.

    2015-01-01

    We study the extended thermodynamics, obtained by considering the cosmological constant as a thermodynamic variable, of STU black holes in 4-dimensions in the fixed charge ensemble. The associated phase structure is conjectured to be dual to an RG-flow on the space of field theories. We find that for some charge configurations the phase structure resembles that of a Van der Waals gas: the system exhibits a family of first order phase transitions ending in a second order phase transition at a critical temperature. We calculate the holographic entanglement entropy for several charge configurations and show that for the cases where the gravity background exhibits Van der Waals behavior, the entanglement entropy presents a transition at the same critical temperature. To further characterize the phase transition we calculate appropriate critical exponents and show that they coincide. Thus, the entanglement entropy successfully captures the information of the extended phase structure. Finally, we discuss the physical interpretation of the extended space in terms of the boundary QFT and construct various holographic heat engines dual to STU black holes.

  18. Multi-scale structural analysis of gas diffusion layers

    Göbel, Martin; Godehardt, Michael; Schladitz, Katja

    2017-07-01

    The macroscopic properties of materials are strongly determined by their micro structure. Here, transport properties of gas diffusion layers (GDL) for fuel cells are considered. In order to simulate flow and thermal properties, detailed micro structural information is essential. 3D images obtained by high-resolution computed tomography using synchrotron radiation and scanning electron microscopy (SEM) combined with focused ion beam (FIB) serial slicing were used. A recent method for reconstruction of porous structures from FIB-SEM images and sophisticated morphological image transformations were applied to segment the solid structural components. The essential algorithmic steps for segmenting the different components in the tomographic data-sets are described and discussed. In this paper, two types of GDL, based on a non-woven substrate layer and a paper substrate layer were considered, respectively. More than three components are separated within the synchrotron radiation computed tomography data. That is, fiber system, polytetrafluoroethylene (PTFE) binder/impregnation, micro porous layer (MPL), inclusions within the latter, and pore space are segmented. The usage of the thus derived 3D structure data in different simulation applications can be demonstrated. Simulations of macroscopic properties such as thermal conductivity, depending on the flooding state of the GDL are possible.

  19. Experimental and numerical investigation of shock wave propagation through complex geometry, gas continuous, two-phase media

    Liu, James Chien-Chih [Univ. of California, Berkeley, CA (United States)

    1993-01-01

    The work presented here investigates the phenomenon of shock wave propagation in gas continuous, two-phase media. The motivation for this work stems from the need to understand blast venting consequences in the HYLIFE inertial confinement fusion (ICF) reactor. The HYLIFE concept utilizes lasers or heavy ion beams to rapidly heat and compress D-T targets injected into the center of a reactor chamber. A segmented blanket of failing molten lithium or Li2BeF4 (Flibe) jets encircles the reactors central cavity, shielding the reactor structure from radiation damage, absorbing the fusion energy, and breeding more tritium fuel.

  20. Solving kinetic equations with adaptive mesh in phase space for rarefied gas dynamics and plasma physics (Invited)

    Kolobov, Vladimir; Arslanbekov, Robert; Frolova, Anna

    2014-01-01

    The paper describes an Adaptive Mesh in Phase Space (AMPS) technique for solving kinetic equations with deterministic mesh-based methods. The AMPS technique allows automatic generation of adaptive Cartesian mesh in both physical and velocity spaces using a Tree-of-Trees data structure. We illustrate advantages of AMPS for simulations of rarefied gas dynamics and electron kinetics on low temperature plasmas. In particular, we consider formation of the velocity distribution functions in hypersonic flows, particle kinetics near oscillating boundaries, and electron kinetics in a radio-frequency sheath. AMPS provide substantial savings in computational cost and increased efficiency of the mesh-based kinetic solvers

  1. Experimental and numerical investigation of shock wave propagation through complex geometry, gas continuous, two-phase media

    Liu, J. Chien-Chih

    1993-01-01

    The work presented here investigates the phenomenon of shock wave propagation in gas continuous, two-phase media. The motivation for this work stems from the need to understand blast venting consequences in the HYLIFE inertial confinement fusion (ICF) reactor. The HYLIFE concept utilizes lasers or heavy ion beams to rapidly heat and compress D-T targets injected into the center of a reactor chamber. A segmented blanket of failing molten lithium or Li 2 BeF 4 (Flibe) jets encircles the reactors central cavity, shielding the reactor structure from radiation damage, absorbing the fusion energy, and breeding more tritium fuel

  2. Solving kinetic equations with adaptive mesh in phase space for rarefied gas dynamics and plasma physics (Invited)

    Kolobov, Vladimir [CFD Research Corporation, Huntsville, AL 35805, USA and The University of Alabama in Huntsville, Huntsville, AL 35805 (United States); Arslanbekov, Robert [CFD Research Corporation, Huntsville, AL 35805 (United States); Frolova, Anna [Computing Center of the Russian Academy of Sciences, Moscow, 119333 (Russian Federation)

    2014-12-09

    The paper describes an Adaptive Mesh in Phase Space (AMPS) technique for solving kinetic equations with deterministic mesh-based methods. The AMPS technique allows automatic generation of adaptive Cartesian mesh in both physical and velocity spaces using a Tree-of-Trees data structure. We illustrate advantages of AMPS for simulations of rarefied gas dynamics and electron kinetics on low temperature plasmas. In particular, we consider formation of the velocity distribution functions in hypersonic flows, particle kinetics near oscillating boundaries, and electron kinetics in a radio-frequency sheath. AMPS provide substantial savings in computational cost and increased efficiency of the mesh-based kinetic solvers.

  3. Comprehensive Analysis of the Gas- and Particle-Phase Products of VOC Oxidation

    Bakker-Arkema, J.; Ziemann, P. J.

    2017-12-01

    Controlled environmental chamber studies are important for determining atmospheric reaction mechanisms and gas and aerosol products formed in the oxidation of volatile organic compounds (VOCs). Such information is necessary for developing detailed chemical models for use in predicting the atmospheric fate of VOCs and also secondary organic aerosol (SOA) formation. However, complete characterization of atmospheric oxidation reactions, including gas- and particle-phase product yields, and reaction branching ratios, are difficult to achieve. In this work, we investigated the reactions of terminal and internal alkenes with OH radicals in the presence of NOx in an attempt to fully characterize the chemistry of these systems while minimizing and accounting for the inherent uncertainties associated with environmental chamber experiments. Gas-phase products (aldehydes formed by alkoxy radical decomposition) and particle-phase products (alkyl nitrates, β-hydroxynitrates, dihydroxynitrates, 1,4-hydroxynitrates, 1,4-hydroxycarbonyls, and dihydroxycarbonyls) formed through pathways involving addition of OH to the C=C double bond as well as H-atom abstraction were identified and quantified using a suite of analytical techniques. Particle-phase products were analyzed in real time with a thermal desorption particle beam mass spectrometer; and off-line by collection onto filters, extraction, and subsequent analysis of functional groups by derivatization-spectrophotometric methods developed in our lab. Derivatized products were also separated by liquid chromatography for molecular quantitation by UV absorbance and identification using chemical ionization-ion trap mass spectrometry. Gas phase aldehydes were analyzed off-line by collection onto Tenax and a 5-channel denuder with subsequent analysis by gas chromatography, or by collection onto DNPH-coated cartridges and subsequent analysis by liquid chromatography. The full product identification and quantitation, with careful

  4. Diffusion Monte Carlo simulations of gas phase and adsorbed D2-(H2)n clusters

    Curotto, E.; Mella, M.

    2018-03-01

    We have computed ground state energies and analyzed radial distributions for several gas phase and adsorbed D2(H2)n and HD(H2)n clusters. An external model potential designed to mimic ionic adsorption sites inside porous materials is used [M. Mella and E. Curotto, J. Phys. Chem. A 121, 5005 (2017)]. The isotopic substitution lowers the ground state energies by the expected amount based on the mass differences when these are compared with the energies of the pure clusters in the gas phase. A similar impact is found for adsorbed aggregates. The dissociation energy of D2 from the adsorbed clusters is always much higher than that of H2 from both pure and doped aggregates. Radial distributions of D2 and H2 are compared for both the gas phase and adsorbed species. For the gas phase clusters, two types of hydrogen-hydrogen interactions are considered: one based on the assumption that rotations and translations are adiabatically decoupled and the other based on nonisotropic four-dimensional potential. In the gas phase clusters of sufficiently large size, we find the heavier isotopomer more likely to be near the center of mass. However, there is a considerable overlap among the radial distributions of the two species. For the adsorbed clusters, we invariably find the heavy isotope located closer to the attractive interaction source than H2, and at the periphery of the aggregate, H2 molecules being substantially excluded from the interaction with the source. This finding rationalizes the dissociation energy results. For D2-(H2)n clusters with n ≥12 , such preference leads to the desorption of D2 from the aggregate, a phenomenon driven by the minimization of the total energy that can be obtained by reducing the confinement of (H2)12. The same happens for (H2)13, indicating that such an effect may be quite general and impact on the absorption of quantum species inside porous materials.

  5. Atmospheric-pressure dielectric barrier discharge with capillary injection for gas-phase nanoparticle synthesis

    Ghosh, Souvik; Liu, Tianqi; Bilici, Mihai; Cole, Jonathan; Huang, I-Min; Sankaran, R Mohan; Staack, David; Mariotti, Davide

    2015-01-01

    We present an atmospheric-pressure dielectric barrier discharge (DBD) reactor for gas-phase nanoparticle synthesis. Nickel nanoparticles are synthesized by homogenous nucleation from nickelocene vapor and characterized online by aerosol mobility measurements. The effects of residence time and precursor concentration on particle growth are studied. We find that narrower distributions of smaller particles are produced by decreasing the precursor concentration, in agreement with vapor nucleation theory, but larger particles and aggregates form at higher gas flow rates where the mean residence time should be reduced, suggesting a cooling effect that leads to enhanced particle nucleation. In comparison, incorporating a capillary gas injector to alter the velocity profile is found to significantly reduce particle size and agglomeration. These results suggest that capillary gas injection is a better approach to decreasing the mean residence time and narrowing the residence time distribution for nanoparticle growth by producing a sharp and narrow velocity profile. (paper)

  6. Visualization for gas-liquid two-phase flow using wire mesh tomography

    Motegi, Yuichi; Wanjiraniran, Weerin; Kikura, Hiroshige; Aritomi, Masanori; Yamauchi, Toyoaki

    2003-01-01

    Wire Mesh Tomography (WMT), which is system to measure two-phase flow, has been developed in our laboratory. Measurement principle of WMT is detecting conductivity difference between gas and liquid. WMT measures void fraction as raw date, and calculates gas velocity and bubble volume etc. In this paper, this measurement technique was applied to vertical circular pipe of 50 mm diameter and about 7 m heights. New Wire Mesh Sensor (WMS), which is measurement part of WMT, for circular pipe, have been made. When experiment was performed, superficial gas and water velocity. The effect of each flow parameter was found for void fraction, true gas velocity and bubble volume and the results was in good agreement with the past research, qualitatively. (author)

  7. Zpif's law in the liquid gas phase transition of nuclei

    Ma, Y.G. [China Center of Advanced Science and Technology (CCAST), Beijing, BJ (China). World Lab.; Shanghai Institute of Nuclear Research, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China)

    1999-12-01

    Zpif's law in the field of linguistics is tested in the nuclear disassembly within the framework of isospin dependent lattice gas model. It is found that the average cluster charge (or mass) of rank n in the charge (or mass) list shows exactly inversely to its rank, i.e., there exists Zpif's law, at the phase transition temperature. This novel criterion shall be helpful to search the nuclear liquid gas phase transition experimentally and theoretically. In addition, the finite size scaling of the effective phase transition temperature at which the Zpif's law appears is studied for several systems with different mass and the critical exponents of {nu} and {beta} are tentatively extracted. (orig.)

  8. Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography.

    Xie, Sheng-Ming; Yuan, Li-Ming

    2017-01-01

    Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Experimental redetermination of the gas-phase enthalpy of formation of ethyl 2-thiophenecarboxylate

    Santos, Ana Filipa L.O.M.; Ribeiro da Silva, Manuel A.V.

    2013-01-01

    The condensed phase standard (p° = 0.1 MPa) molar enthalpy of formation of ethyl-2-thiophenecarboxylate was derived from the remeasured standard molar energy of combustion, in oxygen, at T = 298.15 K, by rotating bomb combustion calorimetry and the standard molar enthalpy of vaporization, at T = 298.15 K, remeasured by Calvet microcalorimetry. Combining these two values, the following enthalpy of formation in the gas phase, at T = 298.15 K, was then derived for ethyl-2-thiophenecarboxylate: −(277.7 ± 2.9) kJ · mol −1 . The calculated gas-phase enthalpy of formation of the title compound, through the G3(MP2)//B3LYP approach was found to be 278.9 kJ · mol −1 , in excellent agreement with the experimental measured value

  10. Effect of duty-cycles on the air plasma gas-phase of dielectric barrier discharges

    Barni, R.; Biganzoli, I.; Dell'Orto, E. C.; Riccardi, C.

    2015-10-01

    An experimental investigation concerning the effects of a duty-cycle in the supply of a dielectric barrier discharge in atmospheric pressure air has been performed. Electrical characteristics of the discharge have been measured, focusing mainly on the statistical properties of the current filaments and on dielectric surface charging, both affected by the frequent repetition of breakdown imposed by the duty-cycle. Information on the gas-phase composition was gathered too. In particular, a strong enhancement in the ozone formation rate is observed when suitable long pauses separate the active discharge phases. A simulation of the chemical kinetics in the gas-phase, based on a simplified discharge modeling, is briefly described in order to shed light on the observed increase in ozone production. The effect of a duty-cycle on surface modification of polymeric films in order to increase their wettability has been investigated too.

  11. Gas-phase spectroscopic studies of heavy elements compounds (group V) using FTIR technique

    Allaf, A. W.; Ajji, Z.

    1998-12-01

    Antimony oxide trihalide, OSbX3 where X=F, CI and Br, and antimony (III) oxychloride, OSbC1 molecules were produced by an on-line process for the first time using antimony chloride SbC13 passed over heated silver oxide then followed by passing the obtained products over heated NaF and heated KBr for SbOF3 and OSbBr3, respectively. The obtained OSbC13 reacts with heated silver to produce OSbC1. The products have been characterized by the infrared spectra of their vapors. The low resolution gas-phase Fourier transform infrared spectrum, reported for the first time, shows the most characteristic band of OSbX3 at 1272, 1217 and 1200 cm -1 and the bands are assigned to the O=Sb stretching fundamental of OSbX3 were X=F, Cl and Br, respectively. The band at 1200 cm -1 needs more experimental investigation. The band at 924 cm -1 is assigned to the O=Sb stretching fundamental of OSbCl molecule. This result is in consistent with expectation and shifted to lower frequency in comparison with arsenic analogous molecule which is investigated by matrix-isolation technique. The work will be continued in order to cover the bismuth and arsenic compounds of similar structures. (author)

  12. An optical spectrum of a large isolated gas-phase PAH cation: C78H26+

    Zhen, Junfeng; Mulas, Giacomo; Bonnamy, Anthony; Joblin, Christine

    2016-01-01

    A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26+- in the 410-610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produce some of the fine structure observed in some diffuse interstellar bands (DIBs). It can also favor the folding of C78H26+ fragments and ultimately the formation of fullerenes. This study opens up the possibility to identify the most promising candidates for DIBs amongst large cationic PAHs. PMID:26942230

  13. Gas-phase spectroscopy of synephrine by laser desorption supersonic jet technique.

    Ishiuchi, Shun-ichi; Asakawa, Toshiro; Mitsuda, Haruhiko; Miyazaki, Mitsuhiko; Chakraborty, Shamik; Fujii, Masaaki

    2011-09-22

    In our previous work, we found that synephrine has six conformers in the gas phase, while adrenaline, which is a catecholamine and has the same side chain as synephrine, has been reported to have only two conformers. To determine the conformational geometries of synephrine, we measured resonance enhanced multiphoton ionization, ultraviolet-ultraviolet hole burning, and infrared dip spectra by utilizing the laser desorption supersonic jet technique. By comparing the observed infrared spectra with theoretical ones, we assigned geometries except for the orientations of the phenolic OH group. Comparison between the determined structures of synephrine and those of 2-methylaminno-1-phenylethanol, which has the same side chain as synephrine but no phenol OH group, leads to the conclusion that the phenolic OH group in synephrine does not affect the conformational flexibility of the side chain. In the case of adrenaline, which is expected to have 12 conformers if there are no interactions between the catecholic OH groups and the side chain, some interactions possibly exist between them because only two conformations are observed. By estimation of the dipole-dipole interaction energy between partial dipole moments of the catecholic OH groups and the side chain, it was concluded that the dipole-dipole interaction stabilizes specific conformers which are actually observed. © 2011 American Chemical Society

  14. Conformal and highly luminescent monolayers of Alq3 prepared by gas-phase molecular layer deposition.

    Räupke, André; Albrecht, Fabian; Maibach, Julia; Behrendt, Andreas; Polywka, Andreas; Heiderhoff, Ralf; Helzel, Jonatan; Rabe, Torsten; Johannes, Hans-Hermann; Kowalsky, Wolfgang; Mankel, Eric; Mayer, Thomas; Görrn, Patrick; Riedl, Thomas

    2014-01-22

    The gas-phase molecular layer deposition (MLD) of conformal and highly luminescent monolayers of tris(8-hydroxyquinolinato)aluminum (Alq3) is reported. The controlled formation of Alq3 monolayers is achieved for the first time by functionalization of the substrate with amino groups, which serve as initial docking sites for trimethyl aluminum (TMA) molecules binding datively to the amine. Thereby, upon exposure to 8-hydroxyquinoline (8-HQ), the self-limiting formation of highly luminescent Alq3 monolayers is afforded. The growth process and monolayer formation were studied and verified by in situ quartz crystal monitoring, optical emission and absorption spectroscopy, and X-ray photoelectron spectroscopy. The nature of the MLD process provides an avenue to coat arbitrarily shaped 3D surfaces and porous structures with high surface areas, as demonstrated in this work for silica aerogels. The concept presented here paves the way to highly sensitive luminescent sensors and dye-sensitized metal oxides for future applications (e.g., in photocatalysis and solar cells).

  15. A computational and spectroscopic study of the gas-phase conformers of adrenaline

    Çarçabal, P.; Snoek, L. C.; van Mourik, T.

    The conformational landscapes of the neurotransmitter l-adrenaline (l-epinephrine) and its diastereoisomer pseudo-adrenaline, isolated in the gas phase and un-protonated, have been investigated by using a combination of mass-selected ultraviolet and infrared holeburn spectroscopy, following laser desorption of the sample into a pulsed supersonic argon jet, and DFT and ab initio computation (at the B3LYP/6-31+G*, MP2/6-31+G* and MP2/aug-cc-pVDZ levels of theory). Both for adrenaline and its diastereoisomer, pseudo-adrenaline, one dominant molecular conformation, very similar to the one seen in noradrenaline, has been observed. It could be assigned to an extended side-chain structure (AG1a) stabilized by an OH → N intramolecular hydrogen bond. An intramolecular hydrogen bond is also formed between the neighbouring hydroxyl groups on the catechol ring. The presence of further conformers for both diastereoisomers could not be excluded, but overlapping electronic spectra and low ion signals prevented further assignments.

  16. Fluid Phase Separation (FPS) experiment for flight on a space shuttle Get Away Special (GAS) canister

    Peters, Bruce; Wingo, Dennis; Bower, Mark; Amborski, Robert; Blount, Laura; Daniel, Alan; Hagood, Bob; Handley, James; Hediger, Donald; Jimmerson, Lisa

    1990-01-01

    The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid which will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on the Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS-42. The design and the production of a fluid phase separation experiment for rapid implementation at low cost is presented.

  17. Structural phase transition and electronic properties in samarium chalcogenides

    Panwar, Y. S., E-mail: yspanwar2011@gmail.com [Department of Physics, Govt. New Science College Dewas-455001 (India); Aynyas, Mahendra [Department of Physics, C.S.A. Govt. P.G. College, Sehore, 466001 (India); Pataiya, J.; Sanyal, Sankar P. [Department of Physics, Barkatullah University, Bhopal, 462026 (India)

    2016-05-06

    The electronic structure and high pressure properties of samarium monochalcogenides SmS, SmSe and SmTe have been reported by using tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA). The total energy as a function of volume is evaluated. It is found that these monochalcogenides are stable in NaCl-type structure under ambient pressure. We predict a structural phase transition from NaCl-type (B{sub 1}-phase) structure to CsCl-type (B{sub 2}-type) structure for these compounds. Phase transition pressures were found to be 1.7, 4.4 and 6.6 GPa, for SmS, SmSe and SmTe respectively. Apart from this, the lattice parameter (a{sub 0}), bulk modulus (B{sub 0}), band structure (BS) and density of states (DOS) are calculated. From energy band diagram we observed that these compounds exhibit metallic character. The calculated values of equilibrium lattice parameter and phase transition pressure are in general good agreement with available data.

  18. The effect of a micro bubble dispersed gas phase on hydrogen isotope transport in liquid metals under nuclear irradiation

    Fradera, J., E-mail: jfradera@ubu.es; Cuesta-López, S., E-mail: scuesta@ubu.es

    2013-12-15

    The present work intend to be a first step towards the understanding and quantification of the hydrogen isotope complex phenomena in liquid metals for nuclear technology. Liquid metals under nuclear irradiation in, e.g., breeding blankets of a nuclear fusion reactor would generate tritium which is to be extracted and recirculated as fuel. At the same time that tritium is bred, helium is also generated and may precipitate in the form of nano bubbles. Other liquid metal systems of a nuclear reactor involve hydrogen isotope absorption processes, e.g., tritium extraction system. Hence, hydrogen isotope absorption into gas bubbles modelling and control may have a capital importance regarding design, operation and safety. Here general models for hydrogen isotopes transport in liquid metal and absorption into gas phase, that do not depend on the mass transfer limiting regime, are exposed and implemented in OpenFOAM® CFD tool for 0D–3D simulations. Results for a 0D case show the impact of a He dispersed phase of nano bubbles on hydrogen isotopes inventory at different temperatures as well as the inventory evolution during a He nucleation event. In addition, 1D and 2D axisymmetric cases are exposed showing the effect of a He dispersed gas phase on hydrogen isotope permeation through a lithium lead eutectic alloy and the effect of vortical structures on hydrogen isotope transport at a backward facing step. Exposed results give a valuable insight on current nuclear technology regarding the importance of controlling hydrogen isotope transport and its interactions with nucleation event through gas absorption processes.

  19. Notes on qubit phase space and discrete symplectic structures

    Livine, Etera R

    2010-01-01

    We start from Wootter's construction of discrete phase spaces and Wigner functions for qubits and more generally for finite-dimensional Hilbert spaces. We look at this framework from a non-commutative space perspective and we focus on the Moyal product and the differential calculus on these discrete phase spaces. In particular, the qubit phase space provides the simplest example of a four-point non-commutative phase space. We give an explicit expression of the Moyal bracket as a differential operator. We then compare the quantum dynamics encoded by the Moyal bracket to the classical dynamics: we show that the classical Poisson bracket does not satisfy the Jacobi identity thus leaving the Moyal bracket as the only consistent symplectic structure. We finally generalize our analysis to Hilbert spaces of prime dimensions d and their associated d x d phase spaces.

  20. Atomic structure of a decagonal Al-Pd-Mn phase

    Mihalkovič, Marek; Roth, Johannes; Trebin, Hans-Rainer

    2017-12-01

    We present a detailed structure solution for the 16 -Å decagonal quasicrystal in the Al-Pd-Mn system by means of cluster decoration and ab initio energy minimization. It is based on structure models of the ɛ and other approximant phases. The ɛ phases can be represented as subsets of a hexagon-boat-star (HBS) tiling. The decagonal phase comprises further HBS tiles. We have constructed several fictitious HBS approximants and optimized their structures individually. All tiles are decorated by two types of atomic clusters: the pseudo-Mackay icosahedron (PMI) and the large bicapped pentagonal prism (LBPP). It turns out that, whereas the PMI clusters can be kept essentially unchanged, the LBPP clusters must be adjusted in occupancy with Al atoms depending on their positions in the various tiles. In this way we obtain cluster decorations for all tiles of the decagonal quasicrystal. The calculations were confirmed by evaluation of an effective tile Hamiltonian.